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CROSS REFERENCE TO RELATED APPLICATIONS This application is a Continuation-in-Part of U.S. application Ser. No. 11/306,336, filed on Dec. 23, 2005, now U.S. Pat. No. 7,533,343; and of U.S. application Ser. No. 12/122,705, filed May 18, 2008; the disclosures of which are incorporated by reference in their entireties. TECHNICAL FIELD The disclosure relates to management of contact information; more specifically to method, system, means and apparatus for sending contact information published on a web page directly to mobile communication devices. BACKGROUND It is a common practice for businesses to have a presence on the internet via a web site. This practice enables businesses to reach out to an ever-growing base of customers who do commerce on the interne. It is also a common practice for businesses to publish their contact information on their web pages. The published contact information usually contains business name, phone number, fax number, email and street address. This gives customers the means to contact the said businesses by multiple means including email, phone, fax, mail and in person. It is a common practice in web commerce for customers to look for a product online and then subsequently purchase the said product by another means such as by making a phone call, faxing or mailing an order form or by visiting a retail outlet in person. In order to remember the contact information of a business published on a web page, a customer has to either 1) print the web page containing the said business's contact information; 2) write it manually on a piece of paper or; 3) enter it manually into a mobile phone such as a mobile phone. This is a cumbersome and time consuming way to remember contact information; especially when a customer has to remember contact information of multiple businesses. There is no invention in the prior art that enables customers to send a contact information published on a web page directly to communication devices such as mobile phones; and thereafter integrate the said contact information into the contact list of the said mobile phone without requiring the customer to enter the said contact information manually into the communication device. SUMMARY The present invention relates to means, methods, system and apparatus to send contact information published on a web page to mobile communication device and automatically save the received contact information into the contact list of the mobile communication device. Additionally the invention relates to management of contact information thus saved in the contact list of mobile communication devices. BRIEF DESCRIPTION OF THE DRAWINGS The drawings are illustrative embodiments. The drawings are not necessarily to scale and certain features may be removed, exaggerated, moved, or partially sectioned for clearer illustration. The embodiments illustrated herein are not intended to limit or restrict the claims. FIG. 1 shows a schematic representation of sending contact information ( 11 A) published in a web page ( 10 ) to a mobile communication device ( 13 ); and thereafter saving the contact information into the native contact list ( 12 ) of the mobile communication device, according to an embodiment. FIG. 2A shows the structure of the ‘web contact information from’ ( 11 ) and a schematic representation of the transfer of data entered into the ‘web contact information form’ ( 11 ) into corresponding data fields of the ‘server contact information’ database ( 22 ). It also shows the generation of a link ( 23 ) responsive to an entry in the ‘server contact information’ database ( 22 ); the link ( 23 ) comprising of an embedded code representative of the location of the corresponding contact information ( 24 ) in the ‘server contact information’ database ( 22 ). FIG. 2B shows an interface ( 21 ) contained in the ‘mobile phone’ application that seamlessly enters data received in mobile communication device from ‘server contact information’ database ( 22 ) into corresponding data fields of the contact list ( 12 ) of the mobile communication device. FIG. 2C shows exemplary data fields for a user account within a user account database, in accordance with an embodiment of the disclosure; FIG. 3 shows link ( 23 ) displayed next to corresponding contact information ( 11 A) published on web page and the command prompt ( 31 ) that is displayed upon selecting the link ( 23 ) prompting user to enter the receiving mobile communication device number (entered at the command prompt 31 ). FIG. 4A shows the method of attaching an advertisement ( 40 ) containing one or more of data ( 40 A), voice ( 40 B), image ( 40 C) and/or video ( 40 D) files to the contact information ( 11 A) published on a web page and thereafter sending the said contact information ( 11 A) along with the attached advertisement ( 40 ) to a mobile communication device ( 13 ). FIG. 4A also shows the display of contact information ( 11 A) and the corresponding advertisement ( 40 ) on the mobile communication device ( 13 ). FIG. 4B shows the method of attaching an advertisement ( 40 ) containing one or more of data ( 40 A), voice ( 40 B), image ( 40 C) and/or video ( 40 D) files to a contact information ( 11 A) published on a web page where the attachment of the advertisement ( 40 ) takes place while the corresponding contact information ( 11 A) is in transit to a receiving mobile communication device ( 13 ). FIG. 4B also shows the display of contact information ( 11 A) and the corresponding advertisement ( 40 ) on the mobile communication device ( 13 ). FIG. 5 is a schematic representation of sending information ( 51 ) published on a web page ( 10 ) to a mobile communication device ( 13 ); and thereafter saving and displaying information ( 51 ) on mobile communication device ( 13 ). FIG. 6 shows a schematic diagram of the process of sending contact information from web page to an application naïve mobile communication device. FIG. 7 shows a schematic diagram of the process of sending contact information from web page to an application experienced mobile communication device. FIGS. 8A-G show schematic representations of the structure of various databases according to an embodiment. DETAILED DESCRIPTION In this respect; before explaining at least one embodiment of the invention in detail; it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting. As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out one or several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. It is a common practice for businesses to publish their contact information on one or more web sites. The purpose of this practice is to enable customers to easily contact them. The published contact information usually contains name, phone number, fax number, email and street address of the business. At the present time, contact information is published on a web page using free text, usually using HTML programming language. There is no standard format or template for publishing contact information; consequently each web page has its unique format and template for publishing contact information. Presently, to save contact information displayed on a web page, customer is required to manually write down the contact information on paper or print the web page containing the contact information and manually enter the contact information into mobile communication device. This is a tedious and cumbersome process and many users choose not to save contact information published on a web page into mobile communication device. Components of an embodiment include: 1) a server application hosted on a server; 2) a mobile phone application downloadable from the server and hosted on a plurality of the mobile communication device; 3) a contact information database in the server receiving data entered into ‘web contact information’ form published on a web page; and 4) a contact list hosted in each mobile communication device. When a user signs up for the service, a user account is created in the server ‘user account’ database, as shown in FIGS. 2C & 8E . The server ‘user account’ database may include the user name, password, user demographics (such as user age, education level, etc.) and contact information that user desires to download from the web page. The user enters the contact information to be displayed on the web page into a ‘web contact information form’ ( 11 ) as shown in FIG. 2A . The ‘web contact information form’ ( 11 ) serves as a data entry portal for data contained in server contact information database ( 22 ) saved in the server; as shown in FIG. 2A . Server contact information database ( 22 ) is created using a database program like MS SQL, My SQL; or into any other suitable database program. The type of software used to create the server contact information database ( 22 ) should not be considered limiting as many software programs can be used to achieve the same end result. The ‘web contact information form’ ( 11 ) contains data fields for business name, business category, phone number, fax number, email, web page uniform resource locator (URL) and street address and any additional fields deemed desirable. The data fields should not be considered limiting as it can be customized according to individual needs. Means is provided to distribute the ‘web contact information form’ ( 11 ) over the Internet to programmers, web masters and other individuals responsible for designing and programming web pages. Contact information entered into ‘web contact information form’ ( 11 ) is preferably displayed on the contact information page of a web site. In the preferred embodiment, ‘web contact information form’ is web page specific, i.e. when a ‘web contact information form’ is generated it contains a web page specific code whereby the ‘web contact information form’ and representative contact information data can only be displayed on the corresponding web page. Once contact information data is entered into ‘web contact information form’ it is saved into corresponding entry in the server contact information database ( 22 , 24 ) as shown in FIG. 2A . The server application generates a link ( 23 ) with embedded code representative of the location of the corresponding contact information ( 24 ) in the server contact information database ( 22 ), also shown in FIG. 2A . In the preferred method, the link ( 23 ) is displayed in close proximity to the corresponding contact information on a web page as shown in FIG. 3 . When the link ( 23 ) is activated on the web page; user is prompted to enter the receiving mobile communication device number i.e. phone number ( 31 ) as shown in FIG. 3 , where after the embedded code contained in the link ( 23 ) directs the user request to appropriate entry ( 24 ) in the server contact information database ( 22 ) as shown in FIG. 2A . As shown in FIG. 2B , once contact information ( 24 ) is entered into the server contact information database ( 22 ), the server application may generate a ‘custom web URL’ ( 25 ) for the contact information ( 24 ). When contact information ( 24 ) is transmitted to and saved into the contact list ( 12 ) in the mobile communication device ( 13 ), a corresponding ‘custom web URL’ ( 26 ) may be saved as well. In one preferred method, web page corresponding to the ‘custom web URL’ ( 25 , 26 ) is, hosted in the server. Alternatively, web page corresponding to the ‘custom web URL’ ( 25 , 26 ) is hosted on another server. When user activates the ‘custom web URL’ ( 26 ) within the mobile communication device, the request is transmitted to the server. The server application contains program code to forward the ‘custom web URL’ ( 26 ) to corresponding web page. In the preferred embodiment the server application also contains program code to block forwarding of the ‘custom web URL’ ( 26 ) to corresponding web page with certain pre determined filters—such as when the corresponding web page contains unlawful content; when payment for forwarding the ‘custom web URL’ to corresponding web page has not been received etc. According to yet another embodiment of the invention; the mobile phone application contains program code that records instances of web link activation from within the contact list of mobile communication device. The mobile phone application may contain program code to communicate at least one of i) instances of web link activation; ii) unique mobile communication device identifier (UDID); iii) corresponding contact information ID; and iv) mobile communication device number (phone number) to the server. Further, this data may be communicated at predetermined intervals or after preselected occurrences, or at other desired instances. The server application may save all instances of web link activation data received from mobile communication devices into ‘web link activation’ database; as shown in FIG. 8G . This data may be used to charge user or vendor for each instance of web link activation; i.e. pay per click. One or more reports based on data contained in the ‘web link activation’ database in the server may be generated. A contact list ( 12 ) is provided for mobile communication devices and is shown in FIG. 2B . The contact list ( 12 ) may be created using a software and database program suitable for the corresponding mobile phone and is usually native to the communication device. One example of such program is Java 2 Micro Edition (J2ME). Most mobile phones can run Java program with MIDP supported. (MIDP: Mobile Information Device Profile). The newer phones support MIDP2.0 while some older phones only support MIDP1.2/1.1. The type of software program used to create the contact list ( 12 ) should not considered limiting as more than one software program can be used to achieve the desired results. Means may be provided to distribute the contact list ( 12 ) to one or more mobile communication devices over the Internet, wireless network or any other network. Alternatively, the contact list ( 12 ) is pre loaded into mobile communication device at the point of manufacture wherein it forms the native contact list of the mobile communication device. An interface ( 21 ), as shown in FIG. 2B , may be provided in the mobile phone application to download, synchronize, and integrate data between the corresponding data fields of the server contact information database ( 22 ) and the contact list ( 12 ). In an exemplary method, the contact list ( 12 ) is the native contact list of the mobile communication device. Further, the data fields in the ‘contact list’ ( 12 ) may be identical to the data fields contained in the ‘web contact information form’ ( 11 ) and the server contact information database ( 22 ). As shown in FIG. 2B , the data fields in the contact list ( 12 ) consist of business name, business category, phone number, fax number, email, web page URL and street address. Also shown in FIG. 2B is an interface ( 21 ) which is a part of the mobile phone application hosted in the mobile communication device. The mobile phone application is created to enable seamless interfacing and integration of contact information data between the ‘web contact information form’ ( 11 ), server contact information database ( 22 ) and the contact list ( 12 ) of the mobile communication device. FIGS. 1 and 3 show the steps involved in sending contact information published on a web page to a mobile communication device. FIG. 1 is a schematic representation of one embodiment of the present invention. Contact information ( 11 A) is published on a web page ( 10 ). As shown in FIG. 3 , the embedded link/icon ( 23 ) is pasted next to the contact information ( 11 A) on the web page. According to the preferred method, when user selects the link/icon ( 23 ), the user is prompted to enter the receiving mobile communication device number ( 31 ) (for example, the mobile phone number or any other identifying data). Then the user may select (click) the link 23 or otherwise submit the request to download the contact information on the receiving mobile communication device. The user request is then transmitted to the server ( 60 ) application (hosted in the server) via a communication link (step 1 of FIGS. 6 and 7 ). Turning our attention to FIG. 6 , when user request from web page is received in the server ( 61 ), the server application checks the receiving mobile communication device number (such as, for example the mobile phone number) in the request against the ‘application experienced mobile communication devices’ database ( 30 , FIG. 8B ) containing list of mobile communication devices where the ‘mobile phone’ application has already been downloaded. Mobile phone application is hosted in the server and is downloadable into mobile communication devices over a communication link. Server application contains ‘application experienced mobile communication devices’ database ( 30 , FIG. 8B ) which stores list of mobile communication devices where ‘mobile phone’ application has been downloaded. If the server application determines the receiving mobile communication device is application naïve, the mobile communication device number (phone number) and the corresponding contact information requested to be sent are saved in a ‘pending contact information’ database the server 62 , 23 ( FIG. 8A ). Thereafter, the server ( 60 ) application sends a message (short message service (SMS) or push notification) to the receiving mobile communication device ( 63 ); the message comprising of a user prompt and a link to the server ( 60 ) hosting the downloadable mobile phone application. In the current mobile architecture, push notification cannot be sent to application naïve mobile communication devices; hence at this step a SMS message is sent. SMS message can be sent either by SMS gateway or email gateway i.e. using the phone email address such as phone_number@wirelesscarrier.com. According to one method, the server application is programmed upon determining the receiving mobile communication device to be application naïve to ask the user for wireless carrier ID at the time when phone number is entered after activation of the link/icon ( 23 ). Alternatively user may be asked to enter wireless carrier ID every time a request is sent from web page. The message prompts the user to download the mobile phone application into the mobile communication device from the server ( 64 ). The mobile phone application comprises of program code to extract unique mobile communication device ID (UDID) and/or device number (phone number) from internal memory of the mobile communication device; and transmit that data to the server ( 65 ). Additionally, the mobile phone application contains program code to send a successful download signal to the server ( 65 ) once the application is successfully downloaded into the mobile communication device ( 13 ). Using the mobile device number (phone number) as the identifying parameter, the server application may integrate the unique mobile device ID (UDID) with the corresponding mobile device number (phone number) and the corresponding pending contact information in the ‘pending contact information’ database ( 66 , 23 , FIG. 8A ). Additionally, the server application may save the mobile communication device ID (UDID) and corresponding mobile communication device number (phone number) into the ‘application experienced mobile communication devices’ database 30 ( FIG. 8B ) in the server. The ‘application experienced mobile communication devices’ database 30 ( FIG. 8B ) contains a list of mobile communication devices where mobile phone application has been successfully downloaded. Once the server application receives confirmation of download of mobile phone application in the receiving mobile communication device ( 13 ); the server application may send the corresponding pending contact information in the ‘pending contact information’ database ( 23 , FIG. 8A ) to the mobile communication device ( 13 ) such as by SMS or by push notification ( 67 ) or other suitable transmission. Now turning our attention to FIG. 7 , if upon receiving request from web page ( 71 ), server application determines from ‘application experienced mobile communication devices’ database ( 30 , FIG. 8B ) that the receiving mobile communication device is application experienced ( 72 ); server application sends a message (such as by push notification or SMS) to the receiving mobile communication device via a push notification server/SMS server ( 74 ); and at the same time saves the request in the ‘pending contact information’ database ( 73 , 23 , FIG. 8A ). When the push notification/SMS is accepted by the user, the mobile phone application is launched on the mobile communication device, where after the mobile phone application pulls contact information destined for corresponding mobile communication device from the server ( 75 , 76 ). The mobile phone application then integrates and saves contact information into the contact list of the mobile communication device. Preferably server application contains program code to determine the wireless carrier and operating system of the receiving mobile communication device prior to initiating communication with the mobile communication device. Most wireless carriers require users to download mobile phone application from their native server. According to one embodiment, in such a situation, the wireless carrier server contains program code to communicate unique mobile communication device ID (such as the UDID) and mobile communication device number (phone number; which it receives upon download of mobile phone application into the mobile communication device) to the server at predetermined intervals or after preselected occurrences, or at other desired instances. It is hoped that in a future open environment, the mobile phone application will be downloaded into mobile communication devices directly from the server. For the sake of simplicity, the term server used in the application should be considered to encompass all servers; including wireless carrier server. It is also preferred that the mobile phone application extracts and communicates unique mobile communication device ID (UDID) to server at each instance of communication with server. The server application may contain program code (instructions) to capture each instance of download of contact information from server into mobile communication devices. The server application saves these instances of download of contact information into a ‘contact information experienced mobile communication devices’ database in the user account corresponding to contact information; as shown in FIG. 8C . In an alternate embodiment mobile phone application contains program code to ping the server application with mobile communication device ID (UDID), mobile communication device number (phone number) and contact information ID, where after the server application saves the dataset into the ‘contact information experienced mobile communication devices’ database ( FIG. 8C ). The ‘contact information experienced mobile communication devices’ database is useful to businesses that want to send a targeted ad campaign to users who have already downloaded their contact information into their mobile communication devices. Such as ad campaign may be SMS or multimedia messaging service (MMS) based; and may contain one or combination of text, image, video and audio files. The mobile phone application may contain program code that records instances of contact information retrieval and activation from within the contact list of the corresponding mobile communication device. Instances of contact information activation may include—making a phone call, opening email client/URL within the contact information, etc. The mobile phone application may contain program code to communicate at least one of i) instances of contact information retrieval and activation; ii) unique mobile communication device ID (UDID); iii) contact information ID; and/or iv), mobile communication device number (phone number) to the server at predetermined intervals. The server application saves all instances of contact information activation from mobile devices into ‘contact information activation’ database in the user account corresponding to the activated contact information in the server; as shown in FIG. 8F . Similarly, the server application saves all instances of contact information retrieval from mobile devices into ‘contact information retrieval’ database in the user account corresponding to the retrieved contact information in the server; as shown in FIG. 8D . This data reflects use of contact information sent from web page to mobile communication devices by end user. One or more reports may be generated from the data contained in the ‘contact information activation’ and ‘contact information retrieval’ databases. According to one preferred report, activation and retrieval data for each contact information is ranked according to total instances of activation and retrieval on all mobile communication devices where said contact information is saved. The ‘contact information activation’ and ‘contact information retrieval’ database is useful to businesses that want to send a targeted ad campaign to mobile communication device users who have downloaded and activated/retrieved their contact information in their mobile communication devices. Such as ad campaign may be SMS or MMS based; and may contain one or combination of text, image, video and audio files When a contact information is updated in the server, a message (push notification, SMS, or other desirable means) is sent to all mobile communication devices where said contact information is saved; using data contained in the ‘contact information experienced mobile communication devices’ database as shown in FIG. 8C . Once the message (push notification or SMS) is accepted by the user, the mobile phone application is launched on the mobile communication device, where after the mobile phone application downloads the updated version of the contact information from the server. The mobile phone application then replaces the older version of the contact information with the updated version in the contact list of the mobile communication device. When a updated version of the mobile phone application is available in the server, a message (push notification/SMS) is sent to all mobile communication devices where said contact information is saved; using data contained in the ‘application experienced mobile communication devices’ database ( FIG. 8B ). Once the message (push notification or SMS) is accepted by the user, the mobile phone application is launched on the mobile communication device, where after the mobile phone application downloads the updated version of the mobile phone application from the server. The updated version of the mobile phone application then replaces the older version in the mobile communication device. Means may be provided in the mobile communication device to execute meaningful applications based on the contact information contained in the ‘contact list’. One example of such meaningful application is auto dialing of a phone number contained in contact information. Another example of such meaningful application is to establish connection to a web page URL contained in contact information without requiring the caller to type the said URL into a web browser on his/her communication device. In addition to data, means is provided to attach voice, images and video files to the ‘web contact information template’. This can be done using existing programming tools and formats such as windows media audio for voice; jpg, gif or tiff for images; and windows media & real for video. The software used to create an advertisement should not be considered limiting as other available software can also be used to create an advertisement. This feature of the invention can be used to advertise products and services of businesses in conjunction with contact information published on web sites. For example, an advertisement comprising of data, voice and/or video files can be attached to contact information in the ‘web contact information template’ published in a web page. When the said contact information is sent to a communication device, the advertisement attached thereto is also sent. Means is provided in the mobile communication device to save and/or display the said advertisement. The said advertisement is displayed when a caller selects or uses the corresponding contact information; as for example when auto dialing a phone number contained therein. According to one method of the invention; advertisement containing data, voice, image and/or video files is attached to contact information published in a web page at the point of publication of the said contact information. The said advertisement is sent to a mobile communication device when the corresponding contact information is. Means is provided in the mobile communication device to save and/or display the said advertisement. The said advertisement is displayed when the caller selects or uses the said contact information such said when auto dialing a phone number contained therein. Means is provided to update advertisements already saved in a mobile communication device as a result. When contact information with an attached advertisement is transmitted to a communication device, the identity of the said mobile communication device is saved at a central location, such as a server. A new or revised version of the said advertisement is created and sent to all such communication devices where the said contact information has been previously saved. Appropriate software is provided in the communication devices to integrate the new or revised advertisement with the corresponding contact information saved therein. Such software can either be pre loaded into the communication devices or can be sent to communication devices separately, such as when the new or revised advertisement is sent. This feature, for example, can be used to send a new version an advertisement to communication devices having a particular contact information saved in their contact list. An example of this method is shown in FIG. 4A . Contact information of ‘Wal-Mart’ ( 11 A) is published on its web page ( 10 ) using the ‘web contact information template’ ( 11 ). The contact information ( 11 A has an advertisement ( 40 ) containing data ( 40 A), voice ( 40 B), image ( 40 C) and video ( 40 D) files attached to it. The said advertisement ( 40 ) contains brief information about Wal-Mart's promotional offers. When a user sends Wal-Mart's contact information ( 11 A) from Wal-Mart's web page ( 10 ) to his mobile communication device such as mobile communication device ( 13 ), the advertisement ( 40 ) attached to Wal-Mart's contact information ( 11 A) is also sent to the said mobile communication device ( 13 ). Both, the contact information ( 11 A) and the attached advertisement ( 40 ) is integrated and saved in the said communication device. Furthermore, when a caller selects or uses Wal-Mart's contact information ( 11 A); as for example when auto dialing Wal-Mart's phone number on his mobile communication device ( 13 ); the attached Wal-Mart's advertisement ( 40 ) is displayed on the said mobile communication device ( 13 ). According to another embodiment of a method, advertisements comprising of data, voice, image and/or video files is attached to contact information while the said contact information is in transit to a communication device. This method enables more customization of the advertisement that is sent to a communication device. For example, an advertiser can attach golf advertisements to a contact information in transit to the mobile communication device of a caller who is a golf player; and attach tennis advertisements when the said contact information is in transit to a caller who is a tennis player. An example of this method is shown in FIG. 4B . Contact information of ‘Wal-Mart’ ( 11 A) is published on its web page ( 10 ) using the ‘web contact information template’ ( 11 ). An advertisement ( 40 ) containing data ( 40 A), voice ( 40 B), image ( 40 C) and video ( 40 D) files contains brief information about Wal-Mart's promotional offers. When a user sends Wal-Mart's contact information ( 11 A) from Wal-Mart's web page ( 10 ) to his mobile communication device such as mobile communication device ( 13 ), the advertisement ( 40 ) is attached to Wal-Mart's contact information ( 11 A) while the said contact information ( 11 A) is in transit to the mobile communication device ( 13 ). The advertisement ( 40 ) is then sent to the mobile communication device ( 13 ) along with the contact information ( 11 A). Both, the contact information ( 11 A) and the attached advertisement ( 40 ) is integrated and saved in the said mobile communication device ( 13 ). Furthermore, when a caller selects or uses Wal-Mart's contact information ( 11 A); as for example when auto dialing Wal-Mart's phone number; on his mobile communication device ( 13 ); the attached Wal-Mart's advertisement ( 40 ) is displayed on the mobile communication device ( 13 ). According to yet another method, a package of advertisements comprising of data, voice, image and/or video files are pre loaded or downloaded into the communication devices. Said communication devices are programmed to play selected advertisements when a caller selects/uses selected contact information or selected category of contact information saved in the communication device. Alternatively, an .exe type file can be attached to the contact information contained in the ‘web contact information template’; wherein the said .exe type file has means to program a mobile communication device to play select advertisements or category of advertisements saved therein; when a caller selects/uses the said contact information or selected category of contact information. Means is provided to change and update the association between an advertisement and contact information. For example, a package of multiple advertisements containing an advertisement of Dell Computers is pre loaded or downloaded into a communication device. When a caller saves the contact information of Dell Computers in the said communication device, it is programmed to display Dell Computers' advertisement when the contact information of Dell Computers is selected/used by the caller. Alternatively, the mobile communication device can be programmed to display Dell's advertisement when the caller selects a different contact information. These methods of advertisement of the present invention serve as a powerful means of targeted advertising; as the product and services is advertised to a select and targeted customer base. In the illustrated examples shown in FIGS. 4A and 4B , promotional offers ( 40 ) of Wal-Mart are advertised only to customers who have willingly saved Wal-Mart's contact information ( 11 A) in their communication devices ( 13 ). Additionally; promotional offers ( 40 ) at Wal-Mart is advertised to the said customer at the time when he/she is selects/uses the contact information of Wal-Mart ( 11 A); such as when auto dialing a phone number contained therein. These features combined, in inventor's opinion, will result in a significantly higher sales and revenue for businesses. The invention is capable of other embodiments and of being practiced and carried out in various ways. As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out one or several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. Some variations of the present inventions are: 1) Although the present invention relates to transmission of contact information from a web page to communication devices; contact information from other sources like MS Outlook, Palm address book and the like can also be sent to one or more communication devices. 2) The present invention relates to methods and means of sending contact information published in a web page to communication devices. However, contact information published on a web page can also be sent to contact management programs such as MS Outlook. 3) In addition to contact information, other types of information can be sent to communication devices similarly. For example, means and methods of the present invention can be used to send data, image, voice and video files published on a web page to one or more communication devices. As shown in FIG. 5 ; data ( 51 ) published on a web page ( 10 ) can be sent to a mobile communication device ( 13 ) using the principles of the invention. 4) Based on the recitals of the present invention, the means and method described can be used to send data, voice, image and video published in an offline source, such as MS Word, to one or more communication devices. In the above mentioned variations of the present invention, preferably means are provided to save, archive and organize the said files in the communication device. Preferably, a reader and a viewer program are provided to enable optimal display of the contents of the said files in communication devices. The preceding description has been presented only to illustrate and describe exemplary embodiments of the methods and systems of the present invention. It is not intended to be exhaustive or to limit the invention to any precise form disclosed. It will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. The invention may be practiced otherwise than is specifically explained and illustrated without departing from its spirit or scope. The scope of the invention is limited solely by the following claims.
A method of transmitting contact information to an approved mobile communication device includes receiving an input representative of desired contact information located on a first web page and an input representative of the identity of a desired mobile communication device. The method also includes saving information representative of the desired contact information in a contact information database. The method also includes determining whether the desired mobile communication device is an approved device and transmitting to the desired mobile communication device information representative of a notification to send the information representative of the desired contact information. The method also includes receiving an input from the desired mobile communication device information representative of an acceptance to receive the information representative of the desired contact information, and transmitting to the desired mobile communication device information representative of the desired contact information.
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RELATED APPLICATIONS [0001] This application claims priority to U.S. provisional patent application No. 60/621,922, filed on Oct. 21, 2004, the entire contents of which are hereby incorporated by reference. FIELD OF THE INVENTION [0002] This invention relates to methods of detecting sepsis. BACKGROUND OF THE INVENTION [0003] Sepsis is a systemic response to infection. It can cause organ failure and death in severe cases. Severe sepsis is one of the most significant challenges in health care. Mortality remains high. Early diagnosis and prompt treatment greatly improve survival. However, an early sepsis condition or an infection with a risk of leading to sepsis has proven difficult to detect. SUMMARY OF THE INVENTION [0004] The invention features methods and compositions for detecting sepsis, e.g., early stage sepsis in a mammal. The method includes the steps of providing a patient-derived clinical sample and contacting the sample with a detectable label that preferentially binds to serine protease granzyme K (GRK, GRMK, tryptase 2, or granzyme 3), e.g., human GRK, or a fragment thereof. The level of GRK is a predictor of early sepsis. The clinical sample is a sample of bodily fluid or bodily tissue from a normal (uninfected individual) or a sample from an individual suffering from or at risk of developing sepsis. Patients at risk of developing severe sepsis include critically ill patients such as those identified as having severe CAP (community-acquired pneumonia), intra-abdominal surgery, meningitis, chronic diseases (e.g., diabetes, heart failure, chronic renal failure, and COPD), a compromised immune status (HIV/AIDS, use of cytotoxic and immunosuppressive agents, malignant neoplasms, and alcoholism), cellulitis, or urinary tract infection. At even greater risk are those identified as being of advanced age (greater than 65 years of age), underlying comorbidity, greater than normal body weight, and disease characteristics such as shock, hypoxemia, organ system failures, disseminated intravascular coagulation . [0005] An increase in the level of GRK in a patient-derived sample compared to that of a normal control (e.g., a sample or pool of samples of same or similar tissue or fluid obtained from normal, healthy individuals) indicates that the tested individual is suffering from sepsis, e.g., an early stage of sepsis, or is at risk of developing sepsis. [0006] The patient-derived sample is preferably a volume of blood, plasma, serum, urine, saliva, or other bodily fluid or tissue from a mammal, e.g., a human subject, dog, wolf, coyote, cat, cow, sheep, horse, goat, mouse, rat, or other animal such as another member of an avian species or rodent species. [0007] The method includes a step of detecting a GRK antigen by contacting the sample with a GRK-specific ligand such as an antibody or GRK binding fragment thereof. Such antibodies include polyclonal and monoclonal antibodies that bind to a GRK epitope of human GRK, e.g., NSQSYYNGDPFITKDM (residues 182-197 of SEQ ID NO:1) or residues 189-205 of SEQ ID NO:1). The ligand is an antibody or a fragment thereof. Preferably, the epitope to which the ligand binds comprises, consists essentially of, or consists of residues 182-205 of SEQ ID NO: 1, or any 8, 9, 10, 11, or 12 residue fragment thereof. Such antibodies are generated by immunizing an animal with the above-defined peptide and selecting for a polyclonal or monoclonal antibody according to standard methods. [0008] In some embodiments, the antibody is a monoclonal antibody. Alternatively, the antibody is a polyclonal antibody. In other embodiments, the antibody is a mixture of monospecific antibodies. Preferably, the determining step is carried out by immunoassay. Preferably, the ligand detects free GRK and bound GRK, said bound GRK being a component of a GRK-inhibitor compound. [0009] Also within the invention is an antibody specific for GRK. The antibody binds to an epitope present on both free and complexed GRK. For example, the antibody binds to an epitope comprising residues 182-197 of SEQ ID NO:1 or an epitope comprising residues 189-205 of SEQ ID NO: 1. In preferred embodiments, the antibody binds to both human and mouse GRK. The antibody is an IgM, IgM, or IgG isotype antibody, such as an IgG1, 2, or 3 isotype. [0010] The method optionally includes the step of determining the concentration of inter-alpha inhibitor proteins (IaIp), wherein an inverse correlation between an increase in GRK and decrease in IaIp indicates a diagnosis of early sepsis. In this method, [0011] A method of making a sepsis-detection reagent such as those described above is carried out by immunizing an animal with a peptide comprising a GRK-specific sequence such as a peptide of 8, 9, 10, 11, 12, 20, 30, 40, 50 or more (up to the full length of mature GRK). For example, the immunizing peptide has a sequence selected from consecutive residues of 182-205 of SEQ ID NO:1. [0012] Also within the invention is a kit for diagnosis of sepsis. The kit contains a ligand that binds to an epitope of the GRK, a detectable label, and instructions regarding detecting a difference in the level or amount of GRK in a patient sample for the purpose of detecting sepsis. [0013] Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIG. 1 is a bar graph showing the specificity of an anti-GRK polyclonal antibody in ELISA. Microplates were coated with synthetic peptides derived from human GRK and GrA (pGRK, pGrA) or human recombinant granzymes (rGRK, rGrA) and incubated with rabbit anti-GRK polyclonal antibody (pAb) or pre-immune serum (PRIS) as a negative control. [0015] FIG. 2 is a bar graph showing the competitive effects of synthetic peptide pGRK. Various concentrations (from 0.01 to 10 ng/μL) of synthetic peptides, pGRK and pGrA were added to anti-GRK pAb and measured for their effect on the binding of the antibody to rGRK. The synthetic peptide pGRK competitively inhibited the binding of anti-GRK pAb to immobilized rGRK in concentration dependent manner. A complete inhibition of antibody binding was achieved at 10 ng/μL of pGRK while control pGrA had no significant effect. [0016] FIGS. 3A and 3B are photographs of electrophoretic gels showing the results of a Western Blot assay. The specificity of anti-GRK polyclonal antibody defined by Western blot analysis with human recombinant GRK (rGRK) and native GRK purified from human NK cells cytotoxic granules (NK-GRK). An identical 26 kDa reactive band was specifically recognized by anti-GRK GRK pAb in both, rGRK and NK-GRK ( FIG. 3A ). Pre-immune rabbit serum (PRIS) was used as a negative control ( FIG. 3B ). [0017] FIG. 4 is a line graph showing a standard curve of GRK assay. The curve was established by using serially diluted pooled human plasma with defined amount of GRK. The concentration of GRK was defined as 2000 Arbitrary Units/mL (U/mL) in the pooled human plasma. The detection range of the GRK assay was 1.5-100 U/mL. The Coefficient of Variation (CV) between three separate experiments was less than 10%. [0018] FIG. 5 is a scatter plot showing the plasma levels of GRK in healthy controls (HC), septic patients from the Emergency Department (Group ED) and septic clinical trials (Group CT). GRK levels were determined by the GRK specific ELISA described herein. Samples were assayed in triplicate, and the levels are expressed in Arbitrary Units/mL (U/mL). The differences between the means of septic groups (ED or CT) and HC were statistically significant (#P<0.0001). Statistically significant difference was also found between both septic groups (ED vs CT, #P<0.0001). [0019] FIGS. 6A and 6B are photographs of electrophoretic gels showing the results of a Western Blot assay. Semi-quantitative Western blot analysis of components detected by anti-GRK polyclonal antibody in human plasma. Plasma samples from healthy controls: HC (lanes 1-3) and septic patient groups: Group ED (lane 4-7) and Group CT (lane 8-11) were analyzed by SDS-PAGE: 4-12% gradient gel ( FIG. 6A ) or 12.5% single gel ( FIG. 6B ) under non-reducing conditions, followed by immunodetection with anti-GRK polyclonal antibody. NK-GRK: GRK purified from human NK cells cytotoxic granules was used as a control. Results are representative of at least three experiments. [0020] FIG. 7 is a scatter plot showing the plasma levels of Inter-alpha inhibitor proteins (IaIp) in HC, ED, and CT patient groups. IaIp levels were determined by a sandwich ELISA using mAb 69.26 and pAb against human IaIp. The lines represent the mean level for each group. A significant decrease of IaIp levels were found in both septic patient groups (Group ED and Group CT) compared to HC (*P<0.0001). The difference between two septic groups were also statistically significant (**P=0.0125). [0021] FIGS. 8A and 8B are scatter plots showing the correlation between plasma GRK and IaIp levels. FIG. 8A shows data from Group ED (n=14; Spaerman; r=−0.5551; P=0.0394) and FIG. 8B shows data from Group CT (n=25; Spaerman; r=0.197; P=0.3451). [0022] FIG. 9 is a diagram showing the temporal development of responses to inflammatory stimuli. DETAILED DESCRIPTION OF THE INVENTION [0023] Sepsis is a consequence of a dysregulated inflammatory immune response that occurs as a result of systemic microbial infections. The mortality associated with sepsis remains high despite antimicrobial therapy and intensive care. The heterogeneous nature of sepsis often makes it difficult to diagnose. Misdiagnoses and inappropriate treatments because of the variety of infectious agents, different sources of infection and individual differences contribute to the increased mortality associated with sepsis. Accurate diagnosis sepsis at early time points using the methods described herein permits the early implementation of early goal directed therapy and reduces mortality. This approach is implemented by the identification of an biomarker (GRK) to stage early sepsis. Intervention at this early stage reduces mortality. [0024] Inter-alpha inhibitor proteins (IaIp) are serpin family members found at relatively high concentration in human plasma. IaIp are composed of heavy and light polypeptide subunits that are covalently linked by a chondroitin sulphate chain. The light chain (also termed ‘bikunin’=bi-kunitz inhibitor=inhibitor with two Kunitz domains) is responsible for the serine protease inhibitory activity of the molecules. The major forms found in human plasma are Inter-alpha Inhibitor (IaI), which consist of two heavy chains (H1 & H2) and a single light chain, and Pre-alpha Inhibitor (PaI), which consist of one heavy (H3) and one light chain. The relatively high levels of IaIp normally circulating in plasma and the fact that no person with complete absence of IaIp has ever been detected, suggests that these proteins have an essential physiological role which remains to be established. The data described herein revealed a significant decrease of plasma IaIp levels in adult patients and newborns with clinically proven sepsis, and established a correlation between the levels of IaIp and mortality in adult septic patients. [0025] To quantitatively analyze the levels of GRK in biological samples, a specific antibody (pAb) against human GRK was made. Using this antibody, a competitive immunoassay for the measurement of GRK levels in plasma was developed. The assay was used to determine and compare the levels of GRK in healthy controls (HC) and two groups of septic patients: patients with early symptoms of sepsis admitted in the Emergency Department (Group ED) and patients enrolled in clinical trials (Group CT) of severe sepsis. The molecular forms of GRK in these plasma samples were defined by immunoblot analysis using GRK specific Ab. [0026] GRK levels were significantly increased in Group ED and significantly decreased in Group CT compared to HC. IaIp levels were decreased in both septic groups. Thus, the biomarker of a decreased level of GRK is useful to identify those individuals with early sepsis, i.e., those that benefit most from immediate intervention. [0027] Immunoblot analysis confirmed the presence of GRK in high molecular weight complexes in healthy controls whereas various reactive lower molecular weight complexes and free GRK were identified in plasma of both sepsis groups. The specific GRK binding reagents described herein detect both free GRK as well as GRK complexes, thereby providing data on total GRK levels in a patient as opposed to a subset of GRK (i.e., only free GRK). These results indicated that the level of total GRK is useful as an early marker and improved marker in patients developing sepsis. Information regarding the amount of total GRK in a patient compared to a normal control or over time facilitates early intervention that is crucial in reducing sepsis related mortality. [0000] Analysis of Granzyme K in Patients with Early Symptoms of Sepsis [0028] An ELISA assay was developed to measure the levels of GRK, a protease, in human plasma. Results obtained using the assay demonstrated significant changes in the level of GRK at different stages during sepsis. In combination with the measurement of inter-alpha trypsin inhibitor (ITI) levels, the results of these assays identified early stages of sepsis. Detection of sepsis at an early stage of development permits early intervention/therapy when the disease is still controllable. [0029] Decreased levels of protein inhibitors, Inter-α-inhibitor proteins (IaIp) were associated with the sepsis patients that as a group exhibited the highest level of mortality. Although these results found a correlation with decreased IaIp levels and increased mortality from sepsis, it did not provide an explanation for the relationship. Thus, studies were carried out to determine whether decreased levels of IaIp resulted in or correlated with increased levels of GRK. Because no assay was available to measure GRK, an immunoassay such as an ELISA to measure GRK levels was developed. The use of herein-described assay demonstrated that emergency room patients with symptoms of early sepsis exhibited low levels of IaIp but significantly increased levels of GRK while sepsis patients enrolled in a clinical trial (indicative of those with advanced or severe sepsis), which would usually occur a day or two after admittance to the emergency room exhibited, significantly lower levels of both IaIp and GRK. Because of the significant mortality associated with sepsis and the finding that early treatment of sepsis is advantageous to survival, the assay was used to define the stage of sepsis facilitating the establishment of the protocols for treating sepsis at any given stage of sepsis. Prior to the invention, no assays were available to identify early sepsis or to define early stages of sepsis to distinguish early sepsis from advanced or severe sepsis. Severe sepsis is a condition known in the art and is e.g., characterized by at least one documented organ dysfunction (Levy et al., 2003, Crit. Care Med. 31: 1250-1256; herein incorporated by reference). [0030] The GRK ligands in the assay preferentially and/or specifically bind to human GRK, the amino acid sequence of which is shown below. TABLE 1 Protein Sequence 264AA NP 002095.1 (underline = mature protein) MTKFSSFSLF FLIVGAYMTH VCFNM EIIGG KEVSPHSRPF MASIQYGGHH VCGGVLIDPQ WVLTAAHCQY RFTKGQSPTV VLGAHSLSKN EASKQTLEIK KFIPFSRVTS DPQSNDIMLV KLQTAAKLNK HVKMLHIRSK TSLRSGTKCK VTGWGATDPD SLRPSDTLRE VTVTVLSRKL CNSQSYYNGD PFITKDMVCA GDAKGQKDSC KGDSGGPLIC KGVFHAIVSG GHECGVATKP GIYTLLTKKY QTWI KSNLVP PHTN (SEQ ID NO: 1) [0031] TABLE 2 DNA Sequence Open Reading Frame underlined: 41 to 835 NM 002104.1 AACACATTTC ATCTGGGCTT CTTAAATCTA AATCTTTAAA ATGACTAAGT TTTCTTCCTT TTCTCTGTTT TTCCTAATAG TTGGGGCTTA TATGACTCAT GTGTGTTTCA ATATGGAAAT TATTGGAGGG AAAGAAGTGT CACCTCATTC CAGGCCATTT ATGGCCTCCA TCCAGTATGG CGGACATCAC GTTTGTGGAG GTGTTCTGAT TGATCCACAG TGGGTGCTGA CAGCAGCCCA CTGCCAATAT CGGTTTACCA AAGGCCAGTC TCCCACTGTG GTTTTAGGCG CACACTCTCT CTCAAAGAAT GAGGCCTCCA AACAAACACT GGAGATCAAA AAATTTATAC CATTCTCAAG AGTTACATCA GATCCTCAAT CAAATGATAT CATGCTGGTT AAGCTTCAAA CAGCCGCAAA ACTCAATAAA CATGTCAAGA TGCTCCACAT AAGATCCAAA ACCTCTCTTA GATCTGGAAC CAAATGCAAG GTTACTGGCT GGGGAGCCAC CGATCCAGAT TCATTAAGAC CTTCTGACAC CCTGCGAGAA GTCACTGTTA CTGTCCTAAG TCGAAAACTT TGCAACAGCC AAAGTTACTA CAACGGCGAC CCTTTTATCA CCAAAGACAT GGTCTGTGCA GGAGATGCCA AAGGCCAGAA GGATTCCTGT AAGGGTGACT CAGGGGGCCC CTTGATCTGT AAAGGTGTCT TCCACGCTAT AGTCTCTGGA GGTCATGAAT GTGGTGTTGC CACAAAGCCT GGAATCTACA CCCTGTTAAC CAAGAAATAC CAGACTTGGA TCAAAAGCAA CCTTGTCCCG CCTCATACAA ATTAA GTTAC AAATAATTTT ATTGGATGCA CTTGCTTCTT TTTTCCTAAT ATGCTCGCAG GTTAGAGTTG GGTGTAAGTA AAGCAGAGCA CATATGGGGT CCATTTTTGC ACTTGTAAGT CATTTTATTA AGGAATCAAG TTCTTTTTCA CTTGTATCAC TGATGTATTT CTACCATGCT GGTTTTATTC TAAATAAAAT TTAGAAGACT Granzyme Proteins [0032] Granzymes (Grs) belong to the family of granule associated serine proteases that are expressed by cytotoxic T lymphocytes (CTL) and Natural killer (NK) cells and play important role in target cell apoptosis. Grs cleave a number of extracellular matrix proteins, thereby facilitating migration of CTL and NK cells through extracellular tissues, and induce cytokine secretion and directly activating various cytokines. GRK plays a role in inflammation responses and has pro-inflammatory properties [0033] A significant decrease of plasma level of natural serine proteases inhibitors (inter-alpha inhibitor proteins, IaIp) is found in septic patients. IaIp is shown to be a physiological inhibitor of GRK. Studies were carried out to determine whether GRK, as a protease, plays a role in pathogenesis of sepsis. [0000] GRK-Specific Antibodies [0034] Human GRK was used to generate GRK-specific antibodies. For example, a peptide with the amino acid sequence, 182-197 NSQSYYNGDPFITKDM of SEQ ID NO:1, a sequence unique to GRK was used to immunize rabbits. Polyclonal antisera as well as 20 monoclonal antibodies were generated using known methods. The antibodies were characterized, and an immunoassay to detect GRK levels in bodily fluids such as plasma was developed. Other GRK antibodies are commercially available and known in the art. [0000] Reagents and Procedures [0035] Synthetic peptides, NSQSYYNGDPFITKDC (pGRK: SEQ ID NO:3) and NDRNHYNFNPVIGMNS (pGrA; SEQ ID NO:4), derived from human Granzyme K and Granzyme A were synthesized using known methods or obtained from Sigma-Genosys (The Woodlands, Tex.). Recombinant human GRK (rGRK) and GrA (rGrA) were purchased from Alexis Biochemicals (San Diego, Calif.). All other chemicals were purchased from Sigma (St. Louis, Mo.) unless otherwise specified. [0000] Cell Culture [0036] The human IL-2 dependent NK cell line 92MI was obtained from the American Type Culture Collection (ATCC, Manassas, Va.). The cells were maintained in alpha minimum essential medium (Gibco, Grand Island, N.Y.), supplemented with 2 mM L-glutamine, 0.2 mM inositol, 0.1 mM 2-mercaptoethanol, 0.02 mM folic acid, 5% heat inactivated fetal calf serum (FCS) and horse serum. The cells were incubated in humidified air with 10% CO 2 at 37° C. and sub-cultured twice per week. [0000] Purification of GRK from Human NK Cell Line (NK-GRK) [0037] GRK was purified from cytotoxic granules of IL-2 dependent human NK cell line according to known methods, e.g., Hanna et al., 1993, Protein Express Purif 4:398-404. [0000] Generation, Characterization and Purification of GRK Specific Polyclonal Antibody (pAb) [0038] Polyclonal antibody against human GRK was generated in rabbits by immunizing with the synthetic peptide pGRK, corresponding to amino acid residues 189-205 of human GRK (SEQ ID NO:1) manufactured by Sigma-Genosys, The Woodlands, Tex. This sequence was identified using the MacVector software (Accelrys Inc, San Diego, Calif.) as a sequence unique to human GRK when compared to the sequence of human Granzyme A, Granzyme B or neutrophil elastase, cathepsin G or proteinase 3. It was also chosen from the sequence with the highest immunogenicity predicted by this software. Pre-immune serum (PRIS) was obtained prior to immunization. Three immunizations were performed at day 0, 14 and 28. Sera were collected and further characterized for its specificity. [0000] Western Blot Analysis of Human GRK [0039] Samples containing GRK: rGRK, NK-GRK or plasma samples were mixed with non-reducing SDS sample buffer, heated to 95° C. for 15 min, and separated by 12.5% SDS-PAGE. The immunodetection was performed using anti-GRK pAb followed by incubation with horseradish peroxidase (HRP)-conjugated goat anti-rabbit IgG (Biosource, Camarillo, Calif.). The blots were visualized by using Enhanced Chemiluminescence system (Pierce, Rockford, Ill). For the analysis of high molecular weight complex forms of GRK in plasma, samples were separated using 4-12% NuPAGE Bis-Tris gels according to the manufacturer's instruction (Invitrogen Corporation, Carlsbad, Calif.). [0000] Direct Binding and Competitive Peptide Inhibition Assay [0040] The specificity of the anti-GRK pAb was determined by a direct solid phase binding assay. pGRK and pGrA or rGRK and rGrA were immobilized onto 96-well microplates (Immulon 4, Dynex) in coating buffer (50 mM sodium bicarbonate, pH 9.6). Following blocking with 5% non-fat dried milk, anti-GRK pAb or PRIS diluted in PBS were added to the wells. The bound antibodies were detected by using HRP-conjugated goat anti-rabbit IgG and visualized by 1-Step ABTS substrate (Zymed, San Francisco, Calif.). The color change was measured at 405 nm on BioTek microplate reader (Bio-Tek Instruments, Winooski, Vt.). For the competitive inhibition assay, anti-GRK pAb was pre-incubated with various concentrations (from 0.01 to 10 ng/μL) of pGRK or pGrA at 37° C. for 45 min prior to being added to the microplates coated with rGRK. [0000] Affinity Purification [0041] Anti-GRK pAb was affinity purified from the rabbit antiserum by using immobilized pGRK to NHS-activated Sepharose column according to the manufacture's instruction (Amersham Bioscience, Piscataway, N.J.). [0000] Granzyme K ELISA Immunoassay [0042] A competitive ELISA using affinity purified anti-GRK pAb was performed as follows: pGRK (250 ng/well) was immobilized in coating buffer onto 96-well microplates overnight at 4° C. After coating, residual binding sites were blocked by 3% BSA. A serial dilution of pooled human plasma (healthy donors) in PBS was used to generate a standard curve on each plate. The concentration of GRK in this pooled human plasma was defined as 2000 Arbitrary Units (U)/mL. For the GRK levels analysis, 50 μL of diluted plasma samples (1:10 in PBS) or serially diluted standard plasma, were added to individual wells in triplicate along with 50 μl of anti-GRK pAb (0.25 mg/mL) and incubated for 1 h at 37° C. Subsequently, HRP-conjugated goat anti-rabbit IgG were added to the wells. 1-step ABTS was used as a substrate and absorbance was measured at 405 nm. The specificity of the developed ELISA was further evaluated by using pGrA or rGRK immobilized on the microplates. [0000] Inter Alpha Inhibitor Proteins (IaIp) ELISA Immunoassay [0043] Plasma levels of IaIp were quantitatively measured by sandwich ELISA using known methods such as that described by Lim et al., 2003, J. Infect. Dis., 2003; 188:919-926. [0000] Clinical Samples [0044] Blood samples of 41 healthy individuals were examined to establish the normal range of GRK levels in plasma. Blood samples from two septic patient groups were analyzed. The first group consisted of 15 patients delivered to the Emergency Department at Rhode Island Hospital (Group ED) with hypotension secondary to pneumonia or urosepsis. Each of these patients was identified and treated using the early-goal directed treatment guidelines for sepsis (Rivers et al., 2001, N. Engl. J. Med., 345:1368-1377; hereby incorporated by reference). These patients met the following criteria: a systolic blood pressure <90 mmHg after 2 liters of crystalloid infusion or a serum lactate >4 mmol/L. Monitoring of central venous pressure was performed in the ED which was used in titrating correct amounts of subsequent crystalloid and dobutamine in achieving normotension. These patients were subsequently transferred to the medical intensive care unit (ICU) for further treatment. Collected plasma from patients at the time of admission in the ED was used for the GRK assay. This represents the samples from the patients with the early stage of sepsis when the diagnosis was established at the time of admission. [0045] The second septic group consisted of 25 severe septic patients enrolled in the phase III multicenter septic clinical trial of an experimental therapeutic agent (Group CT). Blood samples were obtained at study entry within 24 hours of the onset of severe sepsis (according to the consensus definitions established at the American College of Chest Physicians/Society of Critical Care Medicine Consensus conference (Levy et al., 2003, Crit. Care Med. 31 1250-1256; herein incorporated by reference). Plasma was separated from the blood by centrifugation, transported to the research laboratory, and stored at −80° C. [0000] Statistical Analysis [0046] Student's t test was used to analyze the significance of the plasma GRK levels between the septic groups and healthy controls. All data were presented as mean values±SD. Correlation was performed using the Spearman test. A P value <0.05 was considered as statistically significant. [0000] Characterization of Anti-GRK pAb [0047] The specificity of anti-GRK pAb was determined in a direct binding ELISA using immobilized peptides, pGRK and pGrA, and with recombinant granzymes, rGRK and rGrA as shown in FIG. 1 . Anti-GRK pAb bound specifically to pGRK and rGRK but not to pGrA or rGrA. No binding was observed in the control pre-immune serum. To verify the specificity of this antibody, a competitive binding assay was performed. pGRK was able to inhibit the binding of anti-GRK pAb to rGRK immobilized on the 96-well microplates in a concentration dependent manner. A complete inhibition of antibody binding was achieved at 10 ng/μL of pGRK. No significant inhibition was observed with control pGrA ( FIG. 2 ). These results demonstrated that anti-GRK pAb was specifically directed against unique peptide sequence corresponding to human GRK. The anti-GRK pAb was further affinity purified and used in Western blot and GRK ELISA. [0000] Detection of Native Form of GRK from Human NK Cell Line [0048] Granzymes (Grz) are expressed by CTL and NK cells and stored in their cytotoxic granules until degranulation. To identify the native form of GRK and to demonstrate the ability of anti-GRK pAb to bind GRK in its native form, GRK was purified from cytotoxic granules obtained from human IL-2 dependent NK cell line. Human rGRK was included as a positive control. The results of Western blot analysis using affinity purified anti-GRK pAb showed an identical 26 kDa reactive band in both, GRK purified from the human NK cell line and human rGRK ( FIG. 3A ). PRIS was used as a negative control ( FIG. 3B ). The results further confirmed the specificity of anti-GRK pAb and demonstrated its ability to bind native human GRK. [0000] Development of a Competitive ELISA Using Anti-GRK pAb [0049] To measure the levels of GRK in biological fluids such as plasma, a novel competitive ELISA using affinity purified anti-GRK pAb was developed. The immunoassay was based on the ability of GRK in plasma samples to block the binding of anti-GRK pAb to immobilized pGRK. Substitution of pGRK by rGRK showed similar results. A standard curve was established by a serial dilution of pooled human plasma ( FIG. 4 ). The detection range of the GRK assay was 1.5-100 U/mL. The Coefficient of Variation (CV) between three separate experiments was less than 10%. [0000] GRK Levels in Plasma of Septic Patients and Healthy Controls [0050] The developed competitive assay was used to measure the levels of GRK in plasma samples from healthy controls (HC) and septic patients exhibiting early symptoms of sepsis when admitted to the Emergency Department (Group ED) and septic patients with severe sepsis enrolled in a clinical trial (Group CT). The results indicated that the levels of GRK were significantly increased in Group ED (mean±SD=123.4±6.61 U/mL, n=15) and significantly decreased in Group CT (44.9±4.14 U/mL, n=25) compared to HC (69.14±2.39 U/mL, n=41) ( FIG. 5 ). The differences between the plasma GRK levels in HC vs. Group ED and in HC vs. Group CT were statistically significant (P<0.0001). Statistically significant difference was also found between both septic groups (ED vs CT, P<0.0001). [0000] Molecular Form of GRK in Human Plasma [0051] In human plasma, serine proteases often appear in covalent complexes together with their respective inhibitors. In an effort to determine the molecular form of GRK present in plasma from healthy individuals and septic patients, samples were separated by 4-12% or 12.5% SDS-PAGE followed by Western blot analysis using anti-GRK pAb. The 4-12% SDS PAGE and subsequent Western blot analysis revealed that GRK circulates in healthy individuals in a complex form, resistant to SDS and heat, with a major bands of >250 and >150 kDa ( FIG. 6A ). In the plasma of septic patients analyzed, >250 kDa band was clearly absent. Enhanced levels of the 150 kDa band and additional bands corresponding to ˜125, 98 and 60 kDa in the plasma of Group ED were observed while noticeably less of these GRK reactive bands were detected in the plasma of Group CT. Moreover, 12.5% SDS-PAGE and subsequent Western blot analysis showed a lower band of 26 kDa only in plasma of septic patients (Group ED and CT), but not in HC ( FIG. 6B ). The apparent 26 kDa band was similar in size with the GRK purified from human NK cells cytotoxic granules, suggesting the presence of systemic free GRK in septic patients. [0000] IaIp Levels in Plasma of Septic Patients and Healthy Controls [0052] Plasma IaIp levels of patients with sepsis are significantly decreased compared to normal controls. To determine whether the IaIp levels fluctuated with the stage of sepsis, IaIp levels were measured in the same set of samples assayed for GRK levels. The results demonstrated that plasma IaIp levels were significantly decreased in both septic patient groups: Group ED (249.6±24.31 mg/L, n=15) and Group CT (176.0±16.15 mg/L, n=25) compared to HC (597.1±31.69 mg/L, n=41). Statistically significant differences were found between the HC and either septic groups (P<0.0001). Differences between two septic groups (ED vs CT) were also statistically significant (p=0.0125) ( FIG. 7 ). [0000] Correlation between GRK and IaIp in Plasma of Septic Patient [0053] Measured plasma levels of GRK and IaIp from Group ED and Group CT were evaluated by the Spearman correlation test to determine the correlation between these proteins during sepsis progression. The results showed, an inverse correlation between the increase of GRK and decrease of IaIp levels in plasma of Group ED (n=14; Spearman; r=−0.5551; P=0.0394) ( FIG. 8A ). By contrast, no significant correlation between the GRK and IaIp levels of Group CT (n=25; Spearman; r=0.197; P=0.3451) was found ( FIG. 8B ). [0000] Plasma Granzyme K Levels are Altered in Patients with Early Symptoms of Sepsis and Severe Sepsis [0054] Sepsis is not a single disease but a complex and heterogeneous process that can progress rapidly, leading to global tissue hypoxia, organ failure, and death. An early detection and early intervention was found to be crucial in reducing mortality from sepsis. The utility of a marker for sepsis that can identify patients at the early disease state when intervention can alter disease progression is therefore desirable. [0055] Low constitutive plasma levels of Grz, serine proteases found in the cytotoxic granules of NK cells and CTL, have been observed. Because of their potent activity, excess protease inhibitors are usually present to inhibit these enzymes thereby preventing bystander effects. The absence of these inhibitors has been associated with disease pathology when increased serine protease activity is present. Decreased plasma levels of protease inhibitors in the presence of increased levels of serine proteases results in enhanced inflammatory responses resulting from the cleavage of specific substrates. [0056] A highly specific GRK antibody was made and a competitive ELISA assay was developed to quantify the levels of GRK in biological samples. A constitutive level of GRK was observed in healthy controls and found to be present in high molecular weight (>250 and >150 kDa) complexes that were highly specific and stable to SDS and heat treatment. These results are consistent with the finding that IaIp are the physiological inhibitors of GRK as two IaIp include 250 kDa IaI and 125 kDa PaI. [0057] Analysis of patients exhibiting symptoms of early sepsis found increased levels of GRK and decreased levels of IaIp. Biochemical analysis of the GRK present in these samples indicated the loss of the >250 kDa complex with a concordant increase of a number of different complexes of lower molecular weight. In addition, a free 26-kDa GRK form not found in healthy controls appeared in these patients. The result confirms the finding of decreased plasma levels of IaIp in septic patients in which a concomitant increase of IaIp-related fragments in urine was also observed. These findings are consistent with the proteolytic cleavage of IaIp, potentially a consequence of the release of proteases by activated neutrophils, or decreased production of IaIp. NK cells are the likely source of increased amounts of GRK as increased levels of GRK message is observed in activated NK cells. Inflammatory stimuli such as LPS have been shown to induce activation and proliferation of NK cells in vitro and in vivo injection of LPS into human volunteers induced a 5 fold increase in soluble GrA that peaked at 2 hours and an increase of soluble GrB that peaked at 6 hours. [0058] Analysis of patients enrolled in a clinical trial for severe sepsis found significantly decreased GRK levels along with decreased levels of IaIp. Biochemical analysis of GRK indicated further degradation of the GRK complexes and a significant level of the free 26-kDa GRK form. These clinical trial patients were enrolled within 24 hours after the onset of severe sepsis in the ICU. Thus it is estimated that the blood collection from these patients occurred 24-72 hours after their admission to the emergency department. The rapid decrease in GRK levels associated with the progression of sepsis might be due to the combined effects of increased clearance and decreased GRK secretion at the time when sepsis has progressed. These findings are also consistent with the finding of a rapid decrease in Grz levels following a rapid increase in response to inflammatory stimuli. Taken together, the results indicate that measurement of GRK levels is a means for staging of sepsis and that increased levels of GRK are indicative of early sepsis. [0059] The appearance of the free 26-kDa GRK form in the septic patients raises the possibility that the free GRK could impact the septic response. Increased levels of GrA and GrB have been observed in bacteremic melioidosis, and the GrA locus is closely linked to the GRK locus and both of these serine proteases act as tryptases. Incubation of human peripheral blood mononuclear cells with purified GrA has been found to induce the production of the proinflammatory cytokines, IL-6 and IL-8. One mechanism underlying the observed levels is that an innate response to infectious agent results in increased production of GRK, enhanced production of proteases cleaves IaIp, and decreased production of IaIp results in decreased levels of IaIp. The result of these events is the appearance of free uninhibited GRK which then induces increased levels of proinflammatory cytokines causing an amplification of the septic response. [0060] The data described herein indicate that an anti-GRK Ab or mixture of antibodies raised against residues 182-197 and/or 189-205 of SEQ ID NO:1 is unique in its ability to recognize a specific epitope of GRK in both, free form and when complexed to inhibitors or other molecules and that the assay accurately measures the total levels of GRK (both free and complexed) in biological samples. The use of this antibody revealed that GRK appears in plasma of healthy individuals in a complex form. By contrast, free GRK was only found in patients with sepsis. Significantly increased levels of plasma GRK was found in patients with early symptoms of sepsis indicating that measuring plasma GRK levels is an effective tool to detect early sepsis. [0061] The antibodies of the invention, e.g., rabbit polyclonal antibody with an epitope binding specificity of 182-197 NSQSYYNGDPFITKDM, is unique because it is able to detect GRK that is bound to inhibitor as well as free GRK. Other antibodies in the art (e.g., Bade et al, 2005, Eur. J. Immunol. 35:2940-2948) detect only free GRK. Thus, the ligands of the invention have an important clinical advantage in that they detect the total GRK level in an individual at risk of serious life-threatening illness or death. [0062] The monoclonal antibody based assay of Bade et al. is limited in its applicability because it only detects free uncomplexed GRK ( FIGS. 6, 9 ). Because the sequence similarity of the peptide sequence in human and mouse, the antibodies described herein, e.g., the polyclonal antibody, is able to measure human as well as mouse GRK levels. The monoclonal antibody based assay of Bade is unable to do so. [0063] The loss of the GRK inhibitor, inter-alpha-inhibitor protein (IAIP), combined with increased production of GRK via the activation of NK cells results in the appearance of uninhibited GRK which is able to amplify the septic response by the cleavage of specific substrates, and incubation of human peripheral blood lymphocytes with recombinant human GRK results in the production of high levels of IL-6 and IL-8, soluble factors associated with the development of severe sepsis. [0000] GRK Levels in Plasma of Septic Patients: an Early Marker in Sepsis [0064] The assay was tested and found to be highly sensitive and reproducible. For example, GRK concentration in plasma/serum was detected in the range of 15-1000 U/mL. GRK levels were evaluated in healthy normal controls and in patients with sepsis. Plasma was collected from patients enrolled in a septic clinical trial (CT) and septic patients admitted in the Emergency Department (ED). The latter group represents patients with the early stage of sepsis when the diagnosis was established at the time of admission, and the former group represents patients that presented initially as the ED group but had undergone treatment for sepsis. IaIp level in all septic patients were found to be significantly lower than in healthy controls, and GMZK levels were found to be significantly higher in ED patients (mean±SD=1378 ±189 U/mL, n=15) and significantly lower in CT patients (157±19 U/mL, n=10) compared to healthy controls (747±75 U/mL, n=15). The differences between the septic groups (p<0.0001) and ED to healthy controls (p<0.0015) or CT to healthy controls (p<0.0001) were significant. Western blot analysis confirmed the detection of GRK and revealed a reactive band in human plasma corresponding to approximately 28 kDa in the tested groups. [0065] The results indicate that GRK levels in bodily fluids, e.g., plasma, represent an early marker/diagnostic tool to identify patients that are developing sepsis and are in need of therapeutic intervention. Other Embodiments [0066] While the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
Compositions and methods for detecting sepsis by contacting a subject-derived sample with a ligand that binds to GRK and determining the concentration of GRK in the sample. An increase in the concentration of GRK compared to that of a normal, healthy control sample indicates that the subject from which the sample is obtained is suffering from or at risk of developing sepsis.
6
FIELD OF THE INVENTION The invention is related to a structure for a hub, and more particularly to a structure for the connection between the hub and its transceivers. BACKGROUND OF THE INVENTION In a Local Area Network (LAN) characterized by asteroid topology, a twisted-pair cable usually links up the nodes for information transmission, while a hub connects each computer to the server or generates new signals. Most of the known hubs includes several connection ports for receiving the communication module, such as transceivers of RJ-45 connectors or transceivers composed of photoelectric reception and emission components. All known combinations of transceivers and a hub are based on an assembly-disassembly design. FIG. 1 shows a conventional transceiver. While taking this transceiver from a hub, a user has to press a slider 10 located at the top of the front of the transceiver for separating the transceiver from the hub. However, once it is pushed and moved forward, the slider 10 will not return to the previous locking position by itself. A drawback of the design is that, if the transceiver is pushed into the connection port of the hub again, the slider 10 will not lock the transceiver in the connection port of the hub properly. The above-described design still has another drawback. The aforesaid known slider 10 is disposed on the lateral side near the front end of the transceiver, but not extended out of the front of the transceiver. If the transceivers are arranged in pairs and aligned in two rows, that is, each pair of transceivers are put together in a mirror-like (or back-to-back) manner before being pushed into the hub, then the slider will not work. Alternatively, increasing the gap between a pair of transceiver might solve this problem, but it will increase the volume of the hub. THE OBJECT AND SUMMARY OF THE INVENTION The primary object of the invention is to improve the structure for the connection between a hub and its communication modules (such as transceiver), and provide a connection structure for easy assembly and disassembly. The solution put forth by the invention involves re-designing the releaser. In the first embodiment, the releaser is slidably installed in the transceiver. The releaser has an applied end protruding from one end of the transceiver. After the transceiver has been inserted into the connection port of the hub, the applied end is still positioned out of the front of the hub. A user may remove the transceiver from the hub easily by pressing the releaser in front of the hub. In another preferred embodiment of the invention, the lever-style releaser has applied end exposed out of the front of the transceiver. To remove the transceiver from the hub, a user can press the applied end, so as to move a fastener for disassembling the transceiver from the hub. Another object of the invention is to reduce the size of hub. Since the releaser is not positioned on the side of the transceiver, the size of hub will be reduced and the transceivers can be easily installed or removed, whereas pairs of transceivers may be inserted into a hub in a mirror-like (or back-to-back) manner and be aligned in two rows. The explanations and illustrations of the preferred embodiments and a detailed description of the technique for the invention are as follows: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 depicts a conventional transceiver; FIG. 2 depicts the first embodiment of the invention; FIG. 3 depicts the structure of a transceiver for the first embodiment of the invention; FIGS. 4 & 5 illustrate how a releaser works; FIGS. 6A & 6B are the cross-sectional diagrams for the structure of the transceiver in the first embodiment; FIG. 7 depicts the second embodiment of the invention; FIG. 8 is a rear view of the transceiver shown in FIG. 7; FIGS. 9A & 9B are the cross-sectional diagrams for the structure of the transceiver in the second embodiment; FIG. 10 is a front view of the third embodiment of the invention; and FIG. 11 is a rear view of the third embodiment of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The First Embodiment FIG. 2 depicts the structure of the hub 20 and its communication module (exemplified by a transceiver 30 in the figure) for the first embodiment of the invention. The hub 20 has several connection ports 21 arranged in two rows. This kind of transceiver 30 is, basically, a transceiver having a receiver 35 a and a transmitter 35 b for connecting an input optical fiber and an output optical fiber, respectively. The connection structure put forth by the invention includes a stopper 40 installed inside the connection port 21 of the hub 20 (see FIG. 6 A), wherein one end of the stopper 40 is fixed in the hub 20 and the other free end 41 is flexible and extends obliquely toward the transceiver 30 ; a fastener 50 fixed in the transceiver 30 for being engaged with the free end 41 of the stopper 40 after the transceiver 30 has been inserted into the connection port 21 (see FIG. 6 A), so that the transceiver 30 will be fixed in the connection port 21 of the hub 20 ; and a releaser 60 installed on the external side of the transceiver 30 . The releaser 60 can slide between the assembling position (see FIG. 6A) and the disassembling position (see FIG. 6 B). The releaser 60 includes an applied end 61 and a pair of flexible wings 62 a and 62 b (see FIGS. 3 & 4 ). The ends of the pair of wings (see FIG. 6A) extend obliquely along the direction opposite to the insertion direction of the transceiver 30 into the connection port 21 . The ends of the pair of wings 62 a and 62 b can be coupled with the notches 31 a and 31 b on the surface of the transceiver 30 , respectively. Owing to the elasticity of the pair of wings 62 a and 62 b , the releaser 60 is kept in the assembling position in a normal state. There is a surface 63 on the side of the head of the releaser 60 facing the stopper 40 . The surface 63 can contribute to detach the free applied end 41 of the stopper 40 from the fastener 50 (see FIG. 6 B). As a result, a user may remove the transceiver 30 from the connection port 21 of the hub 20 . In the embodiments disclosed by the invention, the aforesaid stopper 40 is, in fact, a part of a metallic housing 4 A that encloses the transceiver 30 (see FIG. 6 A). This metallic housing 4 A not only has the functions of electrical grounding and shielding from electromagnetic interface, but also contributes to the combination of a hub 20 and its transceiver 30 . Hence, a metallic resilient element can be formed on the metallic housing 4 A and extend outwards from the transceiver 30 as the aforesaid stopper 40 . In the preferred embodiment, a hook is formed on the free end 41 , and a hole 411 is made on the surface of the stopper 40 for locking the fastener 50 . The releaser 60 is a flat component. It is inserted into a groove 32 found on the surface of the transceiver 30 and restricted by a cover 33 fixed to the top of the groove 32 so that it can only slide along the groove 32 . As shown in FIG. 4, the ends of the wings 62 a and 62 b can be coupled with the notches 31 a and 31 b , respectively, formed on the surface of the transceiver 30 . In the normal state, the releaser 60 is not pushed against, and there is a gap between the surface 63 on the head of the releaser 60 and the fastener 50 . However, once the transceiver 30 is inserted into the connection port 21 of the hub 20 , the free end 41 of the stopper 40 will urge against the fastener 50 from the gap (see FIG. 6 A). While disassembling the transceiver 30 from the connection port 21 of the hub 20 , the user may apply a force on the applied end 61 of the releaser 60 , and push the surface 63 toward the fastener 50 until it reaches the disassembling position (see FIG. 5 ). As shown in FIG. 5, when the releaser 60 reaches the assembling position, the wings 62 a and 62 b deform under the squeeze of the groove 32 . With the resilient force generated by the deformity of the wings 62 a and 62 b , the releaser 60 returns to the normal position. In the first embodiment, the fastener 50 is a kind of protuberance fixed on the external surface of the transceiver 30 . There is an oblique surface 51 on the side of the fastener 50 facing the stopper 40 . The oblique surface 51 can slide beneath the stopper 40 when the fastener 50 is inserted into the hub 20 along with the transceiver 30 . The Second Embodiment The second embodiment of the invention is characterized by a modification of the fastener 50 put forth in the first embodiment. The second embodiment involves a movable fastener 70 . FIGS. 7 & 8 depict the structure of the movable fastener 70 . The movable fastener 70 includes an elongated body 71 that may be inserted into or stuck out from the transceiver 30 , as well as a spring 72 . In the normal state, the spring 72 can raise the head 710 of the elongated body 71 so that the free end 41 of the stopper 40 stops it after the transceiver 30 has been inserted into the connection port 21 . There is an oblique surface 711 (or an arc-shaped surface) on the side of the head 710 of the elongated body 71 facing the stopper. The oblique surface 711 is slidable beneath the stopper 40 when the fastener 70 is inserted into the hub 20 along with the transceiver 30 , as shown in FIGS. 9A and 9B. A through hole 34 is pierced in the transceiver 30 . By increasing the size of the head 710 , the head 710 of the elongated body 71 can only be inserted into or stick out from a relatively bigger recess 341 at one end of the through hole 34 . Protuberances 73 a and 73 b are formed on both sides of the other end of the elongated body 71 . The spring 72 is telescoped on the elongated body 71 and positioned between the head 710 and the protuberances 73 a & 73 b . As shown in FIG. 8, there is a slit 342 on the inner wall of the other end of the through hole 34 . The slit 342 is characterized by radial widening. As a result, protuberances 73 a & 73 b can only pass through the slit 342 , if aligned. By rotating the elongated body 71 , the protuberances 73 a & 73 b can engage with the slit 342 such that the elongated body 71 and the spring 72 can be installed in the transceiver 30 . With the elasticity of the spring 72 , the head 710 of the elongated body 71 may be lifted in the normal state. As shown in FIGS. 9A & 9B, the oblique surface 63 a of the releaser 60 is formed on the side facing the elongated body 71 . When the releaser 60 is pushed to the assembling position, the oblique surface 63 a may push the head 710 of the elongated body 71 into the transceiver 30 so as to separate the head 710 of the elongated body 71 from the stopper 40 for the removal of the transceiver 30 . The Third Embodiment The third embodiment is similar to the second embodiment except that the aforesaid releaser 60 is replaced by a lever. As shown in FIGS. 10 & 11, an extended lever 80 is installed in the housing 36 of the transceiver 30 . One end of the lever 80 is connected to the housing 36 of the transceiver 30 , while its other end extends toward the direction of the output/input ends 35 a and 35 b of the transceiver 30 to provide an applied end 81 . The aforesaid through hole 34 pierces through the lever 80 . Hence, by pressing the applied end 81 of the lever 80 along the direction of the arrow shown in FIG. 11, the head 710 of the elongated body 71 can be separated from the stopper 40 for the removal of the transceiver 30 . While the invention is described by way of example and in terms of the aforesaid preferred embodiments, it is to be understood that the invention is not limited thereto. It should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. Therefore the scope of protection for the invention should conform to the claims attached below.
A structure for the connection between a hub and its transceivers for installing a transceiver in a connection port of the hub is provided. The connection structure includes a fastener installed in a transceiver, a stopper installed in the hub for coupling with the fastener, and a releaser for separating the fastener and stopper. There is a button-style releaser with an applied end that reaches the front of the hub for separating the transceiver from the hub when the applied end is pressed.
7
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a divisional of co-pending U.S. patent application Ser. No. 11/299,304, filed Dec. 9, 2005, now U.S. patent Ser. No. ______, which application and this application is a divisional of U.S. patent application Ser. No. 10/321,857, filed Dec. 16, 2002, now U.S. Pat. No. 7,067,639, issued Jun. 27, 2006, which application and this application is a continuation of International Appl'n No. PCT/NL02/000383 filed on Jun. 11, 2002, designating the United States of America, published in English on Dec. 19, 2002 as PCT International Publication WO 2002/101026 A2, which applications claim priority to EP 01202239.8, filed Jun. 11, 2001, the contents of the entirety of each of which are incorporated by reference. STATEMENT ACCORDING TO 37 C.F.R. § 1.52(e)(5)-SEQUENCE LISTING SUBMITTED ON COMPACT DISC [0002] Pursuant to 37 C.F.R. § 1.52(e)(1)(iii), a compact disc containing an electronic version of the Sequence Listing has been submitted concomitant with this application, the contents of which are hereby incorporated by reference. A second compact disc is submitted and is an identical copy of the first compact disc. The discs are labeled “copy 1” and “copy 2,” respectively, and each disc contains one file entitled “SeqListCRF.txt” which is 88 KB and created on Dec. 16, 2002. TECHNICAL FIELD [0003] The present invention relates generally to biotechnology, and, more particularly, pertains to a method for obtaining cell-wall material of Gram-positive bacteria with an improved capacity for binding a proteinaceous substance comprising an AcmA cell-wall binding domain, as well as pharmaceutical compositions including the obtained cell-wall material. BACKGROUND [0004] Heterologous surface display of proteins (Stahl and Uhlen, TIBTECH May 1997, 15, 185-192) on recombinant microorganisms via the targeting and anchoring of heterologous proteins to the outer surface or the cell wall of host cells, such as yeast, fungi, mammalian cells, plant cells, and bacteria, has been possible for several years. Display of heterologous proteins at the surface of these cells has taken many forms including the expression of reactive groups such as antigenic determinants, heterologous enzymes, single-chain antibodies, polyhistidyl tags, peptides, and other compounds. Heterologous surface display has been applied as a tool for applied and fundamental research in microbiology, molecular biology, vaccinology and biotechnology. Another application of bacterial surface display has been the development of live-bacterial-vaccine delivery systems. The cell-surface display of heterologous antigenic determinants has been considered advantageous for inducing antigen-specific immune responses in live recombinant cells used for immunization. Another application has been the use of bacterial surface display in generating whole-cell bioadsorbents or biofilters for environmental purposes, microbiocatalysts, and diagnostic tools. [0005] Generally, chimeric proteins include an anchoring or targeting portion that is specific and selective for the recombinant organism, wherein the anchoring portion is combined with the reactive group, such as the antigenic determinant, heterologous enzyme, single-chain antibody, polyhistidyl tag, peptide, or other compound. A well-known anchoring portion comprises the so-called LPXTG (SEQ ID NO: 1) box, which covalently binds to a Staphylococcus bacterial surface, i.e., in the form of a fully integrated membrane protein. In this manner, at least two polypeptides of different genetic origins may be joined by a normal peptide bond to produce a chimeric protein. For example, PCT International Patent Publication No. WO 94/18330, which relates to the isolation of compounds from complex mixtures and the preparation of immobilized ligands (bioadsorbents), discloses a method for obtaining a ligand comprising anchoring a binding protein in or at the exterior of a cell wall of a recombinant cell. The binding protein is essentially a chimeric protein produced by the recombinant cell and includes an N-terminal part derived from an antibody that is capable of binding to a specific compound, wherein the N-terminal part is joined to a C-terminal anchoring part, derived from an anchoring protein purposely selected for being functional in the specific recombinant cell chosen. PCT International Patent Publication No. WO 97/08553 discloses a method for selectively targeting proteins to the cell wall of Staphylococcus sp., using anchoring proteins which include long stretches of at least 80-90 amino acid long amino acid cell-wall-targeting signals. The signals are derived from the lysostaphin gene or amidase gene of Staphylococcus and encode for proteins that selectively bind to Staphylococcus cell-wall components. [0006] Vaccine delivery or immunization systems with attenuated bacterial vector strains that express distinct antigenic determinants against a wide variety of diseases are currently being developed. Mucosal vaccines for nasal or oral passages using these attenuated bacterial vectors have received a great deal of attention. For example, both systemic and mucosal antibody responses against an antigenic determinant of hornet venom have been detected in mice orally colonized with a genetically engineered human oral commensal Streptococcus gordonii strain that expresses the hornet venom antigenic determinant on its surface (Medaglini et al., PNAS 1995, 2; 6868-6872). A protective immune response was also elicited by oral delivery of a recombinant bacterial vaccine that included tetanus toxin fragment C constitutively expressed in Lactococcus lactis (Robinson et al., Nature Biotechnology 1997, 15; 653-657). Mucosal immunization is considered an effective means of inducing IgG and secretory IgA antibodies directed against specific pathogens of mucosal surfaces. [0007] Immunogens expressed by bacterial vectors may be presented in a particulate form to antigen-presenting cells, such as M-cells, of the immune system and therefore should be less likely to induce tolerance when compared to soluble antigens. Additionally, the existence of a common mucosal immune system permits immunization of one specific mucosal surface in order to induce secretion of antigen-specific IgA and other specific immune responses at distant mucosal sites. A drawback to using bacterial vectors for immunization is the potential of the bacterial strain causing inflammation or disease and potentially leading to fever or bacteremia. Instead of using attenuated bacterial strains that may become pathogenic, recombinant commensal bacteria, such as Streptococcus sp. or Lactococcus sp., may be used as vaccine carriers. [0008] A potential problem with recombinant commensal microorganisms is that they may colonize the mucosal surfaces and generate a long-term exposure to the target antigens expressed and released by the recombinant microorganisms which may cause immune tolerance. [0009] Additionally, the use of genetically modified microorganisms that contain recombinant nucleic acid has met considerable opposition from the public as a whole, stemming from a low-level acceptance of products which contain recombinant DNA or RNA. Similar objections exist against even the use of attenuated pathogenic strains or against proteins, or parts of proteins, derived from pathogenic strains. Further, the heterologous surface display of proteins described herein entails the use of anchoring or targeting proteins specific and selective for a limited set of microorganisms, which are of recombinant or pathogenic nature which greatly restricts their potential applications. [0010] The protein anchor of L. lactis , AcmA (cA), its homologs and functional derivatives (PCT International Patent Publication No. WO99/25836) bind in a non-covalent manner to a wide variety of Gram-positive bacteria. Binding also occurs to isolated cell-wall material. The ligand to which the protein anchor of L. lactis binds in these cell walls is currently unknown. [0011] The use of a gram-positive, food-grade bacterium, such as Lactococcus lactis , offers significant advantages over the use of other bacteria, such as Salmonella , as a vaccine delivery vehicle. For instance, L. lactis does not replicate in or invade human tissues and reportedly possesses low intrinsic immunity (Norton et al. 1994). Further, mucosal-delivered L. lactis that expresses tetanus toxin fragment C has been shown to induce antibodies that protect mice against a lethal challenge with tetanus toxin even if the carrier bacteria was killed prior to administration (Robinson et al. 1997). The killed bacteria still contain recombinant DNA that will be spread into the environment, especially when used in wide-scale oral immunization programs. However, the uncontrollable shedding of recombinant DNA into the environment may have the risk of being taken up by other bacteria or other microorganisms. SUMMARY OF THE INVENTION [0012] Disclosed is a method for improving binding of a proteinaceous substance to cell-wall material of a Gram-positive bacterium. The proteinaceous substance comprises at least one repeat, but may comprise two or three repeat sequences of an AcmA cell-wall binding domain, homolog or functional derivative thereof. The method comprises treating the cell-wall material with a solution capable of removing a cell-wall component, such as a protein, lipoteichoic acid or carbohydrate, from the cell-wall material and contacting the proteinaceous substance with the treated cell-wall material. Improved binding may be obtained by treating the cell-wall material with a solution capable of removing a cell-wall component. The cell-wall material may be subsequently stored until it is contacted with a desired fusion protein. The fusion protein may comprise an AcmA cell-wall binding domain, homolog or functional derivative thereof where the cell-wall material is contacted with the fusion protein. The method of the present invention may be used to obtain cell-wall material with an improved capacity for binding a proteinaceous substance comprising the AcmA cell-wall binding domain, homolog or functional derivative thereof. [0013] Also disclosed is a method for removing components from a bacterial cell wall comprising treating whole cells with a solution capable of removing a cell-wall component such as a protein, lipoteichoic acid or carbohydrate from the cell-wall material. The cell-wall material obtained by the present invention yields cell-wall material with at least 20%, better 30%, best 40% or even 50% of relatively empty, but intact, cell envelopes which include inert spherical microparticles. The inert spherical microparticles will be referred to herein as bacterial “ghosts.” The term “ghosts” reflects the size and shape of the bacterium from which the ghosts are obtained. [0014] Also disclosed is a method for obtaining cell-wall material of a Gram-positive bacterium with an improved capacity for binding with a proteinaceous substance comprising an AcmA cell-wall binding domain, homolog or functional derivative thereof. The method comprises treating the cell-wall material with a solution capable of removing a cell-wall component such as a protein, lipoteichoic acid or carbohydrate from the cell-wall material, wherein the cell-wall material comprises spherical peptidoglycan microparticles referred to herein as ghosts. [0015] Methods to extract bacterial cell-wall material with a solution have been described in EP 0 545 352 A and Brown et al. (Prep. Biochem. 6:479, 1976). A method to obtain purified soluble peptidoglycan from bacteria by exposure to TCA has been disclosed. The cited references describe procedures in which cells are mechanically disrupted, wherein the resulting cell fragments are treated with TCA to extract peptidoglycans from the cell wall. The cited methods provide a peptidoglycan preparation and a lysed, randomly fragmented cell-wall preparation from which cell-wall components have been removed. However, these methods do not yield ghosts. Furthermore, the methods do not allow targeting with a proteinaceous substance comprising an AcmA cell-wall binding domain, homolog or functional derivative thereof. [0016] The method of the present invention is aimed at yielding ghosts from which cell-wall components have been removed. The use of ghosts for display of proteinaceous substances has advantages over the use of the disrupted cell-wall material. For example, binding the proteinaceous substance to bacterial ghosts results in a higher packing density when compared to binding a substance to mechanically disrupted cell-wall material. A high density surface display of proteins is favorable for application in industrial processes. In one embodiment, the present invention discloses a method for obtaining the cell-wall material not involving rupture. [0017] Cell-wall material obtained by mechanical disruption methods suffers from several practical drawbacks. Because cells are completely broken with mechanical disruption, intracellular materials are released from the cell and cell-wall fragments need to be separated from a complex mixture of proteins, nucleic acids, and other cellular components. The released nucleic acids may increase the viscosity of the solution and complicate processing steps, especially chromatography. The cell debris produced by mechanical lysis also often includes small cell fragments which are difficult to remove. These problems are overcome when ghosts are produced using methods of the present invention. The uniform composition of a ghost preparation including particle size and shape offers other advantages for subsequent purification and isolation steps. The invention thus discloses a method of obtaining cell-wall material not involving rupture of the cell wall, wherein the resulting cell-wall material comprises ghosts. [0018] The use of bacterial ghosts is often preferable when compared to the use of mechanically disrupted cell-wall bacteria for the surface display of immunogenic determinants. In contrast to mechanical disruption procedures, ghosts are produced by a process that preserves most of the bacteria's native spherical structure. Bacterial ghosts are better able to bind to and/or are more easily taken up by specific cells or tissues than mechanically disrupted cell-wall material. The ability of bacterial ghosts to target macrophages or dendritic cells enhances their functional efficacy. Thus, the non-recombinant, non-living ghost system disclosed by the present invention is well suited as a vaccine delivery vehicle. Accordingly, the invention discloses a method for obtaining ghosts, wherein the ghosts have an improved capacity for binding with a proteinaceous substance and have an enhanced induction of the cellular immune response. [0019] The invention also discloses a method for binding a proteinaceous substance to the cell-wall material of a Gram-positive bacterium, wherein the proteinaceous substance comprises an AcmA cell-wall binding domain, homolog or functional derivative thereof. The method comprises treating the cell-wall material with a solution capable of removing a cell-wall component such as a protein, lipoteichoic acid or carbohydrate from the cell-wall material, and subsequently contacting the proteinaceous substance with the cell-wall material. The cell-wall material comprises ghosts which have been produced by the present invention which does not involve rupture of the bacterial cell-wall. [0020] In another embodiment, the solution capable of removing the cell-wall material has a pH that is lower than the calculated Pi value of the AcmA cell-wall binding domain, homolog or functional derivative thereof. Particularly, the solution comprises an acid such as acetic acid (HAc), hydrochloric acid (HCl), sulphuric acid (H 2 SO 4 ), trichloro acetic acid (TCA), trifluoro acetic acid (TFA), and monochloroacetic acid (MCA). The concentration of the acid in the solution will be dependent on the desired pH value which may be determined by calculation using a computer program such as DNA star or Clone Manager. For instance, when the calculated pI is >8, pH values of about 6 to 4 may suffice for effecting appropriate binding. When pI values are calculated to be lower, such as around 6, pH values of 3-4 may be selected. When domains with calculated pI values ranging from 8 to 12 are encountered, using the solution comprising 0.06 to 1.2 M TCA, or comparable acid, may suffice. [0021] The binding may be improved by heating the cell-wall material or ghosts in the solution. However, precise requirements for the heating may vary depending on the cell-wall material or ghosts. However, heating for 5-25 minutes at approximately boiling temperature (i.e., 100° C.) will often generate the desired cell-wall material with improved binding capacity. The cell-wall material may then be washed and pelleted (e.g., by centrifugation) from the treatment solution and subsequently stored (e.g., by freezing or freeze-drying) until further use. Such cell-wall material includes spherical peptidoglycan microparticles that usually reflect the size and shape of the bacterium from which they were obtained. [0022] In one embodiment, the cell-wall material is derived from a Lactococcus , a Lactobacillus , a Bacillus or a Mycobacterium sp. The cell walls of Gram-positive bacteria include complex networks of peptidoglycan layers, proteins, lipoteichoic acids and other modified carbohydrates. Generally, chemical treatment of the cell-wall material may be used to remove cell-wall components such as proteins, lipoteichoic acids and carbohydrates, wherein the chemical treatment yields purified peptidoglycan (Morata de Ambrosini et al. 1998). Sodium dodecyl sulphate (SDS) is also commonly used to remove proteins. Trichloro acid (TCA) is known to specifically remove lipoteichoic acids and carbohydrates from cell-wall isolates. Phenol, formamide and mixtures of chloroform and methanol are other examples of organic solvents that may be used to enhance the purification of peptidoglycan. [0023] In the present invention, the effect of the pretreatment of whole cells of gram-positive bacteria with these and other chemicals in relation to binding technology provides the possibility to obtain bacterial ghosts or cell-wall material derived from the bacteria which possess new traits (i.e., different binding properties) without the introduction of recombinant DNA. [0024] In another embodiment, the present invention discloses the incorporation of cell-wall material with improved binding capacity for AcmA-type anchors into a composition, such as a pharmaceutical composition, with a proteinaceous substance comprising an AcmA-type anchor. Reactive groups, such as antigenic determinants, heterologous enzymes, single-chain antibodies, polyhistidyl tags, peptides, and other compounds may be bound to the cell-wall material as disclosed herein by providing reactive groups with an AcmA-type anchor, and subsequently contacting the cell-wall material with the reactive groups to improve binding capacity. Other reactive groups include fluorescing protein, luciferase, binding protein or peptide, antibiotics, hormones, non-peptide antigenic determinants, carbohydrates, fatty acids, aromatic substances or reporter molecules. [0025] In another embodiment, the invention discloses the use of cell-wall material in generating bioadsorbents or biofilters for environmental purposes, microbiocatalysts, and diagnostic tools. For instance, the use of immobilized biocatalysts, such as enzymes or whole microbial cells, has increased steadily during the past decade in the food, pharmaceutical and chemical industries. The immobilized biocatalysts are more stable, easier to handle, and can be used repeatedly in industrial processes in comparison to their free counterparts. Immobilization of enzymes typically requires a chemical step to link the enzyme to an insoluble support. However, chemical treatments may negatively affect the enzymes. Alternatively, enzymes may be immobilized by incorporation in gels with the disadvantage that diffusion of the substrate into the gel slows down the process. [0026] As disclosed herein, large-scale immobilization of enzymatically active proteins may be accomplished by surface displaying proteins on gram-positive cells or cell-wall material. For instance, the immobilization of a fusion protein comprising α-amylase or β-lactamase fused to the AcmA-protein anchor domain has been demonstrated herein in L. lactis . The addition of the AcmA-anchor fusion protein resulted in the stable attachment of heterologous proteins to the surface of L. lactis and other gram-positive bacteria. Further, pre-treating L. lactis cells and other gram-positive cells with acid as described herein results in a high density surface display of heterologous proteins and is a prerequisite for application in industrial processes. Further, the carrier or gram-positive cells may be obtained in high yield and be non-recombinant. Thus, a method disclosed herein may be used to economically produce the immobilized enzyme and make the AcmA-protein anchor a useful approach for the surface display of enzymes on gram-positive cells. [0027] Another industrial application of an immobilized enzyme is the isomerization of glucose which is catalyzed by glucose isomerase and used during the production of high-fructose corn syrup. This process may be made economically feasible by immobilizing the glucose isomerase. The productivity of glucose isomerase is improved by increasing the stability of epoxide hydrolase in organic solvents by immobilization to microbial cells or cell-wall material as described herein. [0028] Immobilized enzymes may also be used to treat waste water or industrial effluent. For instance, industrial effluents containing low value chemicals produced during synthesis of the commodity chemicals epichlorohydrin and propylene oxide may be treated by using immobilized haloalkane dehalogenase to recycle these low value products into the manufacturing process. [0029] The invention further discloses chimeric or hybrid AcmA-type anchors for the preparation of a composition that has new binding properties. The AcmA-type anchors can be divided into two groups of hybrids based on their pI (see, Table 3). A large group includes hybrids with a pI higher than 8, but lower than 10, and a smaller group includes hybrids with a relatively low pI (i.e., <5). Hybrid AcmA-type anchors are disclosed with at least one AcmA-type domain and a relatively high calculated pI, and another AcmA-type domain is disclosed with a relatively lower calculated pI. The resulting hybrid anchor has an intermediate calculated pI which is useful when release of the bound proteinaceous substance at a higher pH is contemplated. Such a composition may be routed through the stomach, which has a relative low pH, such that the composition releases its anchor bound reactive groups in the intestines, which have a higher pH. [0030] The invention also discloses a proteinaceous substance comprising an AcmA cell-wall binding domain, homolog or functional derivative thereof wherein the binding domain is a hybrid of at least two different AcmA-type cell-wall binding domains, homologs or functional derivatives thereof. The proteinaceous substance may comprise an AcmA cell-wall binding domain, homolog or functional derivative thereof where the binding domain is a hybrid of at least two different AcmA repeat sequences and has a calculated pI lower than 10. For instance, a hybrid protein anchor including the A1 and A2 repeat sequences of AcmA and the D1 repeat sequence of AcmD may be constructed. Such a hybrid domain may comprise at least one AcmA-type domain with a relatively high calculated pI and another AcmA-type domain with a relatively lower calculated pI. The domain with the relatively high pI may be derived from, or be functionally equivalent to, the AcmA-type domain of the lactococcal cell-wall hydrolase AcmA. Of course; many other domains with a high pI are known, such as those disclosed in Table 3. A domain with a relatively low pI may be derived from, or be functionally equivalent to, the AcmA-type domain of the lactococcal cell-wall hydrolase AcmD. However, other domains with relatively low pI are known, including those disclosed in Table 3. [0031] The invention further discloses a proteinaceous substance comprising a hybrid domain with at least two stretches of amino acids, wherein each stretch corresponds to a domain repeat sequence and is located adjacent to each other. The stretches may be separated by one or more amino acid residues of a short distance, i.e., 3-6 to 10-15 amino acids apart, by a medium distance, i.e., 15-100 amino acids apart, or by longer distances, i.e., >100 amino acid residues apart. [0032] In another embodiment, the invention discloses a proteinaceous substance with a hybrid AcmA domain that further comprises a reactive group. Reactive groups that may be used include, without limitation, antigenic determinants, heterologous enzymes, single-chain antibodies or fragments thereof, polyhistidyl tags, fluorescing proteins, luciferase, binding proteins or peptides, antibiotics, hormones, non-peptide antigenic determinants, carbohydrates, fatty acids, aromatic substances, inorganic particles such as latex, and reporter molecules. The reactive group may also include AcmA cell-wall binding domains, homologs or functional derivatives thereof wherein the binding domain is a hybrid of at least two different AcmA cell-wall binding domains, homologs or functional derivatives thereof that are useful in heterologous surface display and are broadly reactive with cell-wall components of a broad range of micro-organisms. As used herein, the AcmA cell-wall binding domains, homologs and functional derivatives thereof will also be referred to as hybrid AcmA domains. [0033] The invention further discloses reactive groups which are non-protein moieties, including substances such as antibiotics, hormones, aromatic substances, inorganic particles, or reporter molecules. The substances may be constructed by binding an antibiotic, such as penicillin, tetracycline or various other antibiotics, a hormone, such as a steroid hormone, or any other compound to a binding domain produced by the present invention. Such binding may be achieved using various techniques known in the art and may function to label or “flag” the binding domain. For instance, a binding domain may be bound to a reporter molecule such as fluorescent nanoparticles, i.e., FITC or HRPO, wherein tools are generated that may be used in diagnostic assays to detect microorganisms possessing peptidoglycan. Similarly, a binding domain may be bound to an antibiotic and used for in vivo parenteral administration into the bloodstream of humans or animals, or used in vitro to bind microorganisms with peptidoglycan in order to increase the concentration of the antibiotic around the microorganism which may be killed by the antibiotics. [0034] The invention further discloses a reactive group which is a protein moiety which may include, without limitation, antigenic determinants, enzymes, single-chain antibodies or fragments thereof, polyhistidyl tags, fluorescing proteins, binding proteins or peptides. For instance, a protein including a reactive group which is another protein or polypeptide is disclosed. The invention also discloses a nucleic acid molecule encoding the protein produced using the methods of the invention. Such a nucleic acid molecule, comprising single-stranded or double-stranded DNA, RNA or DNA-RNA duplex, comprises nucleic acid sequences which encode a hybrid binding domain. The nucleic acid molecule may also comprise nucleic acid sequences encoding the reactive group polypeptide and may further comprise other nucleic acid sequences encoding a signal peptide comprising promoter sequences or regulatory nucleic acid sequences. [0035] A vector comprising a nucleic acid molecule encoding a proteinaceous substance provided by the invention is also disclosed. Examples of vectors include, without limitation, a plasmid, a phage or a virus, wherein the vectors may be constructed using nucleic acids of the invention and routine skills known in the art. Viral vectors include baculovirus vectors or comparable vector viruses through which a protein produced by the present invention may be expressed or produced in cells, such as insect cells. [0036] A host cell or expression system including a nucleic acid molecule or a vector produced using methods of the present invention is also disclosed. The host cell expressing a protein of the present invention may be a microorganism to which the protein is attached. The host cell, or expression system, may be a Gram-positive bacterium, a Gram-negative bacterium, a yeast cell, an insect cell, a plant cell, a mammalian cell, or a cell-free expression system, such as a reticulocyte lysate. The host cell or expression system may be constructed or obtained using a nucleic acid or vector of the present invention and routine skills known in the art. [0037] In a further embodiment, the invention discloses a pharmaceutical composition comprising cell-wall material with an improved binding capacity with an immunogen bound thereto which may be useful for vaccination purposes, i.e., a vaccine. The vaccine may be used to invoke immunity against pathogens, such as malaria, which undergo life cycle stages where the pathogen is not in the blood but hides in cells. [0038] The vaccines may be delivered to mucosal surfaces instead of being injected since mucosal surface vaccines are easier and safer to administer. An L. lactis -derived cell-wall material may be used for mucosal vaccination since this bacterium is of intestinal origin and no adverse immune reactions are generally expected from L. lactis. [0039] The vaccine of the invention may also be administered by injection. When the vaccine is administered through injection, cell-wall material may be derived from a Mycobacterium sp. since mycobacterial cell-wall preparations have beneficial adjuvant properties. The mycobacterial cell-wall vaccine may be mixed with the proteinaceous substance carrying the immunogenic determinants used in the vaccine. [0040] A vaccine produced using a method of the present invention will likely have a reduced risk of generating undesirable immune responses against cell-wall compounds of unwanted immunogens because the unwanted immunogens are not included in the vaccine. BRIEF DESCRIPTION OF THE DRAWINGS [0041] FIG. 1 . Schematic map of plasmid pNG3041 that encodes the reporter protein MSA2::cA that is secreted as a proprotein using the lactococcal PrtP signal- and prosequences (PrtP.sspro). Pnis represents the nisin inducible promoter of the nisA gene. T represents the transcriptional terminator. CmR is the chloramphenicol resistance gene. repC and repA are genes involved in the replication of the plasmid. [0042] FIG. 2A . Fluorescence microscopic images of bacterial cells with externally bound MSA2::cA. Lb. curvatis, Lb. sake and L. lactis cells that were not pretreated prior to binding. [0043] FIG. 2B . Fluorescence microscopic images of bacterial cells with externally bound MSA2::cA. L. lactis cells that were TCA-pretreated prior to binding. The light colored areas indicate the position where the reporter protein MSA2::cA binds. The difference between L. lactis cells that were not pretreated with TCA (in FIG. 2A ) and those that were TCA pretreated is apparent (in FIG. 2B ). [0044] FIG. 3 . Western blots of chemically pretreated L. lactis cells that were washed after the pretreatment and incubated with MSA2::cA to allow binding. Unbound MSA2::cA was removed by washing. The drawing shows the MSA2::cA that was bound to the chemically pretreated cells and detected using an antibody specific for MSA2. The different pretreatments are indicated above the lanes. MSA2::cA is produced by the producer cells as a proprotein, pro-MSA2::cA. Some pro-MSA2::cA is present in the medium used for binding and binds as indicated by the arrow. A membrane bound protease, HtrA, of the producer cells cleaves off the prosequence, resulting in mature MSA2::cA, which also binds to the pretreated cells as indicated by the asterisk. HtrA also cleaves off the repeats of the cA anchor. Since there are three repeats, MSA2 proteins of several sizes are present in the medium of the producer. As long as more than one repeat is present, binding can still occur. The double asterisks point to MSA2::cA from which one or two repeats have been cleaved. M is a molecular weight marker. The molecular weights are indicated in the left margin. The two blots have different signal intensities. As a reference, both blots contain the same TCA-pretreated samples. The difference in signal intensity is due to differences in stain developing time. It is apparent that the TCA and other acid pretreatments produce pronounced effects on the subsequent binding of MSA2::cA. The conclusions for all chemical pretreatments are summarized in Table 1. [0045] FIG. 4 . Coomassie stained SDS-PAGE gel with chemically pretreated L. lactis cells. Pretreatments: (1) no-treatment; (2) HCl; (3) H 2 SO 4 ; (4) HAc; (5) TFA; and (6) TCA. It is apparent that treatment of the cells with HCl, H 2 SO 4 , TFA or TCA significantly removes an amount of protein from the cells. [0046] FIG. 5 . Western blot of L. lactis cells pretreated with different TCA concentrations and externally bound with MSA2::cA. Arrow and asterisks: as in FIG. 3 . Pretreatments: (1) no TCA treatment; (2) 1% TCA; (3) 5% TCA; (4) 10% TCA; and (5) 20% TCA. An increase in the binding of MSA2::cA is shown to correlate with increasing amounts of TCA used in the pretreatment. [0047] FIG. 6 . Alignment of cA repeats with cD repeats. AcmA (A1) (SEQ ID NO:16) is aligned to AcmD (D1) (SEQ ID NO:19). AcmA (A2) (SEQ ID NO:17) is aligned to AcmD (D2) (SEQ ID NO:20). AcmA (A3) (SEQ ID NO:18) is aligned to AcmD (D3) (SEQ ID NO:21). Consensus repeats SEQ ID NOS: 163, 164 and 165 are aligned. The amino acids that are in agreement with the consensus sequence are shown at the bottom of the figure (defined in PCT Publication WO99/25836) are underlined. The asterisks indicate residues that are identical between the compared repeats. [0048] FIG. 7 . Binding of various anchor-fusion proteins to L. Lactis with and without TCA pretreatment. Multiple bands shown in one lane are caused by the different processed forms of MSA2 fusions. Lanes: (1) non-pretreated L. lactis +MSA2::cA; (2) non-treated L. lactis +MSA2::cD; (3) non-pretreated L. lactis +MSA2; (4) TCA-pretreated L. lactis +MSA2::cA; (5) TCA-pretreated L. lactis +MSA2::cD; and (6) TCA-pretreated L. lactis +MSA2. The effect of TCA pretreatment on the binding of MSA2::cA is shown (i.e., compare lanes 1 and 4). A minor improvement for MSA2::cD and no improvement for MSA2 without anchor is observed. Since there is a signal for MSA2 without the anchor means that MSA2 by itself has a weak affinity for bacterial cell walls. However, MSA2::cD or MSA2 binding to the pretreated cells cannot be detected using fluorescence or electron microscopy (see text). The difference in results is probably due to a difference in sensitivity of the techniques. [0049] FIG. 8 . Fluorescence microscopy image of TCA-pretreated L. lactis cells incubated with MSA2::cA or MSA2::cD. Light colored areas indicate the position were the reporter fusion protein binds. It appears that binding only occurred with MSA2::cA and not with MSA2::cD. [0050] FIG. 9A . Electron microscopy images of L. lactis cells incubated with different MSA2 constructs. The black dots represent the position of bound MSA2 fusion protein. Image A depicts non-pretreated cells incubated with MSA2::cA. [0051] FIG. 9B . Electron microscopy images of L. lactis cells incubated with different MSA2 constructs. The black dots represent the position of bound MSA2 fusion protein. Image B depicts TCA-pre-treated cells incubated with MSA2::cA. Significant binding, shown by black dots, is only visible in the TCA-pre-treated cells incubated with MSA2::cA. [0052] FIG. 9C . Electron microscopy images of L. lactis cells incubated with different MSA2 constructs. The black dots represent the position of bound MSA2 fusion protein. Image C depicts TCA-pre-treated cells incubated with MSA2::cD. [0053] FIG. 9D . Electron microscopy images of L. lactis cells incubated with different MSA2 constructs. The black dots represent the position of bound MSA2 fusion protein. Image D depicts TCA-pre-treated cells incubated with MSA2. [0054] FIG. 10 . Binding of different anchor-fusion proteins to B. subtilis with and without TCA pretreatment. The drawing is a Western blot similar to FIGS. 3 and 7 . Lanes: (1) non-pretreated cells+MSA2::cA; (2) non-pretreated cells+MSA2::cD; (3) non-pretreated cells+MSA2; (4) TCA-pretreated cells+MSA2::cA; (5) TCA-pretreated cells+MSA2::cD; (6) TCA-pretreated cells+MSA2; and (7) non-pretreated B. subtilis (negative control). TCA pretreatment improves the binding of MSA2::cA in a manner similar to L. lactis (i.e., compare lanes 1 and 4). Only background binding is observed for MSA2::cD and MSA2 without anchor. [0055] FIG. 11 . Fluorescence microscopy image of MSA2::cA binding to Lb. casei with or without TCA pretreatment. The light colored areas represent bound MSA2::cA. TCA pretreatment improves binding of MSA2::cA and Lb. casei. [0056] FIG. 12 . Fluorescence microscopy image of MSA2::cA and MSA2::cD binding to M. smegmatis pretreated with TCA. The light colored areas represent bound MSA2 fusion protein. As illustrated, only MSA2::cA binds. [0057] FIG. 13 . Western blot of L. lactis cells with externally bound MSA2::cA treated with LiCl or stored under different conditions. The bands in the various lanes represent the amount of MSA2::cA that remained bound to the TCA-pretreated cells. Arrow and asterisks: as in FIG. 3 . Lanes: (1) marker; (2) non-pretreated L. lactis incubated without MSA2::cA; (3) non-pretreated L. lactis incubated with MSA2::cA; (4) TCA-pretreated L. lactis incubated with MSA2::cA; (5) TCA-pretreated L. lactis incubated with MSA2::cA, subsequently washed with 8 M LiCl; (6) TCA-pretreated L. lactis incubated with MSA2::cA, subsequently stored in water for 3 weeks at 4° C.; (7) TCA-pretreated L. lactis incubated with MSA2::cA, subsequently stored in 10% glycerol for 3 weeks at −80° C.; and (8) TCA-pretreated L. lactis incubated with MSA2::cA, subsequently stored in water for three weeks at −80° C. As illustrated, TCA pretreatment improves binding of MSA2::cA to L. lactis cells (i.e., compare lanes 3 and 4). Washing with 8 M LiCl and storage in water for 3 weeks at 4° C. has minor effects on the bound MSA2::cA (i.e., compare lane 4 with 5 and 6). Storage at −80° C. has no effect on the bound MSA2::cA (i.e., compare lane 4 with 7 and 8). [0058] FIG. 14A . Fluorescence microscopy image of MSA2::cA surface expression in the recombinant strain NZ9000(pNG3041). The light colored areas indicate the position of MSA2 fusion protein. The recombinant strain producing MSA2::cA has the protein on the surface in some specific spots. [0059] FIG. 14B . Fluorescence microscopy image of MSA2::cP surface expression in the recombinant strain NZ9000(pNG3043). The recombinant strain producing MSA2::cP has more on the surface organized in several areas. [0060] FIG. 14C . Fluorescence microscopy image of MSA2::cA binding to TCA pretreated L. lactis cells. The surface of the TCA-pretreated non-recombinant L. lactis with bound MSA2::cA is completely covered with the protein. [0061] FIG. 15 . Western blots of L. lactis total protein extracts reacted with rabbit immune serum diluted at 1:100. 0: preimmune serum. 2 and 3: serum after the second and third immunization, respectively. A1: subcutaneously immunized rabbit with NZ9000Δ acmA (pNG3041) cells (recombinant, MSA2::cA surface anchored). B1: subcutaneously immunized rabbit with NZ9000ΔacmA (negative control). C2: orally immunized rabbit with NZ9000ΔacmA(pNG3043) cells (recombinant, MSA2::cP surface anchored). E1: orally immunized rabbit with TCA-pretreated NZ9000ΔacmA to which MSA2::cA had been externally bound (non-recombinant, MSA2::cA surface anchored). The staining bands in the lanes illustrates that L. lactis proteins react with the indicated rabbit antiserum. It is visible that the non-recombinant TCA-pretreated strain with bound MSA2::cA (E1) evokes a minimal response to L. lactis proteins indicating that the response to the carrier is reduced, while the response to the malaria antigen is not negatively influenced (see, Table 2). [0062] FIG. 16 . Schematic representation of the domains in AcmA and AcmD. SS represents signal sequence. Both enzymes include a cell-wall binding domain that includes 3 repeats indicated by A1, 2, 3 and D1, 2, 3. The alignments of these repeats are shown in FIG. 6 . In addition, an example of one of the hybrid protein anchors is described in Table 5. [0063] FIG. 17 . Western blot showing the effect of pH supernatant on binding of MSA2::cD to TCA-pretreated L. lactis cells. As previously described, the Western blot shows the amount of MSA2::cD bound by the cells. In addition, the amount of MSA2::cD that was not bound and remained in the medium after binding is shown. The arrow indicates the expected position for pro-MSA2::cD and the asterisk indicates the position of mature MSA2::cD. Lanes: (1) pH during binding 6.2, cells; (2) pH during binding 6.2, supernatant after binding; (3) pH during binding 3.2, cells; (4) pH during binding 3.2, supernatant after binding; and (5) positive control: L. lactis , TCA-pretreated with bound MSA2::cA at pH 6.2. It is visible that MSA2::cD binds better at pH 3.2 than at pH 6.2 (i.e., compare lanes 1 and 3). [0064] FIG. 18 . Western blot of medium supernatant (S) after binding to ghost cells at the indicated pH and ghost (G) with the bound protein anchor. Lanes 1 and 2 illustrate binding at pH 3; lanes 3 and 4 illustrate binding at pH 5; lanes 5 and 6 illustrate binding at pH 7. The drawing shows considerable binding at pH 5. At pH 5, the native cD anchor (D1D2D3) shows little binding. The addition of the A3 repeat, which has a high pI value, results in increased binding at pH 5. [0065] FIG. 19 . Immunization schedule. Mice immunizations were started at day 1 and repeated after 14 and 28 days. A lethal nasal challenge with S. pneumoniae was given 14 days after the last oral immunization. S.c. represents subcutaneous immunization. [0066] FIG. 20 . Serum antibody response. Mean anti-PpmA serum antibody titers. OV represents orally immunized; IN represents intranasally immunized; SC represents subcutaneously immunized; Freund's PpmA refers to soluble PpmA subcutaneously administered with Freund's complete adjuvants. High titers were obtained with the intranasally and subcutaneously administered Ghosts-PpmA::cA. [0067] FIG. 21 . Survival times. The orally vaccinated mice were challenged with a lethal dose of S. pneumonia . Mice vaccinated with soluble PpmA or Ghost alone died within 72 hours. Forty percent of the mice immunized with Ghosts-PpmA::cA survived the challenge, indicating they were protected by the vaccination. DETAILED DESCRIPTION Example 1 Acid Pretreatment of Gram-Positive Bacteria Enhances Binding of AcmA Protein Anchor Fusions Materials and Methods [0068] Bacterial Strains and Growth Conditions. Lactococcus lactis strain MG1363 (Gasson 1983) or derivatives thereof, such as MG1363ΔacmA (Buist et al. 1995) or NZ9000Δ acmA, were used as recipients for binding of reporter fusion protein. NZ9000 (Kuipers et al. 1997), which carries one of the reporter plasmids, was used as a production strain. L. lactis strains were grown in M17 broth (Oxoid) supplemented with 0.5% glucose in standing cultures at 30° C. Chloramphenicol was added to the M17 medium to an end-concentration of 5 μg/ml when appropriate. For expression, mid-log phase cultures were induced for 2 hours with the culture supernatant of the nisin producing L. lactis strain NZ9700 as described by Kuipers et al. (1997). Lactobacillus casei , ATCC393, was grown in MRS broth (Oxoid) in standing cultures at 30° C. Mycobacterium smegmatis , ATCC700084, was grown in Middlebrook medium (Oxoid) at 37° C. in aerated cultures. Bacillus subtilis, 168, was grown in TY broth (per liter: 10 g tryptone, 5 g yeast extract, 5 g NaCl pH 7.4) at 37° C. in aerated cultures. [0069] Construction of Reporter Plasmids. The merozoite surface antigen 2 (MSA2) of Plasmodium falciparum strain 3D7 (Ramasamy et al. 1999) fused to the three repeats of AcmA (MSA2::cA) was used as the reporter anchor protein. The reporter anchor protein is encoded by plasmid pNG3041 based on the nisin inducible expression vector pNZ8048 (Kuipers et al. 1997) and contains a modified multiple cloning site in which the hybrid reporter gene was cloned. An in-frame fusion of the reporter was made at the 5′ end, the lactococcal PrtP signal—and prosequence, and at the 3′ end, the AcmA protein anchor sequence. The sequence of the MSA2 gene that was included in the construct corresponds to nucleotides (nt) 61 to 708 in GenBank accession number A06129. Primers used for the amplification of the MSA2 gene were MSA2.1 (5′-ACCATGGCAAAAAATGAAAGTAAATATAGC (SEQ ID NO:2)) and MSA2.4 (5′-CGGTCTCTAGCTTATAAGCTTAGAATTCGGGATGTTGCTGCTCC ACAG (SEQ ID NO:3)). The primers contain tags with restriction endonuclease recognition sites that were used for cloning. For cloning of the PrtP signal and prosequence (nt 1206 to 1766 in Kok et al. 1988), the primers PrtP.sspro.fw (5′-CCGTCTCCCATGCAAAGGAAAAAAGA AAGGGC (SEQ ID NO:4)) and PrtP.sspro.rev (AAAAAAAGCTTGAATTCCCAT GGCAGTCGGATAATAAACTTTCGCC (SEQ ID NO:5)) were used. The primers include restriction sites that were used for cloning. The AcmA protein anchor gene fragment (nt 833 to 1875) was obtained by subcloning a PvuII-HindIII fragment from plasmid pAL01 (Buist et al. 1995). Restriction endonuclease enzymes and Expand High Fidelity PCR polymerase were used in accordance with the instructions of the supplier (Roche). The final expression vector was designated pNG3041 ( FIG. 1 ). [0070] A construct including a stop codon introduced after the MSA2 sequence in pNG3041 was designated pNG304. The protein secreted using this construct is substantially the same as the protein expressed from the pNG3041 plasmid except that the protein produced from pNG304 does not contain the AcmA protein anchor. The protein produced from pNG304 is used as a negative control in the binding assays. A vector was also made in which the AcmA protein anchor was exchanged for a protein anchor. The putative cell-wall binding domain of L. lactis AcmD (Bolotin et al. 2001) was cloned (nt 1796 to 2371 in GenBank accession number AE006288) using primers pACMB2 (5′-CGCAAGCTTCTGCAGAGCTCTTAGATTCTAATT GTTTGTCCTGG (SEQ ID NO:6)) and pACMB3 (5′-CGGAATTCAAGGAGGAGAAATA TCAGGAGG (SEQ ID NO:7)) to produce the plasmid pNG3042. pNG3042 contains an in-frame fusion between MSA2 and the protein anchor of AcmD (MSA2::cD) and differs from plasmid pNG3041 only in the gene fragment encoding the protein anchor. [0071] Cell Pretreatment and Binding Conditions. Chemical pretreatment of L. lactis NZ9000ÄacmA was done with 10% TCA (0.6 M) in the following manner. Cells of 0.5 ml stationary phase cultures were sedimented by centrifugation and washed once with 2 volumes of demineralized water. Cells were resuspended in 1 volume of a 10% TCA solution and incubated by placing the reaction tube in boiling water for 15 minutes. Subsequently, cells were washed once with 2 volumes PBS (58 mM Na 2 HPO 4 .2H 2 O, 17 mM NaH 2 PO 4 .H 2 O, 68 mM NaCl; pH 7.2) and three times with 2 volumes demineralized water. The cells were used directly for binding experiments or stored (as described herein) until further use. [0072] The following chemicals and conditions were used to examine the effect of different chemicals on the binding capacity of L. lactis cells for AcmA-type protein anchor fusions: acetic acid (HAc), hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), TCA, trifluoroacetic acid (TFA), and monochloro acetic acid (MCA). The acids were used at a final concentration of 0.6 M and incubated for 15 minutes in boiling water. SDS, dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) were used at a concentration of 10%. The SDS pretreatment was incubated for 15 minutes in boiling water and DMF and DMSO treatments were incubated at room temperature for 15 minutes. Cells were also pretreated with phenol (Tris buffer saturated) and incubated for 15 minutes at 55° C. Other chemicals pretreated at the 55° C. incubation temperature were: 4 M guanidine hydrochloride (GnHCl), 37% formaldehyde, chloroform:methanol (CHCL 3 :CH 3 OH (2:1)) and 0.1% sodium hypochlorite (NaOCl). In addition, incubation with 25 mM dithiothrietol (DTT) for 30 minutes at 37° C. and a pretreatment with hexane (100%) were analyzed. [0073] The effect of enzymatic pretreatment of cells with lysozyme was also tested. For lysozyme pretreatment, the cells were resuspended in buffer (20% sucrose, 10 mM Tris pH 8.1, 10 mM EDTA, 50 mM NaCl) with lysozyme (2 mg/ml) and incubated at 55° C. for 15 minutes. After the chemical and enzymatic pretreatments, the washing steps were the same as the washing steps used for the TCA-treated cells. TCA pretreatment of Bacillus subtilis, Lactobacillus casei and Mycobacterium smegmatis was done as described herein for L. lactis. [0074] Cell-free culture supernatants containing MSA2::cA, MSA2::cD or MSA2 without anchor were incubated in four-fold excess for 10 minutes at room temperature with pretreated cells (e.g., cells from 0.5 ml culture were incubated with 2.0 ml culture supernatant). After binding, cells were sedimented by centrifugation, washed twice in 2 volumes of demineralized water, resuspended in SDS-denaturation buffer, heated for 5 minutes at 98° C., subjected to SDS-PAGE, and analyzed by Western blot analysis. [0075] Storage Conditions. Cell-free supernatants containing MSA2::cA, MSA2::cD or MSA2 were stored at −20° C. with or without 10% glycerol prior to binding. TCA-pretreated L. lactis cells were stored at −80° C. in 10% glycerol prior to binding. TCA pretreated L. lactis cells with bound MSA2::cA were stored at +4° C. or −80° C. with or without 10% glycerol. Cells stored in 10% glycerol were washed once with 1 volume of demineralized water prior to binding. [0076] Cell pellets (in demineralized water) of TCA-pretreated L. lactis cells with or without bound MSA2::cA were frozen by contacting the vials with liquid nitrogen and removing the water with lyophilization. Alternatively, non-frozen cell pellets were dried under vacuum at 30° C. for 2 hours prior to binding. [0077] Western Blotting. For detection of MSA2 proteins, cell pellets corresponding to 500 μl culture were resuspended in 50 μl SDS-denaturation buffer. Cell-free culture supernatants (1 ml) were concentrated by phenol-ether precipitation (Sauvé et al. 1995), vacuum dried and resuspended in 50 μl SDS-denaturation buffer. Proteins were separated with standard SDS-PAGE techniques. After separation, proteins were electroblotted onto PVDF membranes (Roche). In immunoblots, MSA2 proteins were detected with 1:10,000 diluted rabbit MSA2-specific antiserum (Ramasamy et al. 1999) and 1:5,000 diluted anti-rabbit IgG-conjugated alkaline phosphatase (Roche) using known procedures. [0078] Fluorescence Microscopy. 100 μl cell suspensions incubated with MSA2::cA, MSA2::cD or MSA2 fusion proteins were washed twice with demineralized water and resuspended in an equal volume of PBS containing 1% BSA and MSA2-specific rabbit antiserum diluted to 1:200. After incubation for 20 minutes at room temperature, the cells were washed three times with 2 volumes PBS. Subsequently, the cells were incubated for 20 minutes in 1 volume PBS with 1% BSA and 1:100 diluted Oregon green labeled goat anti-rabbit immunoglobulin G (Molecular Probes). After washing once with 2 volumes PBS and twice with 2 volumes demineralized water, the cells were resuspended in 100 μl demineralized water. A 10 μl aliquot of the resuspended cells was spread onto a Polysin microslide (Menzel-Gläser), air dried, and examined under a fluorescence microscope (Zeiss). [0079] Electron microscopy. TCA-pretreated L. lactis cells incubated with MSA2::cA, MSA2::cD or MSA2 were collected and washed as described herein. Immunogold labeling was performed on whole mount preparations of glutaraldehyde fixed cells on Formvar-carbon coated nickel grids using Auroprobe 15 nm goat anti-rabbit IgG gold marker (Amersham). Primary antibodies against MSA2 were diluted 1:1000 in PBS-glycine buffer. The labeled samples were stained with 0.1% uranyl acetate (W/V in water) and examined in a Philips CM10 transmission electron microscope at 100 kV. [0080] Pretreatment of L. Lactis Cells with Different Chemicals. The cA protein anchor of L. lactis AcmA can be used to bind fusion proteins to a wide variety of Gram-positive bacteria. However, the amount of fusion protein that binds varies greatly among this group of bacteria. Binding of MSA2::cA that covers the entire cell surface of some lactobacilli was observed, whereas other bacteria such as L. lactis showed only limited localized binding ( FIG. 2A ). This phenomenon may be due to the fact that the cell walls of some bacterial species contain components that interfere with cA anchor binding. Since chemicals like SDS, TCA, chloroform/methanol and others may be used to remove components from isolated bacterial cell walls (Morata de Ambrosini et al. 1998), the effect of the removal of cell-wall components from L. lactis whole cells on the binding of the reporter fusion protein MSA2::cA was investigated. L. lactis cells were pretreated as described herein with various chemicals or with lysozyme. [0081] FIG. 3 shows typical Western blots of pretreated whole cells to which MSA2::cA was bound. Mature MSA2::cA migrates at a position of a 75 kDa protein (indicated by an asterisk). The arrow represents MSA2::cA that contains the PrtP prosequence. The double asterisks represent MSA2::cA from which one or two of the repeats have been removed. A cell membrane anchored protease HtrA has been shown to be involved in processing proproteins and in removing repeats from AcmA (Poquet et al. 2000). From the results of FIG. 3 , it may be concluded that pretreatment with TCA (lanes 8 and 16 contain the same samples, the difference in signal intensity is due to differences in stain developing time), HCl, H 2 SO 4 and HAc substantially improves the subsequent binding of MSA2::cA (compare with the negative control in lane 15). Other tested acids, TFA and MCA, had similar effects (not shown). Phenol, GnHCl, formamide and chloroform/methanol pretreatments showed a moderate improvement of binding (lanes 4, 5, 6, 7, respectively). Minor binding improvements were observed after pretreatment with SDS, DMF, DMSO and DTT. The results are summarized in Table 1. Based on the results, it appears that pretreatment of L. lactis cells with the acids TCA, TFA, MCA, HCl, H 2 SO 4 and HAc are the most effective agents for improving binding of cA anchor fusion proteins to lactococcal cells. Acids such as TCA are known to remove lipoteichoic acids from cell walls. [0082] Whether proteins are removed from the cell walls by these acid treatments was also analyzed. FIG. 4 shows a Coomassie stained gel of lysed pretreated cells. Most of the acid treatments, except for HAc, removed a substantial amount of proteins from the lactococcal cells. Since HAc removed only a trace amount of proteins (compare lane 1 and 4) and SDS pretreatment (which is known to remove proteins from the cell walls) showed only a minor improvement of MSA2::cA binding ( FIG. 3 , lane 1), it may be concluded that removal of proteins from the cell wall is not critical for improving the binding of cA anchor fusions. This conclusion may be due to the fact that lipoteichoic acids or carbohydrates occupy sites in the cell walls of L. lactis that interfere with efficient binding. Alternatively, acid pretreatment may result in altering the compactness of peptidoglycan strands that make cA binding sites more available. [0083] TCA pretreatment was also used in all other experiments. The optimal TCA concentration in the boiling procedure was determined. TCA percentages of 1, 5, 10 and 20% were tested. Although 1% TCA pretreatment already showed a significant improvement in binding of MSA2::cA and 5% TCA pretreatment showed a further increase, no further improvement was observed at concentrations higher than 10% TCA ( FIG. 5 ). Therefore, the boiling procedure with 10% TCA was selected as the standard procedure for the experiments. [0084] The binding characteristics of the lactococcal cA homolog cD in an MSA2 fusion were analyzed using the standard TCA pretreatment procedure. Two of the three AcmD repeats are highly homologous to those of AcmA. An alignment is shown in FIG. 6 . Secreted MSA2 without an anchoring domain was included in these experiments as a negative control. In Western blots, the effect of TCA pretreatment on the binding of MSA2::cA was evident ( FIG. 7 , compare lanes 1 and 4). The effect of TCA pretreatment was also studied using fluorescence microscopy ( FIG. 2 , compare L. lactis in A and B; FIG. 8 ) and electron microscopy ( FIG. 9 , compare A and B). Independent of the technique used, the effect of TCA pretreatment on the binding of MSA2::cA can be detected. [0085] The binding of MSA2::cD to non-TCA-pretreated L. lactis cells was low as detected in Western blots ( FIG. 7 , lane 2) and was undetectable in fluorescence microscopy and electron microscopy ( FIG. 9A ). TCA pretreatment only had minor effects on the intensity of the MSA2::cD signal in Western blots ( FIG. 7 , lane 5). At the same time, no MSA2::cD specific signal associated with the pretreated cells could be observed in fluorescence microscopy ( FIG. 8 ) and only low levels of labeling were observed in electron microscopy ( FIG. 9C ). Some cell-associated signal was observed for MSA2 without anchoring domain for both non-TCA pretreated and TCA-pretreated L. lactis cells ( FIG. 7 , lanes 3 and 6, respectively). However, for MSA2::cD, this was not observed in fluorescence microscopy (not shown) and only minor labeling signals were found in electron microscopy ( FIG. 9D ). Taken together, it may be concluded that: (i) the reporter protein MSA2 does have some low degree of affinity for bacterial cell walls that can be detected in Western blots; (ii) the cA anchor domain specifically stimulates the binding of the reporter fusion to non-pretreated cells; (iii) chemical pretreatment, especially with acids, enhances this binding; and (iv) the cD anchor domain does not promote binding of fusion proteins under the conditions applied. [0086] The fluorescence microscopic images and electron microscopic images of TCA pretreated lactococcal cells ( FIGS. 2 , 8 and 9 ) showed that pretreatment leaves the integrity of the cell intact. However, cells are no longer viable (plating efficiency 0) and therefore may be considered as inert spherical peptidoglycan microparticles with a diameter of approximately 1 μm, “ghost cells.” [0087] Binding to Other Gram-Positives. The binding of MSA2::cA, MSA2::cD and MSA2 without anchor domain to the Gram-positive bacteria B. subtilis, Lb. casei and M. smegmatis was also analyzed. FIG. 10 shows a Western blot summarizing binding of MSA2::cA, MSA2::cD and MSA2 to non-pretreated and TCA-pretreated B. subtilis cells. As for L. lactis , an increase in binding is observed for MSA2::cA. An MSA::cA specific signal could also be visualized in fluorescence microscopy of non-pretreated B. subtilis cells, but with a highly improved signal for the TCA-pretreated cells (not shown). Binding of MSA2::cD and MSA2 to non-pretreated or TCA-pretreated cells could not be demonstrated in fluorescence microscopy (not shown). [0088] Similar results were obtained for Lb. casei and M. smegmatis . The improved binding of MSA2::cA to TCA-pretreated Lb. casei cells is shown in FIG. 11 . For MSA2::cD and MSA2, no fluorescence signals were detected (not shown). The TCA pretreatment of M. smegmatis also had a positive effect on the binding of MSA2::cA, whereas no binding was observed for MSA2::cD or MSA2 ( FIG. 12 ). Taken together, it may be concluded that acid pretreatment, such as with TCA, improves the binding of cA protein anchor fusions to the cell surface of Gram-positive bacteria. [0089] Binding strength and storage conditions. The strength of the MSA2::cA binding to TCA-pretreated L. lactis cells was analyzed with a treatment of LiCl after the binding. LiCl is commonly used to remove proteins from bacterial cell walls. From the Western blot of FIG. 13 , it may be concluded that 8 M LiCl partially removes MSA2::cA from the L. lactis cells (compare lanes 4 and 5). Therefore, although MSA2::cA binds non-covalently to cell walls, the binding interactions are most likely very strong. [0090] Cell-free culture supernatants with MSA2::cA were stored with or without 10% glycerol at −20° C. MSA2::cA stored in this manner for several weeks had the same capacity to bind to TCA-pretreated L. lactis cells (not shown). [0091] TCA-pretreated L. lactis cells with bound MSA2::cA were stored for 3 weeks at +4° C. in demineralized water or at −80° C. in demineralized water with or without 10% glycerol. The samples were analyzed in Western blots. Storing pretreated cells with bound MSA2::cA for 3 weeks in water at +4° C. only resulted in a loss of signal of about 50% ( FIG. 13 , compare lanes 4 and 6). Whether this loss of signal was due to degradation or due to release of the protein into the water was not determined. Storage at −80° C. with or without 10% glycerol had no effect on the binding ( FIG. 13 , compare lanes 4, 7 and 8). [0092] In addition, the effects of drying and lyophilization on the binding of MSA2::cA to TCA-pretreated L. lactis cells were studied. Drying of pretreated cells had no observable negative effect on binding of MSA2::cA afterwards. Dried pretreated cells with bound MSA2::cA could be resuspended in water without losing bound fusion protein. This was also observed for lyophilized cells with bound MSA2::cA. Lyophilization of TCA-pretreated cells prior to binding resulted in loss of the binding capacity for MSA2::cA (results not shown). [0093] From these data, it may be concluded that: (i) in spite of the non-covalent character of cA anchor binding to cell walls, the binding is very strong; (ii) cell-free culture supernatants can be stored safely at −20° C.; and (iii) drying of TCA-pretreated cells provides an efficient and simple method for storage of such cells either with or without bound cA-anchor fusions. Example 2 Oral Immunizations of Rabbits with Non-Recombinant Lactococcus Lactis Preloaded with the Plasmodium falciparum Malaria Antigen MSA2 Fused to the Lactococcal AcmA Protein Anchor [0094] In Example 1, a technology is described that efficiently binds protein hybrids when externally added to the cell surface of non-recombinant gram-positive bacteria by means of an AcmA-type protein anchor. This technology provides the possibility to provide bacteria or bacterial cell walls with new traits without introducing recombinant DNA into them. The immunogenicity in rabbits of the Plasmodium falciparum merozoite surface protein, MSA2 of strain 3D7 (Ramasamy et al. 1999), presented on the cell surface of non-recombinant non-living L. lactis cells as an AcmA anchor fusion protein was investigated. Materials and Methods [0095] Bacterial Strains and Growth Conditions. The L. lactis strain which produces MSA2::cA, the strain's growth conditions, the induction for expression, the TCA pretreatment of the L. lactis recipient cells and the binding of MSA2::cA to the cells was described in Example 1 with the following modification: a ratio of 1 (TCA-pretreated cells) to 5 (cell-free culture supernatant with MSA2::cA) was used for binding. An L. lactis NZ9000 strain carrying plasmid pNG3043 was used as a positive control in the immunization experiments (was positive in a previous, unpublished experiment). Plasmid pNG3043 encodes an MSA2 hybrid protein that contains the lactococcal PrtP cell-wall anchoring domain at its C-terminus (MSA2::cP) instead of the AcmA protein anchor. The PrtP cell-wall anchoring domain contains the LPXTG (SEQ ID NO: 1) motif that enables a membrane-linked sortase to covalently couple the protein to the cell wall (Navarre and Schneewind 1994). The cP domain used in construct pNG3043 corresponds to nt 6539 to 6914 in Kok et al. (1988). Primers used for the amplification of this fragment were PrtP.cwa.fw3 (5′-ATATAAAGCTTGCAAAGTCTGAAAACGAAGG (SEQ ID NO:8)) and PrtP.cwa.rev (5′-CCGTCTCAAGCTCACTATTCTTCACGTTGTTTCCG (SEQ ID NO:9)). The primers include restriction endonuclease recognition sites for cloning. Plasmid pNG3043 differs from plasmid pNG3041 in the cell-wall binding domain. Growth conditions and induction of expression of strain NZ9000ΔacmA(pNG3043) were the same as for strain NZ9000Δ acmA(pNG3041). [0096] Rabbit Immunizations. Ten barrier-reared, New Zealand white rabbits obtained from Harlan laboratories, The Netherlands, were used in groups of 2 for experimental immunizations. The care and use of animals were according to WHO guidelines (WHO/LAB/88.1). The rabbits were ear bled prior to immunization to obtain preimmune sera. Details of the rabbits and immunogens are as follows: [0097] Rabbits A1 and A2 were subcutaneously immunized with NZ9000Δ acmA(pNG3041) cells (recombinant, MSA2::cA partly surface anchored). [0098] Rabbits B1 and B2 were subcutaneously immunized with NZ9000ΔacmA (negative control). [0099] Rabbits C1 and C2 were orally immunized with NZ9000ΔacmA(pNG3043) cells (recombinant, MSA2::cP surface anchored). [0100] Rabbits D1 and D2 were orally immunized with NZ9000ΔacmA(pNG3041) cells (recombinant, MSA2::cA surface anchored). [0101] Rabbits E1 and E2 were orally immunized with TCA treated NZ9000ΔacmA to which MSA2::cA had been bound from NZ9000ΔacmA(pNG3041) culture supernatant (non-recombinant, MSA2::cA surface anchored). [0102] Stocks of NZ9000ΔacmA(pNG3043) with MSA2::cP expressed at its surface were stored in aliquots of 10 11 cells in growth medium containing 10% glycerol at −80° C. The cells remain viable under these conditions and retain MSA2 on the surface as demonstrated by immunofluorescence (not shown). The first immunization was carried out with freshly grown bacteria. For subsequent immunizations, stocks of bacteria were freshly thawed, washed and resuspended in buffer at the appropriate concentration for immunizations. [0103] On the other hand, the non-pretreated NZ9000ΔacmA (negative control), the non-pretreated NZ9000ΔacmA(pNG3041) and the TCA-pretreated NZ9000ΔacmA with the externally bound MSA2::cA were prepared daily from fresh cultures. [0104] Subcutaneous injections were performed with a total of 5×10 9 cells in 100 μl PBS without any adjuvant into two sides on either side of the spine. The subcutaneous injections were repeated two more times at three-week intervals. Prior to oral immunization, the rabbits were deprived of water and food for two to four hours. The rabbits were then fed 5×10 10 cells resuspended in 1 ml of 0.5% sucrose. Each dose was repeated for three successive days to obtain reproducible oral immunization. Altogether, three series of oral immunizations were given at three-week intervals. Adverse effects consequent to the immunizations, including granulomas at the sites of subcutaneous injections, were not observed, indicating that L. lactis was well tolerated by the animals. [0105] Serum Antibody Responses. Rabbits were ear bled two weeks after each immunization to obtain sera for antibody assays. The sera were stored at −20° C. until use. Ten-fold serial dilutions of the antisera in 2% BSA in PBS were used in immunofluorescence assays (IFA) to determine the titer of the antibodies against MSA2 on the surface of 3D7 P. falciparum merozoites. IFA was performed on acetone-methanol fixed late stage 3D7 P. falciparum parasites as previously described (Ramasamy 1987). For detection of antibody isotypes, Oregon Green conjugated goat anti-rabbit Ig (Molecular Probes) was used as the second antibody. For detection of IgG antibodies, a fluorescein conjugated, affinity purified, mouse monoclonal with specificity against rabbit IgG chains (Rockland) was used. Results and Discussion [0106] Surface Expression of MSA2 in Different L. Lactis Strains. Coomassie staining of SDS-PAGE gels and fluorescence microscopy were used to determine, in a semi-quantitative way, the number of MSA2 molecules expressed and surface exposed by the recombinant lactococcal strains carrying plasmid pNG3041 or pNG3043 that produce MSA2::cA or MSA2::cP, respectively, and by the non-recombinant TCA-pretreated L. lactis cells to which MSA2::cA had been bound from the outside. The recombinant strains were estimated to produce approximately 1.4×10 5 molecules of MSA2::cA or MSA2::cP. The surface exposure of MSA2::cA and MSA2::cP differed considerably as shown by fluorescence microscopy in FIG. 14 . The non-recombinant TCA-pretreated L. lactis cells with bound MSA2::cA showed a uniform staining of the entire cell surface. However, the semiquantitative SDS-PAGE analysis indicated that about 1×10 4 molecules of MSA2::cA per cell were represented. [0107] Accordingly, it may be concluded that the number of surface-exposed MSA2::cA and MSA2::cP on the recombinant lactococcal strains is less than 10% of the total number of molecules produced by these strains. The other molecules are most likely trapped in the membrane or the cell wall. Similar observations were made by Norton et al. (1996) for the expression of TTFC fused to the cP cell-wall anchoring domain. In that study, only membrane-associated or cell-wall-associated TTFC could be demonstrated and no surface-exposed TTFC::cP was demonstrated. Thus, it appears that binding from the outside to TCA-pretreated cells is a more efficient method to surface-exposed proteins on L. lactis cells. [0108] Anti-MSA2 Antibody Responses in Orally Immunized Rabbits. Characteristics of the anti-MSA2 antibody response to the immunizations are summarized in Table 2. The oral immunizations with the recombinant L. lactis that produces MSA2::cP (rabbits C1 and C2) were done before (unpublished results) and used as a positive control. In the previous experiment, a similar antibody response was found. The present experiment showed that specific antibodies against near native MSA2 were detectable after two immunizations for group A, D and E rabbits, and that antibody titers increased in all instances after a third immunization. IgG antibodies were predominant after three immunizations in either the subcutaneous or oral route. A comparatively weak anti-MSA2 surface IFA, attributable to the generation of cross-reactive antibodies (as described herein), was also observed after three control subcutaneous immunizations with L. lactis cells alone. [0109] Taken together, the results indicate that: (i) MSA2 produced by lactococcal cells elicits serum antibodies that recognize native P. falciparum parasite MSA2; (ii) MSA2-specific T h cells are activated through mucosal immunization due to the presence of systemic IgG antibodies (Table 2) that can be boosted (unpublished results); and (iii) oral immunizations with MSA2::cA bound to non-recombinant non-living TCA-pretreated L. lactis cells are as efficient in evoking specific serum antibody responses as the live recombinant strain producing MSA2::cA that was administered subcutaneously or orally, or as efficient as the live recombinant strain producing MSA2::cP that binds MSA2 covalently to its cell wall delivered orally. [0110] Anti-lactococcal Antibody Responses. Western blots ( FIG. 15 ) demonstrated significant antibody responses against L. lactis antigens after two and three immunizations of the rabbits. The responses were notably greater after subcutaneous (group A and B rabbits) than oral immunization with L. lactis (group C rabbits). Oral immunization with the TCA-pretreated lactococcal cells (group E rabbits) elicited antibodies that reacted at a lower intensity with fewer L. lactis antigens than oral immunization with viable L. lactis cells. This is most likely due to the fact that proteins are removed from the lactococcal cells by the TCA pretreatment (see, Example 1). The lower anti-carrier response observed for the TCA-pretreated (non-recombinant) cells renders this type of delivery vehicle more suitable for repeated immunization strategies than its untreated (recombinant) counterpart. Example 3 pH-Dependent Cell-Wall Binding of AcmA Protein Anchor Homologs and Hybrids [0111] The cell-wall binding domain or anchor of the lactococcal cell-wall hydrolase AcmA includes three repeats of 45 amino acids that show a high degree of homology (Buist et al. 1995). These three repeats belong to a family of domains that meet the consensus criteria as defined in PCT publication WO 99/25836 and can be found in various surface-located proteins in a wide variety of organisms. Another feature that most of these domains have in common is that their calculated pI values are high, approximately 8 or higher (Table 3). The pH used in previous binding experiments with MSA2::cA (i.e., Examples 1 and 2) was approximately 6, indicating that the binding domain was positively charged. [0112] The AcmA protein anchor homolog of the lactococcal cell-wall hydrolase AcmD (cD) (Bolotin et al. 2001) also includes three repeats ( FIG. 16 ) with a calculated pI that is lower (approximately pI 3.8) than that of the cA domain (Table 4). Consequently, the cD anchor was negatively charged at the binding conditions used in Example 1. No binding of the MSA2::cD reporter protein occurred under these conditions as demonstrated herein. Therefore, the influence of the pH during binding of a cD fusion protein (MSA2::cD) was investigated. Furthermore, a hybrid protein anchor including the three cD repeats and one cA repeat that has a calculated pI value that is higher than that of the cD repeats alone was constructed. The hybrid protein anchor showed better binding pH values above the pI of the cD repeats alone, indicating that the pH binding range of AcmA-type protein anchors can be manipulated by using the pI values of the individual repeats in hybrids. Materials and Methods [0113] Bacterial strains, growth and induction conditions, TCA pretreatment of L. lactis cells, incubation of the MSA2 protein anchor fusion proteins to TCA-pretreated cells, washing conditions, protein gel electrophoresis, Western blotting and immunodetection were the same as described herein with reference to Example 1. The cell-free culture supernatants with MSA2::cA, MSA2::cD or A3D1D2D3 have a pH of approximately 6.2. The influence of pH was examined by adjusting the pH of the cultures by the addition of HCl or NaOH to obtain the required pH. [0114] Plasmid Constructions. The plasmid that expresses the MSA2::cD fusion was described herein with reference to Example 1. Plasmid pPA43 is based on the same expression plasmid and contains an in-frame fusion of the lactococcal signal sequence of Usp45 (ssUsp; van Asseldonk et al. 1990. Gene 95: 155-160), the c-myc epitope for detection purposes, the A3 cA repeat and repeats D1, D2 and D3 of cD. Primers used for cloning A3 were cA repeat3.fw (CCG TCT CCA ATT CAA TCT GCT GCT GCT TCA AAT CC (SEQ ID NO: 10)) and cA repeat3.rev (TAA TAA GCT TAA AGG TCT CCA ATT CCT TTT ATT CGT AGA TAC TGA CCA ATT AAA ATA G (SEQ ID NO: 11)) (the primers include the A3 specific sequences). The primers used for cloning the three cD repeats were cDrepeat1.fw (CCGTCTCCAATTTCAGGAGGAACTGCTGTTACAACTAG) (SEQ ID NO: 12) and cDrepeat3.rev (TAATAAGCTTAAAGGTCTCCAATTCCAGCAACTTGCAAAACTTCTCCT AC) (SEQ ID NO: 13) (the primers include the cD specific sequences). Results and Discussion [0115] Binding of MSA2::cD at Low pH. Since binding of MSA2::cD was not observed at a pH (the pH of the culture medium after growth and induction is about 6.2) higher than the calculated pI for the cD domain (i.e., pI 3.85), binding was studied when the pH of the medium was adjusted to pH 3.2. TCA-pretreated L. lactis cells were used as the binding substrate and the relative amounts of bound MSA2::cD were analyzed in Western blots. The amounts of unbound reporter protein remaining in the culture supernatant after binding were also analyzed. FIG. 17 shows a clear increase in bound MSA2::cD when binding is performed at pH 3.2 (compare lanes 1 and 3). At the same time, less unbound reporter protein remained in the supernatant (compare lanes 2 and 4). This result indicates that positive charges are important for binding of cA-type anchoring domains. [0116] Binding of cAcD Hybrid Anchors. Analysis of the pI values of the cA homologs in Table 3 indicates that two classes of repeats can be distinguished: a majority (99 out of 148) of homologs that have a high pI value (>8) and a smaller group (33 out 148), of which cD is a representative, that has pI values lower than 6. Based on the experimental results, it is shown that these types of anchoring domains only bind to bacterial cell walls at a pH that is lower than the anchoring domains pI. Notably, most cell-wall binding domain homologs include repeats with a pI that are representatives of one of the two groups, i.e., only repeats with a high or low pI. Some proteins with cell-wall binding domains, e.g., those of DniR of Trepanoma pallidum and an amidase of Borrelia burgdorferi , include repeats with high and low pI. Since the binding pH of such “natural hybrid” cell-wall binding domains is below the intermediate pI value of the total number of repeats present in the domain, a hybrid cell-wall protein anchor was constructed using the cA and cD repeats with an intermediate pI value. Table 5 lists the native AcmA and AcmD anchors and a number of examples of cA/cD hybrids. The constructed hybrid protein anchor (A3 D1D2D3) has a calculated pI value of approximately 5.1. A protein anchor including only D1D2D3 shows little binding at a pH above its calculated pI (as described herein). The A3 (pI 10) domain shows similar binding at pH 5 and pH 7. [0117] The binding of the hybrid anchor A3D1D2D3 was tested at pH 3, pH 5 and pH 7. At pH 3, most protein had been bound to the ghost cells ( FIG. 18 ). At pH 5, there was considerable binding (+/−40%), whereas there was only minimal binding at pH 7 (+/−20%). This result indicates the pH range of binding for cD repeats was shifted to higher pH values by the addition of one cA repeat (A3) that caused a shift in calculated pI values of 3.8 to 5.1. The increase of binding at pH 5 for the A3D1D2D3 hybrid cannot be attributed to binding of the A3 repeat alone. If this was the case, then the same level of binding should occur at pH 7 since the A repeats show the same binding at these pH values. In addition, the increased binding at pH 5 is not an additive effect in the sense that an extra binding domain results in increased binding. It has previously been shown that addition of one repeat to the cA anchor did not result in increased binding. The binding at the higher pH values of the A3D1D2D3 repeats, as compared to the D1D2D3 repeats alone, thus may be attributed to the increase in the calculated pI value of the hybrid cA/cD anchor. This demonstrates that pH binding properties of these types of protein anchors may be manipulated on the basis of the pI values of individual repeats present in the hybrid anchor. Example 4 Induction of Cellular Immune Responses in Mice after Oral Immunizations with Lactococcal Ghosts Displaying the Malaria Plasmodium Falciparum Antigen MSA2 Fused to the Lactococcal AcmA Protein Anchor [0118] Non-genetically modified non-living Lactococcus lactis cells (ghosts) preloaded with the Plasmodium falciparum MSA2 antigen fused to the AcmA protein anchor (MSA2::cA) were used to orally immunize mice in a similar way as described herein with reference to Example 2. In this experiment, the question of whether immunizations through the oral route with the non-recombinant non-living Ghosts carrying MSA2::cA on their surface (Ghosts-MSA2::cA) can elicit typical Th1-type immune responses, such as IgG2 antibodies and gamma-interferon (γIFN)-producing T cells in the spleen is addressed. These responses are particularly relevant to obtain immunity for pathogens, such as malaria, that undergo stages in their life cycle where they are not in the blood but hide in cells. Materials and Methods [0119] Groups of five mice of different strains were used for immunization. The strains of mice used were Balb/c (with the major histocompatibility locus allotype of H2d), C57 Black (H2b), C3H (H2k) and ICR (outbred, i.e., of varying H2 types). Oral immunizations were performed at three weekly intervals. Immunizations were performed with MSA2::cA absorbed onto the surfaces of TCA-treated Lactococcus lactis cells (Ghosts-MSA2::cA) or with recombinant L. lactis that displayed MSA2 on the surface through the use of a covalently linked cell-wall anchor ( L. lactis (MSA2::cP)) as described herein with reference to Example 2. The mice were tail bled to obtain serum samples two weeks after the second, third and fourth immunizations. Fecal pellets were collected and extracted to examine intestinal IgA antibody production. The mice were sacrificed at the end of each experiment and the spleens were removed for examining T-cell responses by ELISPOT. MSA2-his tag produced in E. coli was used as antigen in the ELISA and ELISPOT assay. The growth of bacterial strains and the preparation of Ghost cells were as described herein with reference to Example 2. Results and Discussion [0120] Kinetics and Isotypes of the Serum IgG Antibodies Generated Oral Immunizations. Differences in the kinetics of the antibody response and the isotype distribution were observed between different murine strains. The antibody response was also different when living recombinant L. lactis (MSA2::cP) or Ghosts-MSA2::cA were used as immunogens. With Ghosts-MSA2::cA, high serum antibody levels were detectable in the C3H mice after two immunizations. IgG antibodies were detectable in all four murine strains after three and four immunizations. Antibody titers were highest in C3H mice. IgG antibodies that reacted with native MSA2 on parasites were detected in the sera of immune mice by fluorescence microscopy (IFA) confirming that the immunizing form of the protein elicits biologically relevant antibodies. Control immunizations were performed with Ghosts alone where no MSA2-specific antibodies were elicited. In parallel experiments using MSA2cP as the immunogen, high serum IgG antibody levels were only seen with Balb/c mice after two immunizations. After three and four immunizations, good antibody responses developed in C3H mice. Antibody titers were highest in Balb/c mice. [0121] Significant differences existed between the strains in the isotypes of the elicited serum IgG antibodies in response to immunization with Ghosts-MSA2::cA. Balb/c mice showed higher levels of IgG2a and IgG2b antibodies, some IgG3 antibodies and negligible IgG1, which demonstrates a possible Th1 bias. On the other hand, C57 Black and C3H mice had high IgG1, IgG2a and IgG2b, and lower IgG3 antibodies to MSA2, which is more characteristic of a mixed Th1 and Th2 response. ICR mice, as expected, showed a range of responses. Some ICR mice had the Balb/c and others the C3H/C57 Black pattern of IgG isotypes. [0122] Formation of Mucosal Antibodies. IgA antibodies were detected by ELISA in the fecal pellets of the ICR and Balb/c mice, but were not detected in C3H or C57 Black mice when immunization was performed with living recombinant L. lactis (MSA2::cP) or Ghost-MSA2::cA. [0123] T-Cell Responses. The increase of the intensity of the IgG ELISA reactions seen in mice immunized with Ghosts-MSA2::cA with each immunization demonstrates that boosting takes place and that a Th-dependent antibody response exists in these animals. The IgG isotype distribution further confirms this conclusion. Therefore, Th cells are generated in ICR, Balb/c, C57 Black and C3H mice. [0124] The ELISPOT assay for detecting gamma-interferon (γIFN) producing cells detects mainly CD8 + Tc cells, which are an important component of the immune response to many pathogens, including malaria parasites. His-tagged MSA2 produced in E. coli was used as antigen in the assay. MSA2-specific γIFN producing cells could be detected in the spleens of Balb/c, C57 Black and C3H mice that were immunized with Ghosts-MSA2::cA. MSA2-specific γIFN producing cells were not observed in the spleens of control mice immunized with Ghosts alone or with the living recombinant L. lactis (MSA2-cP). The latter group showed a high level of non-specific γIFN producing cells. The high background observed may be due to ongoing inflammation. [0125] The sensitization of MSA2-specific Tc cells in the spleen after immunization with the non-recombinant non-living L. lactis Ghost system carrying a foreign protein is a novel finding which is applicable to malaria since protection against sporozoite-infection is associated with γIFN producing cells being produced in the spleen. [0126] The non-recombinant non-living Ghost system can be used in oral immunizations to elicit typical Th1-type immune responses. These types of responses are particularly relevant to obtain immunity for pathogens that undergo stages in their life cycle where the pathogens are not in the blood but rather hide in cells. The responses are more pronounced and more specific for the Ghost system than for the living recombinant system. The Ghost system has the additional advantage of eliminating the risk of spreading recombinant DNA into the environment. Example 5 Protection of Mice for Lethal Streptococcus pneumoniae Challenge after Oral Immunizations with Lactococcal Ghosts Preloaded with PpmA Antigen Fused to the Lactococcal AcmA Protein Anchor [0127] Streptococcus pneumoniae is the leading etiological agent of severe infections including septicemia, meningitis, pneumonia, and otitis media. Recent studies on the molecular epidemiology and pathogenesis of S. pneumoniae have identified pneumococcal proteins with vaccine potential. One of these proteins, the protease maturation protein PpmA, has been shown to elicit immune protective potential in a mouse pneumonia model. [0128] The non-genetically modified lactococcal ghosts have been shown to be an efficient carrier for use in oral immunizations of rabbits and mice in order to elicit strong anti-malaria immune responses. The construction of lactococcal ghosts that display the S. pneumoniae PpmA fused to the lactococcal AcmA cell-wall binding domain on their surface is described herein. The ability of these ghosts to protect orally immunized mice from a lethal nasal dose of S. pneumoniae was investigated. Materials and Methods [0129] Bacterial Strains and Growth Conditions. L. lactis was grown and ghost cells were prepared as described herein with reference to Example 1. S. pneumoniae was grown as described before (Gingles et al. 2001 , Infect. Immun. 69: 426-434). [0130] Construction of ppmA Protein Anchor Fusion Expression Plasmid. The expression plasmid for ppmA protein anchor fusion (PpmA::cA) was substantially similar to the expression plasmid for the MSA2 protein anchor fusion as described herein with reference to Example 2. For the secretion of PpmA::cA, the secretion signal sequence of the Usp45 protein (ssUsp) of L. lactis (van Asseldonk et al. 1990. Gene 95: 155-160) was used. The PpmA gene was cloned by PCR using primers ppmA.1 (CGGTCTCACATGTCGAAAGGGTCAGAAGGTG CAGACC) (SEQ ID NO: 14) and ppmA.2 (CGGTCTCGAATTGCTTCGTTTGATGTACTACTG CTTGAG) (SEQ ID NO:15) resulting in plasmid pPA32 which contains ppmA as an in-frame fusion with ssUsp45 and the protein anchor (ssUsp::ppmA::cA). Expression of the fusion gene results in the secreted product PpmA::cA. The primers include an Eco31I restriction enzyme recognition site that was used for digestion of the PCR fragment. This restriction digest produced NcoI and EcoRI sticky ends which were used for cloning. The primers also included the ppmA sequences. Chromosomal DNA of S. pneumoniae strain D39 was used as a template for the PCR reactions. [0131] Preparation of the Vaccine. Three liters of M17 medium with PpmA::cA, obtained after growth and used to induce producer cells for expression of L. lactis (pPA32) was centrifuged and filter sterilized (0.2 μm) to remove the producer cells. Ghost cells were prepared from 0.5 liter of L. lactis NZ9000(ΔacmA). After binding, the ghost cells with PpmA::cA (Ghosts-PpmA::cA) were isolated by centrifugation and washed with PBS. The ghost cells were stored in PBS in aliquots of 2.5×10 10 Ghosts/ml at −80° C. Two control groups included: (i) Ghosts without bound PpmA::cA; for the sample preparation, the same amounts of ghost cells were used and the same centrifugation and washing steps were performed, but the binding step was omitted; and (ii) soluble PpmA was isolated as a his-tagged fusion. [0132] Mice Immunizations. Groups of 10 mice (CD-1) were used in the immunizations. Oral doses included 5×10 9 Ghosts with or without PpmA::cA (50 μg) or 50 μg soluble PpmA in PBS. Nasal doses included 5×10 8 Ghosts with or without PpmA::cA (5 μg) or 5 μg soluble PpmA. 10 8 Ghosts-PpmA::cA (1 μg) were subcutaneously injected. For intranasal immunizations, the mice were slightly anesthetized with Isofluorane. [0133] Intranasal Challenge. The groups of orally immunized mice were intranasally challenged 14 days after the last booster immunization with a dose of 10 6 colony forming units (CFU) S. pneumoniae D39 as described (Kadioglu et al. 2000 , Infect. Immun. 68: 492-501). Mice were monitored after the challenge for visible clinical symptoms for 7 days, at which point the experiment was ended. Mice that were alive after 7 days were considered to have survived the pneumococcal challenge and mice that became moribund during the 7-day period were judged to have reached the endpoint of the assay. The time the animal became moribund was recorded, and the animal was sacrificed by cervical dislocation. [0134] ELISA Analysis. Serum samples were taken from each mouse before the intranasal challenge and stored at −20° C. before use. Microtiter plates were coated with 100 μg PpmA/ml in 0.05 carbonate buffer. Serial 10-fold dilutions of pooled serum of each group were incubated on the plates as described (Gingles et al. 2001 , Infect. Immun. 69: 426-434). Anti-mouse immunoglobulin-horseradish peroxidase conjugate was used for detection and the absorbance was measured at 492 nm. Results and Discussion [0135] Serum Antibody Response. Mice were immunized orally, nasally and subcutaneously according to the scheme shown in FIG. 19 . Anti-PpmA antibody titers in the blood serum were determined for each group by ELISA assays. The results are given in FIG. 20 . As expected, ghosts alone administered orally or nasally, OV Ghosts or IN Ghosts, respectively, did not induce anti-PpmA antibodies. Soluble PpmA given by the nasal route resulted in only a low anti-PpmA antibody titer, which agrees with the general findings that soluble antigens are not very immunogenic when given by the mucosal routes. Ghosts-PpmA::cA provided by the oral route (OV PpmA+Ghost) induced only a low level of anti-PpmA serum antibodies. This contrasts the results for the oral immunization experiments described herein with reference to Examples 2 and 4 with MSA2::cA. However, the contrast may be antigen-type related. [0136] Intranasal administration of Ghosts-PpmA::cA resulted in a high titer of anti-PpmA antibodies (IN PpmA+Ghosts). A high titer was also obtained by subcutaneous administration of Ghosts-PpmA::cA. These titers were lower by a factor of 5 to 10 when compared to soluble PpmA that was subcutaneously administered and formulated with the strong Freund's complete adjuvant (Peter Adrian, Erasmus University Rotterdam, The Netherlands, unpublished results). In addition, the Freund's PpmA vaccine contained 50 μg PpmA per dose, whereas the intranasally administered Ghosts-PpmA:cA contains only 5 μg/dose and the subcutaneous Ghost-PpmA::cA vaccine contains only 1 μg PpmA/dose. This result demonstrates the adjuvant effect of the ghost cells. Side effects of the orally, nasally or subcutaneously administered ghosts were not observed, which is in contrast to the severe side effects that are usually seen with the use of Freund's adjuvants. [0137] The results demonstrate that high titer serum antibodies can be obtained by the mucosal route of administration. These data also show that ghost cells may be safely used in traditionally injected vaccines without side effects in order to induce high titer serum antibodies. [0138] Protection Against Challenge. The mice orally immunized with soluble PpmA, Ghosts alone or Ghosts-PpmA::cA were challenged 14 days post-immunization with a lethal intranasal dose of S. pneumoniae . The mice immunized with soluble PpmA or Ghosts alone died within 72 hours after challenge. The group immunized with Ghosts-PpmA::cA showed a survival rate of 40% ( FIG. 21 ). These results show that mucosal immunization of mice with Ghosts-PpmA induces protective immunity against a lethal S. pneumoniae challenge. In conclusion, the non-recombinant non-living Ghost system may be used to elicit high titer serum antibodies and the mucosal route of administration may be used to obtain protective immunity against a mucosally acquired pathogen. [0000] TABLE 1 Effect of different pretreatments of L. lactis on binding of MSA2::cA. Treatment Signal on Western blot H 2 O − 10% TCA (0.6 M) ++++ 0.6 M HAc ++++ 0.6 M HCl ++++ 0.6 M H 2 SO 4 ++++ 0.6 M TFA ++++ 0.6 M MCA ++++ Phenol ++ 4 M GnHCl ++ 37% formaldehyde ++ CHCl 3 /MeOH ++ 10% SDS + 10% DMF + 10% DMSO + 25 mM DTT + 0.1% NaHC1O* − Hexane − Lysozyme* − *Lysis of cells occurred during treatment or washing steps. [0000] TABLE 2 MSA2 antibody titers of rabbit serum determined by IFA on Plasmodium falciparum 3D7 asexual blood stage parasites. Immunization Rabbit 3 rd serum Immunogen P 2 nd 3 rd IgG A1 s.c. L. lactis [MSA2::cA] 0 2 4 4 A2 s.c. L. lactis [MSA2::cA] 0 2 5 5 B1 s.c. L. lactis 0 0 1 n.d. B2 s.c. L. lactis 0 0 1 n.d. C1 oral L. lactis [MSA2::cP] 0 3 5 5 C2 oral L. lactis [MSA2::cP] 0 2 5 5 D1 oral L. lactis [MSA2::cA] 0 2 4 5 D2 oral L. lactis [MSA2::cA] 0 2 4 5 E1 oral TCA L. lactis + MSA2::cA 0 2 5 5 E2 oral TCA L. lactis + MSA2::cA 0 2 5 4 L. lactis strain used: NZ9000ΔacmA (lactococcal cells lacking the cell wall hydrolase AcmA). L. lactis [MSA2::cA] and L. lactis [MSA2::cP] are the recombinant strains with surface-expressed MSA2, cell wall anchored through the non-covalent AcmA binding domain (cA) or the covalent PrtP anchoring domain (cP), respectively. TCA L. lactis + MSA2::cA are the non-recombinant TCA-pretreated lactococcal cells to which MSA2::cA had been bound externally. P: pre-immune serum. S.C.: subcutaneous injection. Titers are expressed as the negative logarithms of the lowest ten-fold dilution of sera giving a detectable reaction on the merozoite surface. The last column represents the IgG fraction of the antibody response. 0: indicates no detectable reaction at a 1:10 dilution of the serum. n.d.: not done. [0000] TABLE 3 AcmA cell wall binding domain homologs and their calculated pI values. (the pI values are indicated directly behind the amino acid sequences) Lactococcus * acmA YTVKSGDTLWGISQRYGISVAQIQSAN SEQ ID NO:16 9.75 lactis NLKST IIYIGQKLVLT VKVKSGDTLWALSVKYKTSIAQLKSWN SEQ ID NO:17 9.64 HLSSD TIYIGQNLIVS HKVVKGDTLWGLSQKSGSPIASIKAWN SEQ ID NO:18 10.06 HLSSD TILIGQYLRIK * acmD YKVQEGDSLSAIAAQYGTTVDALVSAN SEQ ID NO:19 4.15 SLENANDIHVGEVLQVA YTVKSGDSLYSIAEQYGMTVSSLMSAN SEQ ID NO:20 3.78 GIYDVNSMLQVGQVLQVTV YTIQNGDSIYSIATANGMTADQLAALN SEQ ID NO:21 4.15 GFGIND MIHPGQTIRI ØTuc2009 * lys YVVKQGDTLSGIASNWGTNWQELARQN SEQ ID NO:22 6.31 SLSNPNMIYAGQVISFT YTVQSGDNLSSIAILLGTTVQSLVSMN SEQ ID NO:23 3.45 GISNPNLIYAGQTLNY Ø-LC3 * lysB YIVKQGDTLSGIASNLGTNWQELARQN SEQ ID NO:24 6.31 SLSNPNMIYSGQVISLT YTVQSGDNLSSIARRLGTTVQSLVSMN SEQ ID NO:25 8.79 GISNPNLIYAGQTLNY Enterococcus * autolysin YTVKSGDTLNKIAAQYGVSVANLRSWN SEQ ID NO:26 9.74 faecalis GISGD LIFVGQKLIVK YTVKSGDTLNKIAAQYGVTVANLRSWN SEQ ID NO:27 9.74 GISGD LIFVGQKLIVK YTIKSGDTLNKIAAQYGVSVANLRSWN SEQ ID NO:28 9.74 GISGD LIFAGQKIIVK YTIKSGDTLNKISAQFGVSVANLRSWN SEQ ID NO:29 9.85 GIKGD LIFAGQTIIVK HTVKSGDSLWGLSMQYGISIQKIKQLN SEQ ID NO:30 9.35 GLSGD TIYIGQTLKVG hirae * mur2 YTVKSGDSVWGISHSFGITMAQLIEWN SEQ ID NO:31 9.35 NIKNN FIYPGQKLTIK YTVKSGDSVWKIANDHGISMNQLIEWN SEQ ID NO:32 7.14 NIKNN FVYPGQQLVVS YTVKAGESVWSVSNKFGISMNQLIQWN SEQ ID NO:33 9.91 NIKNN FIYPGQKLIVK YTVKAGESVWGVANKNGISMNQLIEWN SEQ ID NO:34 9.64 NIKNN FIYPGQKLIVK YTVKAGESVWGVANKHHITMDQLIEWN SEQ ID NO:35 7.31 NIKNN FIYPGQEVIVK YTVKAGESVWGVADSHGITMNQLIEWN SEQ ID NO:36 7.15 NIKNN FIYPGQQLIVK Listeria * P60 VVVEAGDTLWGIAQSKGTTVDAIKKAN SEQ ID NO:37 8.61 monocytogenes NLTTD KIVPGQKLQVN NAVKSGDTIWALSVKYGVSVQDIMSWN SEQ ID NO:38 9.35 NLSSS SIYVGQKLAIK innocua * P60 VVVEAGDTLWGIAQSKGTTVDAIKKAN SEQ ID NO:39 8.61 NLTTD KIVPGQKLQVN HNVKSGDTIWALSVKYGVSVQDIMSWN SEQ ID NO:40 8.35 NLSSS SIYVGQKPAIK ivanovii * P60 VVVEAGDTLWGIAQDKGTTVDALKKAN SEQ ID NO:41 6.35 NLTSD KIVPGQKLQIT YTVKSGDTIWALSSKYGTSVQNIMSWN SEQ ID NO:42 9.37 NLSSS SIYVGQVLAVK YTVKSGDTLSKIATTFGTTVSKIKALN SEQ ID NO:43 9.89 GLNSD NLQVGQVLKVK seeligeri * P60 VVVEAGDTLWGIAQDNGTTVDALKKAN SEQ ID NO:44 6.35 KLTTD KIVPGQKLQVT HTVKSGDTIWALSVKYGASVQDLMSWN SEQ ID NO:45 8.64 NLSSS SIYVGQNIAVK YTVKSGDTLGKIASTFGTTVSKIKALN SEQ ID NO:46 9.62 GLTSD NLQVGDVLKVK welshimeri * P60 VVVEAGDTLWGIAQSKGTTVDALKKAN SEQ ID NO:47 8.61 NLTSD KIVPGQKLQVT HTVKSGDTIWALSVKYGASVQDLMSWN SEQ ID NO:48 9.35 NLSSS SIYVGQKIAVK YTVKSGDSLSKIANTFGTSVSKIKALN SEQ ID NO:49 9.89 NLTSD NLQVGTVLKVK grayi * P60 VVVASGDTLWGIASKTGTTVDQLKQLN SEQ ID NO:50 9.42 KLDSD RIVPGQKLTIK YKVKSGDTIWALSVKYGVPVQKLIEWN SEQ ID NO:51 9.57 NLSSS SIYVGQTIAVK YKVQNGDSLGKIASLFKVSVADLTNWN SEQ ID NO:52 8.59 NLNATITIYAGQELSVK Haemophilus * amiB HIVKKGESLGSLSNKYHVKVSDIIKLN SEQ ID NO:53 10.11 influenzae QLKRK TLWLNESIKIP HKVTKNQTLYAISREYNIPVNILLSLN SEQ ID NO:54 10.49 PHLKNG KVITGQKIKLR * yebA YTVTEGDTLKDVLVLSGLDDSSVQPLI SEQ ID NO:55 3.87 ALDPELAHLKAGQQFYWI lppB YKVNKGDTMFLIAYLAGIDVKELAALN SEQ ID NO:56 6.40 NLSEPNYNLSLGQVLKIS somnus lppB YKVRKGDTMFLIAYISGMDIKELATLN SEQ ID NO:57 8.56 NMSEPYHLSIGQVLKIA Helicobacter dniR HVVLPKETLSSIAKRYQVSISNIQLAN SEQ ID NO:58 10.02 pylori DLKDS NIFIHQRLIIR Pseudomonas lppB YIVRRGDTLYSIAFRFGWDWKALAARN SEQ ID NO:59 10.06 aeruginosa GIAPPYTIQVGQAIQFG Putida nlpD YIVKPGDTLFSIAFRYGWDYKELAARN SEQ ID NO:60 9.77 GIPAPYTIRPGQPIRFS Sinorhizoblum nlpD IMVRQGDTVTVLARRFGVPEKEILKAN SEQ ID NO:61 10.27 meliloti GLKSASQVEPGQRLVIP Synechocystis nlpD HQVKEGESLWQISQAFQVDAKAIALAN SEQ ID NO:62 4.38 sp. SISTDTELQAGQVLNIP slr0878 HVVKAGETIDSIAAQYQLVPATLISVN SEQ ID NO:63 5.41 NQLSSGQVTPGQTILIP Aquifex nlpD1 YKVKKGDSLWKIAKEYKTSIGKLLELN SEQ ID NO:64 10.08 acolicus PKLKNRKYLRPGEKICLK YRVKRGDSLIKIAKKFGVSVKEIKRVN SEQ ID NO:65 10.95 KLKGN RIYVGQKLKIP YRVRRGDTLIKIAKRFRTSVKEIKRIN SEQ ID NO:66 12.11 RLKGN LIRVGQKLKIP Volvox YTIQPGDTFWAIAQRRGTTVDVIQSLN SEQ ID NO:67 9.03 carteri PGVVPTRLQVGQVINVP f. YTIQPGDTFWAIAQRRGTTVDVIQSLN SEQ ID NO:68 9.03 nagariensis PGVNPARLQVGQVINVP Staphylo - ProtA HVVKPGDTVNDIAKANGTTADKIAADN SEQ ID NO:69 5.58 coccus KLADKNMIKPGQELVVD aureus lytN YTVKKGDTLSAIALKYKTTVSNIQNTN SEQ ID NO:70 10.03 NIANPNLIFIGQKLKVP Colletotrichum cih1 HKVKSGESLTTIAEKYDTGICNIAKLN SEQ ID NO:71 4.76 NLADPNFIDLNQDLQIP lindemuthianum YSVVSGDTLTSIAQALQITLQSLKDAN SEQ ID NO:72 5.46 PGVVPENLNVGQKLNVP Chlamydophila aniB IVYREGDSLSKIAKKYKLSVTELKKIN SEQ ID NO:73 9.46 KLDSD AIYAGQRLCLQ Pneumoniae CPn0593 YVVQDGDSLWLIAKRFGIPMDKIIQKN SEQ ID NO:74 10.01 GLNHH RLFPGKVLKLP NlpD VVVKKGDFLERIARANNTTVAKLMQIN SEQ ID NO:75 10.17 DLTTT QLKIGQVIKVP YIVQEGDSPWTIALRNHIRLDDLLKMN SEQ ID NO:76 8.64 DLDEYKARRLKPGDQLRIR Chlamydia NlpD VIVKKGDFLERIARSNHTTVSALMQLN SEQ ID NO:77 9.99 trachomatis DLSST QLQIGQVLRVP YVVKEGDSPWAIALSNGIRLDELLKLN SEQ ID NO:78 10.00 GLDEQKARRLRPGDRLRIR papQ HIVKQGETLSKIASKYNIPVVELKKLN SEQ ID NO:79 9.89 KLNSD TIFTDQRIRLP Prevotella phg HTVRSNESLYDISQQYGVRLKNIMKAN SEQ ID NO:80 10.72 intermedia RKIVKRGIKAGDRVVL Leuconostoc lys YTVQSGDTLGAIAAKYGTTYQKLASLN SEQ ID NO:81 9.23 oenos  Ø10MC GIGSPYIIIPGEKLKVS YKVASGDTLSAIASKYGTSVSKLVSLN SEQ ID NO:82 9.68 GLKNANYIYVGENLKIK Oenococcus Lys44 YTVRSGDTLGAIAAKYGTTYQKLASLN SEQ ID NO:83 9.58 oeni  ØfOg44 GIGSPYIIIPGEKLKVS YKVASGDTLSAIASKYGTSVSKLVSLN SEQ ID NO:84 9.95 GLKNANYIYVGQTLRIK Thermotoga TM0409 YKVQKNDTLYSISLNFGISPSLLLDWN SEQ ID NO:85 5.49 maritime PGLDPHSLRVGQEIVIP YTVKKGDTLDAIAKRFFTTATFIKEAN SEQ ID NO:86 9.73 QLKSY TIYAGQKLFIP TM1686 HVVKRGETLWSIANQYGVRVGDIVLIN SEQ ID NO:87 8.76 RLEDPDRIVAGQVLKIG Treponema dniR HTIRSGDTLYALARRYGLGVDTLKAHN SEQ ID NO:88 10.58 pallidum RAHSATHLKIGQKLIIP HVVQQGDTLWSLAKRYGVSVENLAEEN SEQ ID NO:89 4.81 NLAVDATLSLGMILKTP TP0155 YEVREGDVVGRIAQRYDISQDAIISLN SEQ ID NO:90 9.58 KLRSTRALQVGQLLKIP TP0444 HVIAKGETLFSLSRRYGVPLSALAQAN SEQ ID NO:91 10.98 NLANVHQLVPGQRIVVP Borrelia BB0262 HKIKPGETLSHVAARYQITSETLISFN SEQ ID NO:92 9.72 burgdorferi EIKDVRNIKPNSVIKVP YIVKKNDSISSIASAYNVPKVDILDSN SEQ ID NO:93 4.58 NLDNE VLFLGQKLFIP * B80625 YKVVKGDTLFSIAIKYKVKVSDLKRIN SEQ ID NO:94 10.02 KLNVD NIKAGQILIIP YTAKEGDTIESISKLVGLSQEEIIAWN SEQ ID NO:95 5.00 DLRSK DLKVGMKLVLT YMVRKGDSLSKLSQDFDISSKDILKFN SEQ ID NO:96 9.20 FLNDD KLKIGQQLFLK HYVKRGETLGRIAYIYGVTAKDLVALN SEQ ID NO:97 10.05 GNRAI NLKAGSLLNVL HSVAVGETLYSIARHYGVLIEDLKNWN SEQ ID NO:98 7.41 NLSSN NIMHDQKLKIF BB0761 YKVKKGDTFFKIANKINGWQSGIATIN SEQ ID NO:99 9.34 LLDSP AVSVGQEILIP Lactobacillus * lys YTVVSGDSWNKIAQRNGLSMYTLASQN SEQ ID NO:100 9.83 Øgle GKSIYSTIYPGNKLIIK Bacillus * lytE IKVKKGDTLWDLSRKYDTTISKIKSEN SEQ ID NO:101 9.55 subtilis HLRSD IIYVGQTLSIN YKVKSGDSLWKISKKYGMTINELKKLN SEQ ID NO:102 10.16 GLKSD LLRVGQVLKLK YKVKSGDSLSKIASKYGTTVSKLKSLN SEQ ID NO:103 10.03 GLKSD VIYVNQVLKVK spoV1D CIVQQEDTIERLCERYEITSQQLIRMN SEQ ID NO:104 4.20 SLALDDELKAGQILYIP yaaH MVKQGDTLSAIASQYRTTTNDITETN SEQ ID NO:105 3.89 EIPNPDSLVVGQTIVIP YDVKRGDTLTSIARQFNTTAAELARVN SEQ ID NO:106 10.32 RIQLNTVLQIGFRLYIP yhdD IKVKSGDSLWKLAQTYNTSVAALTSAN SEQ ID NO:107 9.56 HLSTT VLSIGQTLTIP YTVKSGDSLWLIANEFKNTVQELKKLN SEQ ID NO:108 9.62 GLSSD LIRAGQKLKVS YKVQLGDSLWKIANKVNMSIAELKVLN SEQ ID NO:109 9.72 NLKSD TIYVNQVLKTK YTVKSGDSLWKIANNYNLTVQQIRNIN SEQ ID NO:110 9.65 NLKSD VLYVGQVLKLT YTVKSGDSLWVIAQKFNVTAQQIREKN SEQ ID NO:111 9.72 NLKTD VLGVGQKLVIS yojL IKVKSGDSLWKLSRQYDTTISALKSEN SEQ ID NO:112 9.93 KLKST VLYVGQSLKVP YTVAYGDSLWMIAKNHKMSVSELKSLN SEQ ID NO:113 9.81 SLSSD LIRPGQKLKIK YTVKLGDSLWKIANSLNMTVAELKTLN SEQ ID NO:114 9.27 GLTSD TLYPKQVLKIG YKVKAGDSLWKIANRLGVTVQSIRDKN SEQ ID NO:115 9.84 NLSSD VLQIGQVLTIS yocH ITVQKGDTLWGISQKNGVNLKDLKEWN SEQ ID NO:116 9.25 KLTSD KIIAGEKLTIS YTIKAGDTLSKIAQKFGTTVNNLKVWN SEQ ID NO:117 9.64 NLSSD MIYAGSTLSVK ykvP HHVTPGETLSIIASKYNVSLQQLMELN SEQ ID NO:118 8.65 HFKSD QIYAGQIIKIR * xlyB YHVKKGDTLSGIAASHGASVKTLQSIN SEQ ID NO:119 9.72 HITDPNHIKIGQVIKLP yrbA NIVQKGDSLWKIAEKYGVDVEEVKKLN SEQ ID NO:120 8.51 TQLSNPDLIMPGMKIKVP ydhD HIVGPGDSLFSIGRRYGASVDQIRGVN SEQ ID NO:121 5.49 GLDET NIVPGQALLIP ykuD YQVKQGDTLNSIAADFRISTAALLQAN SEQ ID NO:122 6.10 PSLQA GLTAGQSIVIP ØPBSX * xlyA YVVKQGDTLTSIARAFGVTVAQLQEWN SEQ ID NO:123 4.65 NIEDPNLIRVGQVLIVS Ø PZA * orf15 YKVKSGDNLTKIAKKHNTTVATLLKLN SEQ ID NO:124 10.23 PSIKDPNMIRVGQTINVT (= Ø-29) HKVKSGDTLSKIAVDNKTTVSRLMSLN SEQ ID NO:125 10.17 PEITNPNHIKVGQTIRLS Ø B103 * orf15 HVVKKGDTLSEIAKKIKTSTKTLLELN SEQ ID NO:126 10.11 PTIKNPNKIYVGQRINVG YKIKRGETLTGIAKKNKTTVSQLMKLN SEQ ID NO:127 10.61 PNIKNANNIYAGQTIRLK sphaericus * Pep I ILIRPGDSLWYFSDLFKIPLQLLLDSN SEQ ID NO:128 8.86 RNINPQ LLQVGQRIQIP YTITQGDSLWQIAQNKNLPLNAILLVN SEQ ID NO:129 7.15 PEIQPS RLHIGQTIQVP Salmonella nlpD YTVKKGDTLFYIAWITGNDFRDLAQRN SEQ ID NO:130 8.64 dublin SISAPYSLNVGQTLQVG Escherichia * yebA YVVSTGDTLSSILNQYGIDMGDISQLA SEQ ID NO:131 4.13 coli AADKELRNLKIGQQLSWT mltD YTVRSGDTLSSIASRLGVSTKDLQQWN SEQ ID NO:132 10.58 KLRGS KLKPGQSLTIG YRVRKGDSLSSIAKRHGVNIKDVMRWN SEQ ID NO:133 10.18 SDTAN LQPGDKLTLF UUG YTVKRGDTLYRISRTTGTSVKELARLN SEQ ID NO:134 10.16 GISPPYTIEVGQKLKLG nlpD YTVKKGDTLFYIAWITGNDFRDLAQRN SEQ ID NO:135 8.64 NIQAPYALNVGQTLQVG Drosophila Q9VNAI YTVGNRDTLTSVAARFDTTPSELTHLN SEQ ID NO:136 7.15 melanogaster RLNSS FIYPGQQLLVP Drosophila Q961P8 YTVGNRDTLTSVAARFDTTPSELTHLN SEQ ID NO:136 7.15 melanogaster RLNSS FIYPGQQLLVP Caenorhabditis F43G9.2 RKVKNGDTLNKLAIKYQVNVAEIKRVN SEQ ID NO:137 10.01 elegans NMVSEQDFMALSKVKIP Caenorhabditis F52E1.13 YTITETDTLERVAASNDCTVGELMKLN SEQ ID NO:138 7.08 elegans KMASR MVFPGQKILVP Caenorhabditis F07G11.9 TEIKSGDSCWNIASNAKISVERLQQLN SEQ ID NO:139 8.32 elegans KGMKCDKLPLGDKLCLA LKLKAEDTCFKIWSSQKLSERQFLGMN SEQ ID NO:140 7.84 EGMDCDKLKVGKEVCVA HKIQKGDTCFKIWTTNKISEKQFRNLN SEQ ID NO:141 8.65 KGLDCDKLEIGKEVCIS LKIKEGDTCYNIWTSQKISEQEFMELN SEQ ID NO:142 4.54 KGLDCDKLEIGKEVCVT YRFKKGDTCYKIWTSHKMSEKQFRALN SEQ ID NO:143 9.35 RGIDCDRLVPGKELCVG ITVKPGDTCFSIWTSQKMTQQQFMDIN SEQ ID NO:144 4.21 PELDCDKLEIGKEVCVT VKINPGDTCFNIWTSQRMTQQQFMDLN SEQ ID NO:145 6.30 KRLDCDKLEVGKEVCVA VQINPGDTCFKIWSAQKLTEQQFMELN SEQ ID NO:146 4.60 KGLDCDRLEVGKEVCIA TEVKEGDTCFKIWSAHKITEQQFMEMN SEQ ID NO:147 5.12 RGLDCNRLEVGKEVCIV IKVKEGDTCFKIWSAQKMTEQQFMEMN SEQ ID NO:148 7.85 RGLDCNKLMVGKEVCVS ATITPGNTCFNISVAYGINLT   DLQ SEQ ID NO:149 3.99 KTYDCKALEVGDTICVS IEVIKGDTCWFLENAFKTNQTEMERAN SEQ ID NO:150 4.67 EGVKCDNLPIGRMMCVW Caenorhabditis T01C4.1 HTIKSGDTCWKIASEASISVQELEGLN SEQ ID NO:151 5.01 elegans SKKSCANLAVGLSEQEF IHVKEGDTCYTIWTSQHLTEKQFMDMN SEQ ID NO:152 4.12 EELNCGMLEIGNEVCVD ATVTPGSSCYTISASYGLNLAELQTTY SEQ ID NO:153 3.07 NCDALQVDDTICVS IEILNGDTCGFLENAFQTNNTEMEIAN SEQ ID NO:154 3.85 EGVKCDNLPIGRMMCVW Bacillus # ypbE HTVQKKETLYRISMKYYKSRTGEEKIR SEQ ID NO:155 9.45 subtilis AYNHLNGNDVYTGQVLDIP Citrobacter # eae YTLKTGESVAQLSKSQGISVPVIWSLN SEQ ID NO:156 8.59 fruendii KHLYSSESEMMKASPGQQIILP Escherichia # eae YTLKTGETVADLSKSQDINLSTIWSLN SEQ ID NO:157 5.65 coli KNLYSSESEMMKAAPGQQIILP Micrococcus # rpf IVVKSGDSLWTLANEYEVEGGWTALYE SEQ ID NO:158 3.85 luteus ANKGAVSDAAVIYVGQELVL Bacillus # yneA IEVQQGDTLWSIADQVADTKKINKNDF SEQ ID NO:159 3.81 subtilis IEWVADKNQLQTSDIQPGDELVIP Streptococcus # YTVKYGDTLSTIAEAMGIDVHVLGDIN SEQ ID NO:160 4.23 pyogenes HIANIDLIFPDTILTANYNQHGQATTL T Bacillus # xkdP YTVKKGDTLWDIAGRFYGNETQWRKIW SEQ ID NO:161 11.23 subtilis NANKTAMIKRSKRNIRQPGHWIFPGQK LKIP Bacillus # yqbP YTVKKGDTLWDIAGRFYGNSTQWRKIW SEQ ID NO:161 11.23 subtilis NANKTAMIKRSKRNIRQPGHWIFPGQK LKIP Bacillus # YTVKKGDTLWDLAGKFYGDSTKWRKIW SEQ ID NO:162 10.75 subtilis KVNKKAMIKRSKRNIRQPGHWIFPGQK LKIP Lactococcus 245-287 (33) 437 U1769600 muramidase lactis 321-363 (31) 395-437 194-237 QGCI25 258-303 319-361 ØTuc2009 332-375 (10) 428 L31364 glycosidase (muramidase) 386-428 Ø-LC3 333-376 (10) 429 U04309 muramidase 387-429 Enterococcus 363-405 (25) 671 P37710 muramidase faecalis 431-473 (25) 499-541 (25) 567-609 (19) 629-671 hirae 257-299 (38) 666 P39046 muramidase 338-380 (33) 414-456 (32) 489-531 (33) 565-607 (15) 623-665 Listeria  30-72  (130) 484 P21171 adherence and monocytogenes invasion protein P60 203-245 innocua  30-72  (129) 481 Q01836 adherence and invasion protein P60 201-243 ivanovii  30-72  (125) 524 Q01837 adherence and invasion protein P60 198-240 (73) 314-356 seeligeri  30-72  (127) 523 Q01838 adherence and invasion protein P60 200-242 (77) 320-362 welshimeri  30-72  (125) 524 M80348 adherence and invasion protein P60 198-240 (75) 316-358 grayi  30-72  (104) 511 Q01835 adherence and invasion protein P60 177-219 (79) 299-342 Haemophilus 294-336 432 P44493 N—acetylmuramoyl- influenzae L-alanine amidase 387-430 131-174 475 P44693 homologous to endopeptidase of Staphylococcus 147-190 405 P44833 outer membrane lipoprotein somnus 120-164 279 L10653 outer membrane lipoprotein Helicobacter 319-361 372 AE000654 regulatory protein pylori DniR Pseudomonas  69-113 297 P45682 Lipoprotein aeruginosa Putida  44-87 244 Y19122 lipoprotein Sinorhizoblum 166-209 512 U81296 Lipoprotein meliloti Synechocystis  87-130 715 D90915 Lipoprotein sp.   4-47 245 D90907 Hypothetical protein Aquifex  26-70  (24) 349 AE000700 Lipoprotein acolicus  95-137 (37) 174-216 Volvox  42-85 309 AF058716 chitinase carteri f. 106-149 nagariensis Staphylo - 431-474 524 A04512 protein A coccus 177-220 383 AF106851 autolysin homolog aureus Colletotrichum 110-153 (31) 230 AJ001441 glycoprotein lindemuthianum 185-228 Chlamydophila 159-201 205 AE001659.1 N—Acetylmuramoyl- L-Ala Amidase Pneumoniae 316-358 362 AE001643 124-166 233 AE001670 Muramidase 188-233 Chlamydia 138-180 245 AE001348 Muramidase trachomatis 200-245 155-197 200 AE001330 Prevotella 266-309 309 AF017417 hemagglutinin intermedia Leuconostoc 335-378 432 endolysin oenos  Ø10MC 389-432 Oenococcus 335-378 432 AF047001 Lysin oeni  ØfOg44 389-432 Thermotoga  26-69 271 AE001720 maritime  76-118 212-255 395 AE001809 Treponema 607-650 779 AE001237 membrane-bound pallidum lytic murein transglycosylase D 734-777  87-130 371 AE001200  67-110 342 AE001221 Borrelia 183-226 (6) 417 AE001137 Hypothetical protein burgdorferi 233-275  44-86  (28) 697 AE001164 N—acetylmuramoyl- L-alanine amidase 115-157 (7) 165-207 (8) 216-258 (27) 286-328  59-102 295 AE001176 Lactobacillus 399-442 442 X90511 lysin Øgle Bacillus  28-70  (17) 334 U38819.1 D-Glutamate-M- subtilis diam inopimlate endopeptidase  88-130 (20) 151-193 525-568 575 P37963 stage VI sporulation protein D   1-43  (5) 427 P37531 Hypothetical protein  49-92  29-71  (22) 488 Y14079 Hypothetical protein  94-136 (39) 176-218 (23) 242-284 (24) 309-351  29-71  (18) 414 Z99114 similar to cell wall binding protein  90-132 (26) 159-201 (25) 227-269  28-70  (9) 287 AF027868 similar to papQ  80-122 345-387 399 Z99111 Hypothetical protein 179-222 317 Z99110 N—acetylmuramoyl- L-alanine amidase   4-48 387 Z99118 similar to spore coat protein   4-46 439 Z99107   4-46 164 Z99111 ØPBSX 161-204 297 P39800 N—acetylmuramoyl- L-alanine amidase Ø PZA 163-207 (6) 258 P11187 (=Ø-29) 214-258 P07540 Ø B103 165-209 (9) 263 X99260 lysozyme 219-263 sphaericus   3-46  (6) 396 X69507 carboxypeptidase 1  53-96 Salmonella 121-164 377 AJ006131 dublin Escherichia  77-121 419 p24204 homologous to coli endopeptidase of Staphylococcus 343-385 (16) 452 P23931 membrane-bound lytic murein transglycosylase d precursor 402-443  50-93 259 U28375 Hypothetical protein 123-166 379 P33648 Lipoprotein Drosophila 329-371 1325 AF125384 Lethal 82FD protein melanogaster Drosophila 104-146 678 AAK92873 melanogaster Caenorhabditis  12-55 179 Z79755 elegans Caenorhabditis  24-66 819 U41109 elegans Caenorhabditis  23-66  (11) 1614 U64836/ Putative elegans AF016419 Endochitinase  78-121 (21) 143-186 (21) 208-251 (19) 271-314 (20) 335-378 (23) 402-445 (21) 467-510 (37) 548-591 (44) 636-679 (66) 746-786 (8) 795-838 Caenorhabditis  23-66  (51) 1484 U70858 Putative elegans Endochitinase 118-161 (25) 187-226 (9) 236-279 Bacillus 191-136 240 L47648 subtilis Citrobacter  65-113 936 Q07591 fruendii Escherichia  65-113 934 P43261 Necessary for close coli (intimate) attachment of bacteria Micrococcus 171-218 220 Z96935 Bacterial Cytokine luteus Bacillus  40-90 105 Z73234 subtilis Streptococcus 147-103 393 U09352 pyogenes Bacillus 176-234 235 P54335 subtilis Bacillus 177-234 235 G1225954 subtilis Bacillus 161-218 219 P45932 subtilis Consensus Y x VK x GDTL xx IA xxxxxxxxx L xxx N xx L xxxxx I xx GQ x I x V x (SEQ ID NO:163) repeat H IR  ESV  LS         I      I     L     L I    L     I  V                       V     V L a) Proteins listed were obtained by a homology search in the SWISSPROT, PIRk, and Genbank databases with the repeats of AcmA using the BLAST program. b) *; genes encoding cell wall hydrolases. #; proteins containing repeats that are longer than the consensus sequence. c) The number of aa residues between the repeats is given between brackets. d) Number of aa of the primary translation product. e) Genbank accession number. [0000] TABLE 4 Calculated pIs of individual repeat sequences of the AcmA and AcmD protein anchors. AcmA anchor domain AcmD anchor domain Repeat Calculated pI Repeat Calculated pI A1 9.75 D1 4.15 A2 9.81 D2 3.78 A3 10.02 D3 4.15 A1A2A3 10.03 D1D2D3 3.85 [0000] TABLE 5 Hybrid protein anchors composed of different AcmA and AcmD repeat sequences and their calculated pIs. Composition of hybrids AcmA-repeat sequence AcmD-repeat sequence Calculated pI A1A2A3 — 10.03 A1A2 D1 9.53 A1A2A3 D1D2D3 8.66 A1 D2 8.45 A3 D1D2 7.39 A1A2 D1D2D3 6.08 A3 D1D2D3 5.07 A1 D1D2D3 4.37 — D1D2D3 3.85 REFERENCES [0000] Bolotin et al. (2001) Genome Res. 11: 731-753. Buist et al. (1995) J. Bacteriol. 177: 1554-1563. Gasson (1983) J. Bacteriol. 154: 1-9. Kok et al. (1988) Appl. Environ. Microbiol. 54: 231-238. Kuipers et al. (1997) Tibtech. 15: 135-140. Morata de Ambrosini et al. (1998) J. Food Prot. 61: 557-562. Navarre and Schneewind (1994) Mol. Microbiol. 14: 115-121. Norton et al. (1994) FEMS Microbiol. Lett. 120: 249-256. Norton et al. (1996) FEMS Immunol. Med. Microbiol. 14: 167-177. Poquet et al. (2000) Mol. Microbiol. 35: 1042-1051. Ramasamy (1987) Immunol. Cell Biol. 65: 419-424. Ramasamy et al. (1999) Parasite Immunol. 21: 397-407. Robinson et al. (1997) Nature Biotechnol. 15: 653-657. Sauvé et al. (1995) Anal. Biochem. 226: 382-283.
Methods for improving binding of a proteinaceous substance to cell-wall material of a Gram-positive bacterium are disclosed. The proteinaceous substance includes an AcmA cell-wall binding domain, homolog or functional derivative thereof. The method includes treating the cell-wall material with a solution capable of removing a cell-wall component such as a protein, lipoteichoic acid or carbohydrate from the cell-wall material and contacting the proteinaceous substance with the cell-wall material.
8
This is a Continuation-in-Part application claiming priority from prior application Ser. No. 09/178,060 filed Oct. 26, 1998, now U.S. Pat. No. 6,206,359 B1the prior application being incorporated herein by reference. FIELD OF INVENTION This invention relates generally to electrical stimulation therapy for neurologic and neuropsychiatric disorders, more specifically to neuromodulation therapy for depression, migraine, and neuropsychiatric disorders, as well as adjunct treatment for partial complex, generalized epilepsy and involuntary movement disorders utilizing an implanted lead-receiver and an external stimulator. BACKGROUND It has been observed clinically that electrical stimulation therapy for seizures produced mood improvement independent of the anti-seizure effects. This discovery led to medical research into the therapeutic effects of electrical stimulation for depression. Medical research has shown beneficial medical effects of vagus nerve stimulation (VNS) for severely depressed patients. Vagus nerve stimulation, and the profound effects of electrical stimulation of the vagus nerve on central nervous system (CNS) activity, extends back to the 1930's. Medical studies in clinical neurobiology have advanced our understanding of anatomic and physiologic basis of the anti-depressive effects of vagus nerve stimulation. Some of the somatic interventions for the treatment of depression include electroconvulsive therapy (ECT), transcranical magnetic stimulation, vagus nerve stimulation, and deep brain stimulation. The vagus nerve is the 10 th cranial nerve, and is a direct extension of the brain. FIG. 1A, shows a diagram of the brain and spinal cord 24 , with its relationship to the vagus nerve 54 and the nucleus tractus solitarius 14 . FIG. 1B shows the relationship of the vagus nerve 54 with the other cranial nerves. Vagus nerve stimulation is a means of directly affecting central function and is less invasive than deep brain stimulation (DBS). As shown in FIG. 1C, cranial nerves have both afferent pathway 19 (inward conducting nerve fibers which convey impulses toward the brain) and efferent pathway 21 (outward conducting nerve fibers which convey impulses to an effector). The vagus nerve is composed of 80% afferent sensory fibers carrying information to the brain from the head, neck, thorax, and abdomen. The sensory afferent cell bodies of the vagus reside in the nodose ganglion and relay information to the nucleus tractus solitarius (NTS) 14 . As shown schematically in FIGS. 1A and 1D, the nucleus of the solitary tract relays this incoming sensory information to the rest of the brain through three main pathways; (1) an autonomic feedback loop, (2) direct projection to the reticular formation in the medulla, and (3) ascending projections to the forebrain largely through the parabrachial nucleus (PBN) 20 and the locus ceruleus (LC) 22 . The PBN 20 sits adjacent to the neucleus LC 22 (FIG. 1 A). The PBN/LC 20 / 22 sends direct connections to every level of the forebrain, including the hypothalamus 26 , and several thalamic 25 regions that control the insula and orbitofrontal 28 and prefontal cortices. Perhaps important for mood regulation, the PBN/LC 20 / 22 has direct connections to the amygdala 29 and the bed nucleus of the stria terminalis—structures that are implicated in emotion recognition and mood regulation. In sum, incoming sensory (afferent) connections of the vagus nerve 54 provide direct projections to many of the brain regions implicated in nueropsychiatric disorders. These connections reveal how vagus nerve stimulation is a portal to the brainstem and connected regions. These circuits likely account for the neuropsychiatric effects of vagus nerve stimulation. Increased activity of the vagus nerve is also associated with the release of more serotonin in the brain. Much of the pharmacologic therapy for treatment of migraines is aimed at increasing the levels of serotonin in the brain. Therefore, non-pharmacologic therapy of electrically stimulating the vagus nerve would have benefits for adjunct treatment of migraines and other ailments, such as obsessive compulsive disorders, that would benefit from increasing the level of serotonin in the brain. The vagus nerve provides an easily accessible, peripheral route to modulate central nervous system (CNS) function. Other cranial nerves can be used for the same purpose, but the vagus nerve is preferred because of its easy accessibility. In the human body there are two vagal nerves (VN), the right VN and the left VN. Each vagus nerve is encased in the carotid sheath along with the carotid artery and jugular vein. The innervation of the right and left vagal nerves is different. The innervation of the right vagus nerve is such that stimulating it results in profound bradycardia (slowing of the heart rate). The left vagal nerve has some innervation to the heart, but mostly innervates the visceral organs such as the gastrointestinal tract. It is known that stimulation of the left vagal nerve does not cause any significant deleterious side effects. Complex partial seizure is a common form of epilepsy, and some 30-40% of patients afflicted with this disorder are not well controlled by medications. Some patients have epileptogenic foci that may be identified and resected; however, many patients remain who have medically resistant seizures not amenable to resective surgery. Stimulation of the vagus nerve has been shown to reduce or abort seizures in experimental models. Early clinical trials have suggested that vagus nerve stimulation has beneficial effects for complex partial seizures and generalized epilepsy in humans. In addition, intermittent vagal stimulation has been relatively safe and well tolerated during the follow-up period available in these groups of patients. The minimal side effects of tingling sensations and brief voice abnormalities have not been distressing. Most nerves in the human body are composed of thousands of fibers, of different sizes designated by groups A, B and C, which carry signals to and from the brain. The vagus nerve, for example, may have approximately 100,000 fibers of the three different types, each carrying signals. Each axon (fiber) of that nerve conducts only in one direction, in normal circumstances. The A and B fibers are myelinated (i.e., have a myelin sheath, constituting a substance largely composed of fat), whereas the C fibers are unmyelinated. A commonly used nomenclature for peripheral nerve fibers, using Roman and Greek letters, is given in the table below, External Diameter Conduction Velocity Group (μm) (m/sec) Myelinated Fibers Aα or IA 12-20  70-120 Aβ: IB 10-15 60-80 II  5-15 30-80 Aγ 3-8 15-40 Aδ or III 3-8 10-30 B 1-3  5-15 Unmyelinted fibers C or IV 0.2-1.5 0.5-2.5 The diameters of group A and group B fibers include the thicknesses of the myelin sheaths. Group A is further subdivided into alpha, beta, gamma, and delta fibers in decreasing order of size. There is some overlapping of the diameters of the A, B, and C groups because physiological properties, especially the form of the action potential, are taken into consideration when defining the groups. The smallest fibers (group C) are unmyelinated and have the slowest conduction rate, whereas the myelinted fibers of group B and group A exhibit rates of conduction that progressively increase with diameter. Group B fibers are not present in the nerves of the limbs; they occur in white rami and some cranial nerves. Compared to unmyelinated fibers, myelinated fibers are typically larger, conduct faster, have very low stimulation thresholds, and exhibit a particular strength-duration curve or respond to a specific pulse width versus amplitude for stimulation. The A and B fibers can be stimulated with relatively narrow pulse widths, from 50 to 200 microseconds (μs), for example. The A fiber conducts slightly faster than the B fiber and has a slightly lower threshold. The C fibers are very small, conduct electrical signals very slowly, and have high stimulation thresholds typically requiring a wider pulse width (300-1,000 μs) and a higher amplitude for activation. Selective stimulation of only A and B fibers is readily accomplished. The requirement of a larger and wider pulse to stimulate the C fibers, however, makes selective stimulation of only C fibers, to the exclusion of the A and B fibers, virtually unachievable inasmuch as the large signal will tend to activate the A and B fibers to some extent as well. The vagus nerve is composed of somatic and visceral afferents (i.e., inward conducting nerve fibers which convey impulses toward the brain) and efferents (i.e., outward conducting nerve fibers which convey impulses to an effector). Usually, nerve stimulation activates signals in both directions (bi-directionally). It is possible, however, through the use of special electrodes and waveforms, to selectively stimulate a nerve in one direction only (unidirectionally). The vast majority of vagal nerve fibers are C fibers, and a majority are visceral afferents having cell bodies lying in masses or ganglia in the skull. The central projections terminate largely in the nucleus of the solitary tract which sends fibers to various regions of the brain (e.g., the hypothalamus, thalamus, and amygdala). The basic premise of vagal nerve stimulation for control of seizures is that vagal visceral afferents have a diffuse central nervous system (CNS) projection, and activation of these pathways has a widespread effect on neuronal excitability. The cervical component of the vagus nerve (10 th cranial nerve) transmits primarily sensory information that is important in the regulation of autonomic activity by the parasympathetic system. General visceral afferents constitute approximately 80% of the fibers of the nerve, and thus it is not surprising that vagal nerve stimulation (VNS) can profoundly affect CNS activity. With cell bodies in the nodose ganglion, these afferents originate from receptors in the heart, aorta, lungs, and gastrointestinal system and project primarily to the nucleus of the solitary tract which extends throughout the length of the medulla oblongata. A small number of fibers pass directly to the spinal trigeminal nucleus and the reticular formation. As might be predicted from the electrophysiologic studies, the nucleus of the solitary tract has widespread projection to cerebral cortex, basal forebrain, thalamus, hypothalamus, amygdala, hippocampus, dorsal raphe, and cerebellum as shown in FIG. 1D (from Epilepsia , vol. 3, suppl.2: 1990, page S2). Even though observations on the profound effect of electrical stimulation of the vagus nerve on central nervous system (CNS) activity, extends back to the 1930's, in the mid-1980s it was suggested that electrical stimulation of the vagus nerve might be effective in preventing seizures. Early studies on the effects of vagal nerve stimulation (VNS) on brain function focused on acute changes in the cortical electroencephalogram (EEG) of anesthetized animals. Investigators found that VNS could temporarily synchronize or desynchronize the electroencephalogram, depending on the level of anesthesia and the frequency or intensity of the vagal stimulus. These observations had suggested that VNS exerted its anticonvulsant effect by desynchronizing cortical electrical activity. However, subsequent clinical investigations have not shown VNS-induced changes in the background EEGs of humans. A study, which used awake and freely moving animals, also showed no VNS-induced changes in background EEG activity. Taken together, the findings from animal study and recent human studies indicate that acute desynchronization of EEG activity is not a prominent feature of VNS when it is administered during physiologic wakefulness and sleep, and does not explain the anticonvulsant effect of VNS. The mechanism by which vagal nerve stimulation (VNS) exerts its influence on seizures is not entirely understood. An early hypotheses had suggested that VNS utilizes the relatively specific projection from the nucleus of the solitary track to limbic structures to inhibit partial seizures, particularly those involving cortex, which regulates autonomic activity or visceral sensations such as in temporal lobe epilepsy. Afferent VNS at the onset of a partial seizure could abort the seizure in the same way somatosensory stimuli can abort a seizure from the rolandic cortex; however, chronic intermittent stimulation may also produce an alteration in limbic circuitry that outlasts the stimulus and decreases epileptogenesis or limits seizure spread. Support for this hypothesis comes from studies of fos immunoreactivity in the brain of rats in response to VNS. Fos is a nuclear protein resulting from expression of early immediate genes in highly active neurons. VNS causes a specific fos immunolabeling in amygdala and limbic neocortex, suggesting that the antiepileptic effect may be mediated in these areas. Such activation of genetic mechanisms could account for the apparent sustained antiepileptic effect of intermittent stimulation. Another possible mechanism that is being explored to explain an antiseizure effect of VNS is activation of the brainstem noradrenergic nuclei, lucus ceruleus and A5, which also show fos immunolabeling. Noradrenergic mechanisms are well known to influence seizure activity in genetic epilepsy-prone rats, and the anticonvulsant effects of VNS against maximal electroshock seizures can be blocked inactivation of the loc. ceruleus. Woodbury and Woodbury (1990) suggested that VS acts through increasing release of glycine or GABA since seizures induced by both PTZ and strychnine can be blocked by VNS. Other neruotransmitter systems may also be implicated since VNS increases cerebrospinal fluid homovanilic acid and 5-hydroxyindoleacetate, suggesting modulation of dopaminergic and serotonergic systems. Finally, a nonspecific alteration of activity in the brainstem reticular system with subsequent arousal must be considered. VNS appears to have similar efficacy in both partial and generalized seizures in experimental models and in human epilepsy consistent with a nonspecific effect. Furthermore, the same inhibition of interictal corticalspike activity as seen with VNS occurs in animals during electrical stimulation of the midbrain reticular formation or with thermal stimulation of somatosensory nerves in the rat tail. Reduction of experimental generalized spike wave by arousal has also been documented. Similarly, nonspecific afferent stimulation has been well demonstrated in humans to suppress focal spikes, generalized spike waves, and seizures. VNS may inhibit seizures directly at the level of cerebral cortical neuronal irritability, or at the level of diffuse ascending subcortical projection systems, or both. Thus, VNS is also well suited for the treatment of medication-resistant symptomatic generalized epilepsy (SGE), in which, characteristically both focal and generalized features are found on interictal EEGs and also in clinical seizure types. One type of prior non-pharmacological therapy for depression, migraines, neuropsychiatric disorders, and epilepsy is generally directed to the use of an implantable lead and an implantable pulse generator technology or “cardiac pacemaker-like” technology. In these applications, the pulse generator is programmed via a personnel computer (PC) based programmer that is modified and adapted with a programmer wand which is placed on top of the skin over the pulse generator implant site. Each parameter is programmed independent of the other parameters. Therefore, millions of different combinations of programs are possible. In the instant patent, preferably approximately nine programs are pre-selected. U.S. Pat. No. 3,796,221 (Hagfors) is directed to controlling the amplitude, duration and frequency of electrical stimulation applied from an externally located transmitter to an implanted receiver by inductively coupling. Electrical circuitry is schematically illustrated for compensating for the variability in the amplitude of the electrical signal available to the receiver because of the shifting of the relative positions of the transmitter-receiver pair. By highlighting the difficulty of delivering consistent pulses, this patent points away from applications such as the current application, where consistent therapy needs to be continuously sustained over a prolonged period of time (24 hours a day for years). The methodology disclosed is focused on circuitry within the receiver, which would not be sufficient when the transmitting coil and receiving coil assume significantly different orientation, which is likely in the current application. The present invention discloses a novel approach for this problem. U.S. Pat. No. 5,304,206 (Baker, Jr. et al) is directed to activation techniques for implanted medical stimulators. The system uses either a magnet to activate the reed switch in the device, or tapping which acts through the piezoelectric sensor mounted on the case of the implanted device, or a combination of magnet and tapping sequence. U.S. Pat. Nos. 4,702,254, 4,867,164 and 5,025,807 (Zabara) generally disclose animal research and experimentation related to epilepsy and the like and are directed to stimulating the vagus nerve by using pacemaker technology, such as an implantable pulse generator. These patents are based on several key hypotheses, some of which have since been shown to be incorrect. The pacemaker technology concept consists of a stimulating lead connected to a pulse generator (containing the circuitry and DC power source) implanted subcutaneously or submuscularly, somewhere in the pectoral or axillary region, with an external personal computer (PC) based programmer. Once the pulse generator is programmed for the patient, the fully functional circuitry and power source are fully implanted within the patient's body. In such a system, when the battery is depleted, a surgical procedure is required to disconnect and replace the entire pulse generator (circuitry and power source). These patents neither anticipate practical problems of an inductively coupled system for adjunct therapy of epilepsy, nor suggest solutions to the same for an inductively coupled system for adjunct therapy of partial complex or generalized epilepsy. FIG. 4 in all three above Zabara patents show the stimulation electrode around the right vagus nerve. It is well known that stimulation of right vagus can lead to profound bradycardia (slowing of the heart rate), an unwanted complication. U.S. Pat. No. 5,299,569 (Wernicke et al.) is directed to the use of implantable pulse generator technology for treating and controlling neuropsychiatric disorders including schizophrenia, depression, and borderline personality disorder. U.S. Pat. No. 5,752,979 (Benabid) is directed to a method of controlling epilepsy with stimulation directly into the brain, utilizing an implantable generator. More specifically, Benabid discloses electrically stimulating the external segment of the globus palliaus nucleus of the brain causing increased excitation, thereby increasing inhibition of neural activity in the subthalamic nucleus and reducing excitatory input to the substantia nigra leading to a reduction in the occurrence of seizures. U.S. Pat. No. 5,540,734 (Zabara) is directed to stimulation of one or both of a patient's trigeminal and glossopharyngeal nerve utilizing an implanted pulse generator. U.S. Pat. No. 5,031,618 (Mullett) discloses a position sensor for chronically implanted neuro stimulator for stimulating the spinal cord. The position sensor, located in a chronically implanted programmable spinal cord stimulator, modulates the stimulation signals depending on whether the patient is erect or supine. U.S. Pat. No. 4,573,481 (Bullara) is directed to an implantable helical electrode assembly configured to fit around a nerve. The individual flexible ribbon electrodes are each partially embedded in a portion of the peripheral surface of a helically formed dielectric support matrix. U.S. Pat. No. 3,760,812 (Timm et al.) discloses nerve stimulation electrodes that include a pair of parallel spaced apart helically wound conductors maintained in this configuration. U.S. Pat. No. 4,979,511 (Terry) discloses a flexible, helical electrode structure with an improved connector for attaching the lead wires to the nerve bundle to minimize damage. An implantable pulse generator and lead with a PC based external programmer is advantageous for cardiac pacing applications for several reasons, including: 1) A cardiac pacemaker must sense the intrinsic activity of the heart, because cardiac pacemakers deliver electrical output primarily during the brief periods when patients either have pauses in their intrinsic cardiac activity or during those periods of time when the heart rate drops (bradycardia) below a certain pre-programmed level. Therefore, for most of the time, in majority of patients, the cardiac pacemaker “sits” quietly monitoring the patient's intrinsic cardiac activity. 2) The stimulation frequency for cardiac pacing is typically close to 1 Hz, as opposed to approximately 20 Hz or higher, typically used in nerve stimulation applications. 3) Patients who require cardiac pacemaker support are typically in their 60's, 70's or 80's years of age. The combined effect of these three factors is that the battery in a pacemaker can have a life of 10-15 years. Most patients in whom a pacemaker is indicated are implanted only once, with perhaps one surgical pulse generator replacement. In contrast, patients with partial complex epilepsy or generalized epilepsy in whom electrical stimulation is beneficial are much younger as a group, typically ranging from 12 to 45 years in age. Also, stimulation frequency is typically 20 Hz or higher, and the total stimulation time per day is much longer than for cardiac pacemakers. As a result, battery drain is typically much higher for nerve stimulation applications than for cardiac pacemakers. The net result of these factors is that the battery will not last nearly as long as in cardiac pacemakers. Because the indicated patient population is also much younger, the expense and impact of surgical generator replacement will become significant, and detract from the appeal of this therapy. In fact, it has been reported in the medical literature that the battery life can be as short as one and half years for implantable nerve stimulator. (R. S. McLachlan, p. 233). There are several other advantages of the present inductively coupled system. 1) The hardware components implanted in the body are much less. This is advantageous for the patient in terms of patient comfort, and it decreases the chances of the hardware getting infected in the body. Typically, when an implantable system gets infected in the body, it cannot be easily treated with antibiotics and eventually the whole implanted system has to be explanted. 2) Because the power source is external, the physician can use stimulation sequences that are more effective and more demanding on the power supply, such as longer “on” time. 3) With the controlling circuitry being external, the physician and the patient may easily select from a number of predetermined programs, override a program, manually operate the device or even modify the predetermined programs. 4) The external inductively-coupled nerve stimulation (EINS) system is quicker and easier to implant. 5) The external pulse generator does not need to be monitored for “End-of-Life” (EOL) like the implantable system, thus resulting in cost saving and convenience. 6) The EINS system can be manufactured at a significantly lower cost of an implantable pulse generator and programmer system, providing the patient and medical establishment with cost effective therapies. 7) The EINS system makes it more convenient for the patient or caretaker to turn the device on during an “Aura” that sometimes precedes the seizures. Also, because programming the device is much simpler, the patient or caretaker may reprogram the device at night time by simply pressing one or two buttons to improve patient comfort. 8) Occasionally, an individual responds adversely to an implanted medical device and the implanted hardware must be removed. In such a case, a patient having the EINS systems has less implanted hardware to be removed and the cost of the pulse generator does not become a factor. In the conventional manner of implanting, a cervical incision is made above the clavicle, and another infraclavicular incision is made in the deltapectoral region for the implantable stimulus generator pocket. To tunnel the lead to the cervical incision, a shunt-passing tool is passed from the cervical incision to the generator pocket, where the electrode is attached to the shunt-passing tool and the electrode is then “pulled” back to the cervical incision for attachment to the nerve. This standard technique has the disadvantage that it is time consuming and it tends to create an open space in the subcutaneous tissue. Post surgically the body will fill up this space with serous fluid, which can be undesirable. To make the subcutaneous tunneling simpler and to avoid possible complication, one form of the implantable lead body is designed with a hollow lumen to aid in implanting. In this embodiment, a special tunneling tool slides into a hollow lumen. After the cervical and infraclavicular incisions are made, the tunneling tool and lead are simply “pushed” to the cervical incision and the tunneling tool is pulled out. Since the tunneling tool is inside the lead, no extra subcutaneous space is created around the lead, as the lead is pushed. This promotes better healing post-surgically. The apparatus and methods disclosed herein also may be appropriate for the treatment of other conditions, as disclosed in co-pending applications filed on Oct. 26, 1998, entitled APPARATUS AND METHOD FOR ADJUNCT (ADD-ON) THERAPY OF DEMENTIA AND ALZHEIMER'S DISEASE UTILIZING AN IMPLANTABLE LEAD AND AN EXTERNAL STIMULATOR and APPARATUS AND METHOD FOR ADJUNCT (ADD-ON) THERAPY FOR PAIN SYNDROMES UTILIZING AN IMPLANTABLE LEAD AND AN EXTERNAL STIMULATOR, the disclosures of which are incorporated herein by reference. SUMMARY OF THE INVENTION The apparatus and methodology of this invention generally relates to the adjunct (add-on) treatment of depression, migraine, neuropsychiatric disorders, partial complex epilepsy, generalized epilepsy, and involuntary movement disorders such as in Parkinson's disease. More particularly, the apparatus and methodology in accordance with the invention provides a more adaptable and less intrusive treatment for such conditions. In one embodiment of the invention, the apparatus consists of an easy to implant lead-receiver, an external stimulator containing controlling circuitry and power supply, and an electrode containing a coil for inductively coupling the external pulse generator to the implanted lead-receiver. A separately provided tunneling tool may be used as an aid for implanting the lead-receiver. In another embodiment of the invention, the external stimulator has two modes of operation: one with several pre-determined programs that may be selectively locked-out by the manufacturer or physician and another with a manual override. In another embodiment of the invention, the implantable lead-receiver is inductively coupled to the external stimulator via a patch electrode containing coil. One feature of this invention is to consistently deliver energy from an external coil to an internal coil in an ambulatory patient. A design of the external patch contains means for compensating for relative movement of the axis of the external and internal coils by deflecting the energy via targets located in the external patch. Another feature of this invention is to provide an apparatus to aid in implanting the lead-receiver, including a hollow lumen in the lead body to receive a tunneling tool. BRIEF DESCRIPTION OF THE DRAWINGS For the purpose of illustrating the invention, there are shown in accompanying drawing forms which are presently preferred, it being understood that the invention is not intended to be limited to the precise arrangement and instrumentalities shown. FIG. 1A is a diagram of the lateral view of brain and spinal cord, with its relationship to the vagus nerve. FIG. 1B is a diagram of the base of brain showing the relationship of vagus nerve to the other cranial nerves. FIG. 1C is a diagram of brain showing afferent and efferent pathways. FIG. 1D is diagram of vagal nerve afferents through the nucleus of the solitary tract. FIG. 2A is a diagram showing a patient wearing an external inductively-coupled nerve stimulator (EINS) system. FIG. 2B is a diagram showing two coils along their axis, in a configuration such that the mutual inductance would be maximum. FIG. 3A is a diagram showing the effects of two coils with axes at right angles. FIG. 3B is a diagram showing the effects of two coils with axes at right angles, with a ferrite target included. FIG. 4A is a side view of an external patch showing the transmitting coil and targets. FIG. 4B is top view of an external patch showing the transmitting coil and targets. FIG. 5 is a diagram showing the implanted lead-receiver and the transmitting coil. FIG. 6 is a diagram showing the implanted lead-receiver underneath the skin, also showing the relative position of the external coil. FIG. 7 is a diagram showing the proximal end of the lead-receiver. FIG. 8 is a diagram of circuitry within the proximal portion of the implanted lead-receiver. FIG. 9 is a diagram of the body of the lead-receiver. FIG. 10 is a diagram of a tunneling tool for aiding in the implantation of the lead-receiver. FIG. 11 is diagram of another tunneling tool for aiding in the implantation of the lead-receiver. FIG. 12 is a diagram of an external patch and external pulse generator. FIG. 13 is a prospective view of an external pulse generator. FIG. 14 is a flow diagram of the external pulse generator. FIG. 15 is a diagram of a hydrogel electrode. FIG. 16 is a diagram of a lead-receiver utilizing a fiber electrode at the distal end. FIG. 17 is a diagram of a fiber electrode wrapped around Dacron polyester. FIG. 18 is a diagram of a lead-receiver with a spiral electrode. FIG. 19 is a diagram of an electrode embedded in tissue. FIG. 20 is a diagram of an electrode containing steroid drug inside. FIG. 21 is a diagram of an electrode containing steroid drug in a silicone collar at the base of electrode. FIG. 22 is a diagram of an electrode with steroid drug coated on the surface of the electrode. FIG. 23 is a diagram of cross sections of implantable lead-receiver body showing different lumens. The following are reference numbers in the drawings: 1 . olfactory nerve 2 . optic nerve 3 . oculomotor nerve 4 . trochlear nerve 5 . trigeminal nerve 6 . abducens nerve 7 . facial nerve 8 . acoustic nerve 9 . glossopharyngeal nerve 11 . accessory nerve 12 . hypoglosal nerve 14 . nucleus tractus solitaris 15 . parabrachial nucleus (PB) 17 . nucleus locus coeruleus 18 . pons 19 . afferent pathway 20 . parabrachial nucleus (PB) 21 . efferent pathway 22 . nucleus locus coeruleus (LC) 24 . spinal cord 25 . thalamus 26 . hypothalamus 27 . corebellum 28 . orbito-frontal cortex 29 . amygdala 31 . cingulate gyrus 32 . patient 34 . implantable lead-receiver 35 . muscle 36 . coil-end of the external patch 37 . skin receptors 38 . wire of external patch 39 . primary somatic sensory cortex 40 . terminal end of the external patch 41 . primary motor cortex 42 . external stimulator 43 . external patch electrode 44 . belt of external stimulator 45 . ferrite target 46 . outer (transmitting primary) coil 48 . irner (receiving secondary) coil 49 . proximal end of lead-receiver 50 . adhesive portion of external patch electrode 51 . driving voltage of transmitter coil 52 . distal ball electrode 53 . zero voltage of receiver coil 54 . vagus nerve 55 . signal voltage across receiver coil 56 . carotid artery 57 . ferrite targets in external patch 58 . jugular vein 59 . body of lead-receiver 60 . working lumen of lead-receiver body 62 . hollow lumen of lead-receiver body 64 . schematic of lead-receiver circuitry 65 . cable connecting cathode and anode 68 . tuning capacitor in electrical schematic and in hybrid 69 . selector 70 . zenor diode 71 . pre-determined programs in block diagram 72 . capacitor used in filtering 73 . patient override in block diagram 74 . resister used in filtering 75 . programmable control logic in block diagram 76 . capacitor to block DC component to distal electrode 77 . programming station in block diagram 78 . case of lead-receiver 79 . pulse frequency oscillator in block diagram 80 . distal electrode in schematic of lead-receiver 81 . battery (DC) in block diagram 82 . working lumen in a cross section 83 . amplifier in block diagram 84 . hollow lumen in a cross-section 85 . indicator in block diagram 86 . small handle of alternate tunneling tool 87 . low pass filter in block diagram 88 . big handle of the tunneling tool 89 . antenna in block diagram 90 . skin 91 . metal rod portion of the tunneling tool with big handle 92 . punched holes in body of the lead receiver to promote fibrosis 93 . metal rod portion of the alternative tunneling tool with small handle 94 . alternative tunneling tool 95 . tunneling tool with big handle 96 . silicone covering proximal end 98 . hybrid assembly 100 . hydrogel 102 . platinum electrodes around hydrogel 104 . fiber electrode 105 . spiral electrode 106 . Dacron polyester or Polyimide 108 . platinum fiber 110 . exposed electrode portion of spiral electrode 112 . polyurethane or silicone insulation in spiral electrode 114 . “virtual” electrode 118 . excitable tissue 120 . non-excitable tissue 121 . steroid plug inside an electrode 122 . body of electrode 124 . electrode tip 126 . silicone collar containing steroid 128 . steroid membrane coating 130 . anchoring sleeve 132 A-F lumens 134 A-C larger hollow lumen for lead introduction DESCRIPTION OF THE INVENTION FIG. 2A shows a schematic diagram of a patient 32 with an implantable lead-receiver 34 and an external stimulator 42 , clipped on to a belt 44 in this case. The external stimulator 42 , may alternatively be placed in a pocket or other carrying device. An external patch electrode 36 provides the coupling between the external stimulator 42 and the implantable lead-receiver 34 . The external stimulator 42 is inductively coupled to the lead-receiver 34 . As shown in FIG. 2B, when two coils are arranged with their axes on the same line, current sent through coil 46 creates a magnetic field that cuts coil 48 which is placed subcutaneously. Consequently, a voltage will be induced in coil 48 whenever the field strength of coil 46 is changing. This induced voltage is similar to the voltage of self-induction but since it appears in the second coil because of current flowing in the first, it is a mutual effect and results from the mutual inductance between the two coils. Since these two coils are coupled, the degree of coupling depends upon the physical spacing between the coils and how they are placed with respect to each other. Maximum coupling exists when they have a common axis and are as close together as possible. The coupling is least when the coils are far apart or are placed so their axes are at right angles. As shown in FIG. 5, the coil 48 inside the lead-receiver 34 is approximately along the same axis as the coil 46 in the external skin patch 36 . As shown in FIG. 3A, when the axis of transmitting coil 46 is at right angles to the axis of the receiving coil 48 , a given driving voltage 51 results in zero voltage 53 across the receiving coil 48 . But, as shown in FIG. 3B by adding ferrite target 45 , a given driving voltage 51 through the transmitting coil 46 results in a signal voltage 55 across the receiver coil 48 . The efficiency is improved by having multiple ferrite targets. An alternate external patch shown in FIGS. 4A and 4B contains multiple targets 57 . FIG. 4A shows a side view of the patch, and FIG. 4B shows a top view of the patch. Having multiple targets 57 in the external patch 43 compensates for non-alignment of the axis between the transmitting coil 46 and receiving coil 48 . Since relative rotations between the axis of external transmitting coil 46 and internal receiving coil 48 which may occur during breathing, muscle contractions, or other artifacts are compensated for, results in continuous prolonged stimulation. Referring to FIG. 6, the implantable lead-receiver 34 looks somewhat like a golf “tee” and is the only implantable portion of the system. The “head” or proximal end 49 contains the coil 48 and electronic circuitry (hybrid) 98 which is hermetically sealed, and covered with silicone. It also has four anchoring sleeves 130 for tying it to subcutaneous tissue. FIG. 7 is a close-up view of the proximal portion 49 of the lead-receiver 34 containing the circuitry (hybrid) 98 . This circuitry is shown schematically in FIG. 8. A coil 48 (preferably approximately 15 turns) is directly connected to the case 78 . The external stimulator 42 and external patch 36 transmit the pulsed alternating magnetic field to receiver 64 whereat the stimulus pulses are detected by coil 48 and transmitted to the stimulus site (vagus nerve 54 ). When exposed to the magnetic field of transmitter 36 , coil 48 converts the changing magnetic field into corresponding voltages with alternating polarity between the coil ends. A capacitor 68 is used to tune coil 48 to the high-frequency of the transmitter 36 . The capacitor 68 increases the sensitivity and the selectivity of the receiver 64 , which is made sensitive to frequencies near the resonant frequency of the tuned circuit and less sensitive to frequencies away from the resonant frequency. A zenor diode 70 in the current path is used for regulation and to allow the current that is produced by the alternating voltage of the coil to pass in one direction only. A capacitor 72 and resistor 74 filter-out the high-frequency component of the receiver signal and thereby leave a current of the same duration as the burst of the high-frequency signal. Capacitor 76 blocks any net direct current to the stimulating electrode tip 80 , which is made of platinum/iridium (90%-10%). Alternatively, the stimulating electrode can be made of platinum or platinum/iridium in ratio's such as 80% Platinum and 20% Iridium. The circuit components are soldered in a conventional manner to an upper conductive layer on a printed circuit board. The case 78 is connected to the coil 48 and is made of titanium. The case 78 also serves as the return electrode (anode). The surface area of the anode exposed to the tissue is much greater than the surface area of the stimulating electrode 80 (cathode). Therefore, the current density at the anode is too low to unduly stimulate tissue that is in contact with the anode. Alternatively, a bipolar mode of stimulation can also be used. In the bipolar mode of stimulation the cathode and anode are in close proximity to each other. The body of the lead-receiver 34 is made of medical grade silicone (available from NuSil Technology, Applied silicone or Dow Chemical). Alternatively, the lead body 59 may be made of medical grade polyurethane (PU) of 55D or higher durometer, such as available from Dow Chemical. Polyurethane is a stiffer material than silicone. Even though silicone is a softer material, which is favorable, it is also a weaker material than PU. Therefore, silicone coated with Teflon (PTFE) is preferred for this application. PTFE coating is available from Alpa Flex, Indianapolis, Indiana. FIG. 9 shows a close-up of the lead body 59 showing two lumens 82 , 84 . Lumen 82 is the “working” lumen, containing the cable conductor 65 which connects to the stimulating electrode 52 . The other lumen 84 is preferably slightly larger and is for introducing and placing the lead in the body. Alternatively, lumen 84 may have small holes 92 punched along the length of the lead. These small holes 92 will promote fibrotic tissue in-growth to stabilize the lead position and inhibit the lead from migrating. Silicone in general is not a very slippery material, having a high coefficient of friction. Therefore, a lubricious coating is added to the body of the lead. Such lubricous coating is available from Coating Technologies Inc. (Scotch Plains, N.J.). Since infection still remains a problem in a small percentage of patients, the lead may be coated with antimicrobial coating such as Silver Sulfer Dizene available from STS Biopolymers, Henrietta, N.Y. The lead may also be coated with anti-inflammatory coating. The distal ball electrode 52 , shown in FIG. 6 is made of platinum/iridium (90% platinum and 10% iridium). Platinum/iridium electrodes have a long history in cardiac pacing applications. During the distal assembly procedure, the silicone lead body 59 is first cleaned with alcohol. The conductor cable 65 (available from Lake Region, Minn.) is passed through the “working” lumen 82 . The cable is inserted into the distal electrode 52 , and part of the body of electrode is crimped to the cable 65 with a crimper. Alternatively, the cable conductor 65 may be arc welded or laser welded to the distal electrode 52 . The distal end of the insulation is then slided over the crimp such that only the tissue stimulating portion of the distal electrode 52 is exposed. Following this, a small needle is attached to a syringe filled with medical glue. The needle is inserted into the distal end of insulation, and small amounts of medical glue are injected between the distal end of the insulation and distal electrode 52 . The assembly is then cured in an oven. As shown in FIGS. 9 and 10, a tunneling tool 95 is inserted into the empty lumen 84 to push the distal end (containing the cathode electrode 52 ) towards the vagus nerve 54 . The tunneling tool 95 , is comprised of a metal rod 91 and a handle 88 . As shown in FIG. 11, another tunneling tool 94 with a smaller handle 86 may also be used. Both are available from Popper and Sons, New Hyde Park, N.Y. or Needle Technology. Alternatively, the tunneling tool may be made of strong plastic or other suitable material. An external patch electrode 43 for inductive coupling is shown in FIG. 12 . One end of the patch electrode contains the coil 46 , and the other end has an adapter 40 to fit into the external stimulator 42 . The external patch electrode 43 , is a modification of the patch electrode available from TruMed Technologies, Burnsville, Minn. FIG. 13 shows a front view of an external stimulator 42 , which preferably is slightly larger than a conventional pager. The external stimulator 42 contains the circuitry and rechargeable or replaceable power source. The external stimulator 42 has two modes of operation. In the first mode of operation there are several pre-determined programs, preferably up to nine, which differ in stimulus intensity, pulse width, frequency of stimulation, and on-off timing sequence, e.g. “on” for 10 seconds and “off” for 50 seconds in repeating cycles. For patient safety, any number of these programs may be locked-out by the manufacturer or physician. In the second mode, the patient, or caretaker may activate the stimulation on at any time. This mode is useful for epileptic patients that have the characteristic “aura”, which are sensory signs immediately preceding the convulsion that many epileptics have. When the device is turned on, a green light emitting diode (LED) indicates that the device is emitting electrical stimulation. Pre-determined programs are arranged in such a way that the aggressiveness of the therapy increases from program #1 to Program #9. Thus the first three programs provide the least aggressive therapy, and the last three programs provide the most aggressive therapy. The following are examples of least aggressive therapy. Program #1: 1.0 mA current output, 0.2 msec pulse width, 15 Hz frequency, 15 sec ON time- 1.0 min OFF time, in repeating cycles. Program #2: 1.5 mA current output, 0.3 msec pulse width, 20 Hz frequency, 20 sec ON time- 2.0 min OFF time, in repeating cycles. The following are examples of intermediate level of therapy. Program #5: 2.0 mA current output, 0.2 msec pulse width, 25 Hz frequency, 20 sec ON time- 1.0 min OFF time, in repeating cycles. Program #6: 2.0 mA current output, 0.25 msec pulse width, 25 Hz frequency, 30 sec ON time- 1.0 min OFF time, in repeating cycles. The following are examples of most aggressive therapy. Program #8: 2.5 mA current output, 0.3 msec pulse width, 30 Hz frequency, 40 sec ON time- 1.5 min OFF time, in repeating cycles. Program #9: 3.0 mA current output, 0.4 msec pulse width, 30 Hz frequency, 30 sec ON time- 1.0 min OFF time, in repeating cycles. The majority of patients will fall into the category that require an intermediate level of therapy, such as program #5. The above are examples of the pre-determined programs that are delivered to the vagus nerve. The actual parameter settings for any given patient may deviate somewhat from the above. FIG. 14 shows a top level block diagram of the external stimulator 42 . As previously mentioned, there are two modes of stimulation with the external stimulator 42 . The first mode is a series of pre-determined standard programs 71 , differing in the aggressiveness of the therapy. The second mode is patient override 73 , where upon pressing a button, the device immediately goes into the active mode. The selector 69 which comprises of pre-determined programs 71 and patient override 73 feeds into programmable control logic 75 . The programmable control logic 75 controls the pulse frequency oscillator 79 . The output of the pulse frequency oscillator 79 is amplified 83 , filtered 87 and provided to the external coil (antenina) 89 , which is then transmitted to the implanted receiver 34 for stimulation of the nerve. The programmable control logic 75 is connected to an indicator 85 showing on-off status, as well as the battery status. The external stimulator 42 is powered by a DC battery 81 . A programming station 77 provides the capability to download and change programs if the need arises. Conventional integrated circuits are used for the logic, control and timing circuits. Conventional bipolar transistors are used in radio-frequency oscillator, pulse amplitude ramp control and power amplifier. A standard voltage regulator is used in low-voltage detector. The hardware and software to deliver these pre-determined programs is well known to those skilled in the art. The fabrication of the lead-receiver 34 is designed to be modular. Thus, several different components can be mixed and matched without altering the functionality of the device significantly. As shown in FIG. 6, the lead-receiver 34 components are the proximal end 49 (containing coil 48 , electrical circuitry 98 , and case 78 ), the lead body 59 containing the conductor 65 , and the distal electrode (cathode) 52 . In the modular design concept, several design variables are possible, as shown in the table below. Table of lead-receiver design variables Proxi- mal Con- End ductor Cir- (conn- cuitry ecting and Lead proxi- Distal Return Lead body- mal and End elec- body- Insulation Lead- distal Electrode- Electrode- trode Lumens materials Coating ends) Material Type Bipolar Single Poly- Lubri- Alloy of Pure Standard urethane cious Nickal- Platinum ball (PVP) Cobalt electrode Uni- Double Silicone Anti- Platinum- Hydrogel polar micro- Iridium electrode bial (Pt/Ir) alloy Triple Silicone Anti- Pt/Ir Spiral with Poly- inflam- coated electrode tetra- matory with fluoro- Titanium ethylene Nitride (PTFE) Coaxial Carbon Steroid eluting Fiber electrode Either silicone or polyurethane is suitable material for this implantable lead body 59 . Both materials have proven to have desirable qualities which are not available in the other. Permanently implantable pacemaker leads made of polyurethane are susceptible to some forms of degradation over time. The identified mechanisms are Environmental Stress Cracking (ESC) and Metal Ion Oxidation (MIO). For this reason silicone material is slightly preferred over polyurethane. Nerve-electrode interaction is an integral part of the stimulation system. As a practical benefit of modular design, any type of electrode described below can be used as the distal (cathode) stimulating electrode, without changing fabrication methodology or procedure significantly. When a standard ball electrode made of platinum or platinum/iridium is placed next to the nerve, and secured in place, it promotes an inflammatory response that leads to a thin fibrotic sheath around the electrode over a period of 1 to 6 weeks. This in turn leads to a stable position of electrode relative to the nerve, and a stable electrode-tissue interface, resulting in reliable stimulation of the nerve chronically without damaging the nerve. Alternatively, other electrode forms that are non-traumatic to the nerve such as hydrogel, platinum fiber, or steroid elution electrodes may be used with this system. The concept of hydrogel electrode for nerve stimulation is shown schematically in FIG. 15 . The hydrogel material 100 is wrapped around the nerve 54 , with tiny platinum electrodes 102 being pulled back from nerve. Over a period of time in the body, the hydrogel material 100 will undergo degradation and there will be fibrotic tissue buildup. Because of the softness of the hydrogel material 100 , these electrodes are non-traumatic to the nerve. The concept of platinum fiber electrodes is shown schematically in FIG. 16 . The distal fiber electrode 104 attached to the lead-receiver 34 may be platinum fiber or cable, or the electrode may be thin platinum fiber wrapped around Dacron polyester or Polyimide 106 . As shown in FIG. 17, the platinum fibers 108 may be woven around Dacron polyester fiber 106 or platinum fibers 108 may be braided. At implant, the fiber electrode 104 is loosely wrapped around the surgically isolated nerve, then tied loosely so as not to constrict the nerve or put pressure on the nerve. As a further extension, the fiber electrode may be incorporated into a spiral electrode 105 as is shown schematically in FIG. 18 . The fiber electrode 110 is on the inner side of polyurethane or silicone insulation 112 which is heat treated to retain its spiral shape. Alternatively, steroid elution electrodes may be used. After implantation of a lead in the body, during the first few weeks there is buildup of fibrotic tissue in-growth over the electrode and to some extent around the lead body. This fibrosis is the end result of body's inflammatory response process which begins soon after the device is implanted. The fibrotic tissue sheath has the net effect of increasing the distance between the stimulation electrode (cathode) and the excitable tissue, which is the vagal nerve in this case. This is shown schematically in FIG. 19, where electrode 52 when covered with fibrotic tissue becomes the “virtual” electrode 114 . Non-excitable tissue is depicted as 120 and excitable tissue as 118 . A small amount of corticosteroid, dexamethasone sodium phosphate commonly referred to as “steroid” or “dexamethasone” placed inside or around the electrode, has significant beneficial effect on the current or energy threshold, i.e. the amount of energy required to stimulate the excitable tissue. This is well known to those familiar in the art, as there is a long history of steroid elution leads in cardiac pacing application. It takes only about 1 mg of dexamethasone to produce the desirable effects. Three separate ways of delivering the steroid drug to the electrode nerve-tissue interface are being disclosed here. Dexamethasone can be placed inside an electrode with microholes, it can be placed adjacent to the electrode in a silicone collar, or it can be coated on the electrode itself. Dexamethasone inside the stimulating electrode is shown schematically in FIG. 20. A silicone core that is impregnated with a small quantity of dexamethasone 121 , is incorporated inside the electrode. The electrode tip is depicted as 124 and electrode body as 122 . Once the lead is implanted in the body, the steroid 121 elutes out through the small holes in the electrode. The steroid drug then has anti-inflammatory action at the electrode tissue interface, which leads to a much thinner fibrotic tissue capsule. Another way of having a steroid eluting nerve stimulating electrode, is to have the steroid agent placed outside the distal electrode 52 in a silicone collar 126 . This is shown schematically in FIG. 21 . Approximately 1 mg of dexamethasone is contained in a silicone collar 126 , at the base of the distal electrode 52 . With such a method, the steroid drug elutes around the electrode 52 in a similar fashion and with similar pharmacokinetic properties, as with the steroid drug being inside the electrode. Another method of steroid elution for nerve stimulation electrodes is by coating of steroid on the outside (exposed) surface area of the electrode. This is shown schematically in FIG. 22 . Nafion is used as the coating matrix. Steroid membrane coating on the outside of the electrode is depicted as 128 . The advantages of this method are that it can easily be applied to any electrode, fast and easy manufacturing, and it is cost effective. With this method, the rate of steroid delivery can be controlled by the level of sulfonation. A schematic representation of the cross section of different possible lumens is shown in FIG. 23 . The lead body 59 can have one, two, or three lumens for conducting cable, with or without a hollow lumen. In the cross sections, 132 A-F represents lumens(s) for conducting cable, and 134 A-C represents hollow lumen for aid in implanting the lead. Additionally, different classes of coating may be applied to the implantable lead-receiver 34 after fabrication. These coatings fall into three categories, lubricious coating, antimicrobial coating, and anti-inflammatory coating. The advantage of modular fabrication is that with one technology platform, several derivative products or models can be manufactured. As a specific practical example, using a silicone lead body platform, three separate derivative or lead models can be manufactured by using three different electrodes such as standard electrode, steroid electrode or spiral electrode. This is made possible by designing the fabrication steps such that the distal electrodes are assembled at the end, and as long as the electrodes are mated to the insulation and conducting cable, the shape or type of electrode does not matter. Similarly, different models can be produced by taking a finished lead and then coating it with lubricious coating or antimicrobial coating. In fact, considering the design variables disclosed in table 1, a large number ofcombinations are possible. Of these large number of possible combinations, about 6 or 7 models are planned for manufacturing. These include lead body composed of silicone and PTFE with standard ball electrodes made of platinum/iridium alloy, and silicone lead body with spiral electrode. In addition to the neuromodulation of a cranial nerve such as the vagus nerve described above, neuromodulation of other nerves in the body can be performed. For example, neuromodulation of sacral nerve, which has beneficial effects for urinary incontinance, can be performed using an implantable lead-receiver and an external stimulator containing pre-determined program, where the two are inductively coupled. In such a case, the secondary coil wold be implanted in the lower abdominal region. While various embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention.
An apparatus and method for adjunct (add-on) therapy of depression, migraine, neuropsychiatric disorders, partial complex epilepsy, generalized epilepsy and involuntary movement disorders comprises an implantable lead-receiver, and an external stimulator having controlling circuitry, a power source, and a coil to inductively couple the stimulator to the lead-receiver. The external stimulator emits electrical pulses to stimulate a cranial nerve such as the left vagus nerve according to a predetermined program. In a second mode of operation, an operator may manually override the predetermined sequence of stimulation.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a garment steamer. More particularly, the present invention relates to a transportable garment steamer providing improved efficiency, effectiveness and convenience in use. 2. Description of the Prior Art Garment steamers for use in the home are well known. For example, U.S. Pat. No. 5,609,047, U.S. Pat. No. 5,123,266, U.S. Pat. No. 4,426,857 and EP 0 079 866 each disclose a different variation on such a device. None of the above, provide for a garment steamer that cooperates with a variety of different attachments to create a variety of different steam or vapor emitting effects, generates/emits a concentration of ions and/or ozone, and has a variety of other advantageous features. Such features include a collapsible/telescopic hanger/rod assembly, a separable fluid container, a separable insulated hose, as well as various safety features for improving safety in use. Thus, there is a need for a portable home garment steamer having the aforementioned features to provide greater flexibility, convenience, and efficiency in use. Also, preferably the steamer has a body that is sleek, compact, lightweight, and easily transportable. SUMMARY OF THE INVENTION It is an object of the present invention to provide a garment steamer for use in a home. It is another object of the present invention to provide such a garment steamer that is sleek, compact and lightweight. It is still another object of the present invention to provide such a garment steamer that improves flexibility and efficiency in use. It is yet another object of the present invention to provide such a garment steamer that cooperates with a variety of different attachments for producing a variety of different steam or vapor emitting effects. It is a further object of the present invention to provide such a garment steamer that has a selectively adjustable and collapsible telescopic hanger/rod assembly. It is still a further object of the present invention to provide such a garment steamer that has an ion and/or ozone generating/emitting feature. These and other objects and advantages of the present invention are achieved by a garment steamer having a housing or base, a separable fluid container in separable fluid communication with a fluid heating assembly, a fluid heating assembly, a separable hose in separable fluid communication with the fluid heating assembly as well as with a variety of attachments, an adjustable and collapsible telescopic hanger/rod assembly, and at least one ion/ozone generator/emitter assembly. BRIEF DESCRIPTION OF THE DRAWINGS The present invention is more fully understood by reference to the following detailed description of an illustrative embodiment in combination with the drawings identified below. FIG. 1 is a side view of the garment steamer in accordance with an illustrative embodiment of the present invention; FIG. 2 is a side partially sectional view of the garment steamer of FIG. 1 ; FIG. 3 is a side view of the garment steamer of FIG. 1 , showing the fluid container separated from the base; FIG. 4 is a side section view of an illustrative adapter-hose connection; FIG. 5 is a first view of a collapsible hanger for cooperating with the garment steamer of FIG. 1 , showing the hanger in an extended or open position; FIG. 6 is a second view of the collapsible hanger of FIG. 5 , showing the hanger in a collapsed or closed position; FIG. 7 is a side view of a straightening attachment for cooperating with the garment steamer of FIG. 1 ; FIG. 8 is a top view of the straightening attachment of FIG. 7 ; FIG. 9 is an end view of the straightening attachment of FIG. 7 ; FIG. 10 is a side view of a concentrating attachment for cooperating with the garment steamer of FIG. 1 ; FIG. 11 is a top view of the concentrating attachment of FIG. 10 ; FIG. 12 is an end view of the concentrating attachment of FIG. 10 ; FIG. 13 is a side view of a wand attachment for cooperating with the garment steamer of FIG. 1 ; FIG. 14 is a side view of a nozzle attachment for cooperating with the garment steamer of FIG. 1 ; FIG. 15 is a top view of the nozzle attachment of FIG. 14 ; FIG. 16 is an end view of the nozzle attachment of FIG. 14 ; FIG. 17 is a side view of a brush accessory for cooperating with the nozzle attachment of FIG. 14 ; FIG. 18 is a top view of the brush accessory of FIG. 17 ; FIG. 19 is an end view of the brush accessory of FIG. 17 ; FIG. 20 is a side view of a fluff accessory for cooperating with the nozzle attachment of FIG. 14 ; and FIG. 21 is an end view of the fluff accessory of FIG. 20 . DETAILED DESCRIPTION OF THE INVENTION Referring to the drawings and in particular, FIGS. 1 and 2 , there is shown a garment steamer in accordance with an illustrative embodiment of the present invention generally represented by reference numeral 1 . Garment steamer 1 has a housing or base 10 , a fluid container 20 , a fluid heating assembly 30 , a hose 40 , a hanger/rod assembly 50 , and at least one ion/ozone generator/emitter assembly 70 . Preferably, garment steamer 1 cooperates with a variety of different attachments 80 to provide a variety of different steaming or vaporizing effects. Preferably, base 10 has a wide relatively flat lower portion 12 and a tall relatively cylindrical upper portion 14 configured to distribute the weight of steamer 1 such that the center of gravity thereof is lowered closer to the ground thereby improving the overall stability of the device. Also preferably, lower portion 12 and upper portion 14 each enclose a portion of fluid heating assembly 30 . Lower portion 12 preferably has a number of transport structures 16 mounted to a bottom surface thereof. Preferably, transport structures 16 have at least four lightweight wheels made preferably of a durable plastic material. However, transport structures 16 can be of any type known to facilitate easy transport of steamer 1 . Lower portion 12 preferably also has a cord reel (not shown) for selectively retaining or storing a power chord (not shown). Alternatively, lower portion 12 can have a cord wrap 18 that allows a user to wrap and store a power cord (also not shown). In addition, lower portion 12 preferably has a control 19 disposed thereon for controlling one or more operative functions, including powering the device. Control 19 can be of any type known and sufficient to provide the user with effective access and easy use. Upper portion 14 preferably is centrally disposed above lower portion 12 . Upper portion 14 preferably has a recess 11 with a first connector 13 for receiving fluid container 20 and connecting fluid container 20 to fluid heating assembly 30 , a second connector 15 for connecting fluid heating assembly 30 to hose 40 , and a third connector 17 for connecting hanger/rod assembly 50 . Referring to FIGS. 2 and 3 , fluid container 20 preferably can be removed or separated from recess 11 . Fluid container 20 preferably has a handle 22 and a cap 24 . Handle 22 preferably enables the user to easily manage or cope with fluid container 20 as he/she selectively connects and/or separates the fluid container to and from recess 11 . In the illustrative embodiment shown in FIG. 3 , cap 24 preferably is removable to allow the user to add fluid into fluid container 20 when the container is separated from recess 11 . Cap 24 preferably also has a spring valve 26 and an air vent 28 . Spring valve 26 can release when fluid container 20 has a volume of fluid therein and is placed into recess 11 such that cap 24 is in fluid communication with fluid heating assembly 30 via first connector 13 . The release of spring valve 26 allows gravity to force the fluid in fluid container 20 into fluid heating assembly 30 . Air vent 28 preferably prevents a vacuum from being created to ensure that the fluid can flow until an equilibrium point is reached with respect to the fluid position between fluid container 20 and fluid heating assembly 30 . Once the equilibrium point is reached, the fluid stops flowing. Referring to FIG. 2 , fluid heating assembly 30 preferably is centrally disposed in base 10 and has a fluid inlet 32 located in lower portion 12 of base 10 , a boiler 34 , and a fluid outlet 36 located in upper portion 14 of base 10 . Fluid inlet 32 preferably has a first tube 33 connecting boiler 34 and first connector 13 so that the first connector is in separable or releasable fluid communication with fluid container 20 . Boiler 34 preferably is die-cast and produces steam or vapor within a relatively short period of time (i.e. about 1 to about 2 minutes). Fluid outlet 36 preferably has a second tube 37 connecting boiler 34 to second connector 15 so that the second connector is in separable or releasable fluid communication with hose 40 . Referring to FIG. 4 , hose 40 is preferably an insulated hose that can be removably or separably connected to second connector 15 shown in FIG. 1 . Preferably hose 40 is flexible and has at least an inner tube 42 and an outer tube 44 surrounding inner tube 42 . Inner tube 42 preferably facilitates thermal retention as well as fluid flow. Inner tube 42 can also preferably be formed of any suitable material for conducting heated steam or vapor. Outer tube 44 preferably provides a layer of insulation that improves thermal efficiency and increases safety in user handling. Preferably, hose 40 has an adapter 45 at each end thereof for selectively cooperating with second connector 15 and/or the variety of different attachments 80 . Preferably, adapter 45 has a tubular hollow shaft 46 with a number of annular ribs or barbs 47 and an abutment 48 disposed thereon. Barbs 47 and abutment 48 cooperate with the ends of hose 40 and a fastener 49 to frictionally connect adapter 45 , inner tube 42 , and outer tube 44 . It is noted that various other known connector assemblies may also be employed to accomplish the purpose of securely sealing and connecting hose 40 with the variety of different attachments 80 and second connector 15 , thereby providing fluid communication between heating assembly 30 and the variety of attachments. Thus, preferably when fluid container 20 is filled with fluid and placed in recess 11 such that cap 24 engages first connector 13 , fluid can flow through fluid inlet 32 and into boiler 34 to be rapidly heated or vaporized, which vapor is conveyed through fluid outlet 36 into hose 40 and out one of the variety of attachments 80 . Accordingly, the user is able to direct, manipulate or control the intensity and/or emission of the vapor to provide a variety of different steaming or vaporizing effects. Referring to FIGS. 5 and 6 , in one embodiment of the present invention, garment steamer 1 preferably cooperates with hanger/rod assembly 50 to support or hold garments during the steaming process. Hanger/rod assembly 50 is preferably selectively telescopically adjustable and collapsible. Preferably, assembly 50 has a rod 51 telescopically connected to base 10 and a hanger 52 , connected, preferably integrally to rod 51 to collapsibly cooperate therewith. Preferably, rod 51 is telescopically received and retained in base 10 and can have a number of locks 53 to allow the rod 51 to be securely fixed at a variety of different vertical positions. Also, rod 51 can cooperate with a hose retaining mechanism 41 for storing hose 40 when not in use. Further, rod 51 can be separably connected to base 10 and can have a selectively collapsible tripod or stand (not shown) connected or integral therewith. The collapsible stand preferably cooperates with rod 51 to allow the rod to both stand alone, separate from base 10 , and to be selectively received, supported and/or retained by the base. Thus, base 10 can serve as a holder and/or as a storage container for rod 51 when not in use. Preferably, hanger 52 has an upper support or hub 54 , shown clearly in FIGS. 5 and 6 , having one or more hanging supports 55 . Hanger 52 also preferably has at least two arms 56 pivotally connected to hub 54 . Each arm 56 has at least one hinge 57 pivotally connecting at least two beams 58 . Further, hanger 52 preferably has a lock/release button 59 for selectively positioning and securing arms 56 in a number of different positions to accommodate different types of garments. Still further, hanger 52 has at least two ribs 60 for cooperating with a slider 61 , which is slidable along rod 51 , to facilitate accomplishing the selective positioning of arms 56 . Also, hanger 52 , in addition to being connected, and preferably integral with rod 51 , can be selectively separable therefrom. This creates a greater flexibility in use, enabling the user to separably hang or support a garment on a wall or door. Also preferably, hanger 52 can be slidable along rod 51 such that the hanger can be selectively and securely positioned at any point along the rod. Referring to FIG. 2 , in another embodiment of the present invention, garment steamer 1 preferably cooperates with an ion and/or ozone assembly 70 to infuse a garment with odor-neutralizing ions and/or ozone. Preferably, assembly 70 has one or more ion and/or ozone generator(s) 71 and one or more ion and/or ozone emitter(s) 72 operatively connected with the one ion and/or ozone generator(s). However, it is noted that ion and/or ozone assembly 70 can be any device or system capable of generating and/or emitting ions and/or ozone, such as for example, an ultraviolet (UV) light source (not shown). Preferably, the ion and/or ozone generator 71 and the ion and/or ozone emitter 72 can be positioned at any location in relation to garment steamer 1 , suitable to optimize the effective operation thereof. The ion and/or ozone generator 71 can be any device suitable for adjustably generating voltage outputs of varying intensity and/or polarity as well as different combinations thereof. The ion and/or ozone emitter 72 can have any configuration suitable to conform to the arrangement and operation of garment steamer 1 . For example, the ion and/or ozone emitter 72 can be a conductive needle, a conductive plate or any other like structure. Further, the ion and/or ozone emitter 72 can be formed of any material suitable to effectively emit ions and/or ozone as well as to conform to the constraints associated the arrangement and/or operation of the garment steamer 1 . Examples of materials that might be used include, for example, conductive metal, conductive polymer, carbon material, or silicon based material. It is noted that the ion and/or ozone generator 71 and the ion and/or ozone emitter 72 are preferably configured for safety, as well as protection from damage caused by extensive and prolonged use. It is noted that the variety of different attachments 80 , which cooperate with garment steamer 1 , to provide a variety of different steaming or vaporizing effects, can preferably be of any type suitable for effective use with heated vapor. For example, these attachments 80 may be a straightening attachment, as shown in FIGS. 7 through 9 , a concentrator attachment, as shown in FIGS. 10 through 12 , a wand attachment, as shown in FIG. 13 , and a nozzle attachment, as shown in FIGS. 14 through 16 . It is further noted that each of the variety of different attachments 80 can be configured to selectively cooperate with a variety of different accessory parts. For example, a brush accessory, as shown in FIGS. 17 through 19 , or a fluff accessory, as shown in FIGS. 20 and 21 . Thus, the accessory parts provide greater flexibility and efficiency in use. Having identified and described the preferred embodiments of the present invention, it is appreciated that details may be modified in a variety of ways and that alternative embodiments are also within the scope of the present invention. For example, it is possible to provide at least one of the variety of different attachments 80 , shown in FIGS. 7 through 16 and/or accessory parts shown in FIGS. 17 through 21 , with an ion and/or ozone generator and a corresponding ion and/or ozone emitter (not shown), having at least each of the attributes previously preferably described with respect to each. In this alternative embodiment, the ion and/or ozone emitter is preferably situated to effectively infuse or introduce ions and/or ozone into a garment. This introduction of ions and/or ozone into a garment has an odor-neutralizing effect and thus facilitates in the removal of lingering odors from various garments and fabrics. It is noted that the ion and/or ozone emitter can preferably be located in a selectively removable protective casing (not shown) thus preserving the integrity of the ion and/or ozone emitter and allowing selective access thereto, for cleaning and/or replacement thereof. In another example, it is preferably possible to situate an ion and/or ozone generator and a corresponding ion and/or ozone emitter (not shown), having at least the attributes previously preferably described with respect to each, in base 10 proximate fluid outlet 36 . In this embodiment, the ion and/or ozone emitter is preferably situated to effectively infuse or introduce ions and/or ozone into the vaporized fluid exiting fluid outlet 36 . It is noted that infusing the vaporized fluid with ions and/or ozone can have a beneficial cleansing effect thereon to reduce the build up of dust and other debris, thereby improving efficiency and effectiveness of garment steamer 1 as well as extending the useful life thereof. The present invention having been thus described with particular reference to the illustrated embodiments thereof, it will be obvious that various changes and modifications may be made therein without departing from the spirit of the present invention as defined herein.
There is provided a garment steamer for domestic use that cooperates with a variety of different attachments to provide a variety of different steam or vapor emitting effects. The garment steamer also has an ionic and/or ozone generating/emitting feature to facilitate neutralizing odor and removing undesirable particulate from a garment. The garment steamer may also have a hanger and rod assembly in which a collapsible hanger selectively cooperates with a telescopic rod, which is connected to a base, such that the hanger can be selectively positioned at any location along the height of the rod and/or disengaged from the rod. The garment steamer also includes a fluid heating assembly enclosed in the base, a separable fluid container in separable fluid communication with the fluid heating assembly, and a separable hose in separable fluid communication with the fluid heating assembly, as well as with the variety of different attachments.
3
FIELD OF THE INVENTION This invention relates to dryers used in papermaking in general. More particularly, this invention relates to dryers of the single tier type. BACKGROUND OF THE INVENTION Paper is made by forming a mat of fibers, normally wood fibers, on a moving wire screen. The fibers are in a dilution with water constituting more than ninety-nine percent of the mix. As the paper web leaves the forming screen, it may be still over eighty percent water. The paper web travels from the forming or wet end of the papermaking machine and enters a pressing section where, with the web supported on a felt, the moisture content of the paper is reduced by pressing the web to a fiber content of between thirty-five and fifty-five percent. After the pressing section, the paper web is dried on a large number of steam heated dryer rolls, so the moisture content of the paper is reduced to about five percent. The dryer section makes up a considerable part of the length of a papermaking machine. The web as it travels from the forming end to the take-up roll may extend a quarter of a mile in length. A major fraction of this length is taken up in the dryer section. As the paper industry has moved to higher web speeds, upwards of four- to five-thousand feet per minute, the dryer section has had to become proportionately longer because less drying is accomplished at each dryer as the paper moves more quickly through the dryers. One type of dryer, known as a two-tier dryer, has two rows of steam heated dryer rolls four to seven feet in diameter. The dryer rolls in the upper and lower rows are staggered. The paper web runs in a meandering fashion from an upper dryer roll to a lower dryer roll and then on to an upper roll over as many rolls as is required. An upper felt backs the web as it travels over the upper dryer rolls, and leaves the paper web as it travels to the lower rolls. The upper felt is turned by felt reversing rolls spaced between the upper rolls. On the lower dryer rolls the web is supported by a lower felt, which is also turned between lower dryer rolls by lower felt reversing rolls. This apparatus advantageously dries first one side and then the other of the web, however, the paper web is unsupported for a length as it passes from the upper dryer rolls to the lower dryer rolls, and from the lower rolls to the upper rolls. Unsupported paper webs present a problem as web speed increases. At higher web speeds, the paper interacts with the air and can begin to flutter. This fluttering can wrinkle and crease the paper web, seriously damaging the quality of the paper produced. Further, the fluttering can lead to tears and web failure, with all the cost and downtime associated with paper lost during the rethreading operation. A first approach to overcoming this problem was to use a single felt or a wire which traveled with the paper web over both the upper and lower dryers so that the paper was supported through the open draws. This approach limited paper flutter in the open draws, but, because the blanket was disposed between the paper web to be dried and the lower dryer rolls, the effectiveness of the lower dryer rolls was substantially diminished. A further dryer development is the single tier of dryer rolls with vacuum reversing rolls disposed therebetween. The vacuum rolls, such as shown in U.S. Pat. No. 4,882,854 (Wedel, et al.), use vacuum to clamp the edges of the paper to the reversing roll to prevent edge flutter, and use drilled holes or central grooves to allow passage of the trapped boundary layer between the blanket and the reversing rolls. Single tier dryer systems are successful in increasing the drying rate and shortening the dryer section of a papermaking machine. It is necessary in order to dry both sides of the web effectively to employ both top felted and bottom felted single tiers of dryers. Bottom felted dryers have the disadvantage in that removing broke from between the felt and the dryer can be a difficult and time consuming operation. On the other hand, in the top felted dryers, when the felts are loosened, broke drops with relative ease out from between the felt and the dryer rolls. A further possible problem with single tier dryers is the sequential drying of first one side and then the other. When both sides of the sheet are not dried simultaneously curl can develop in the paper due to the effect of drying on the dimensions of the fibers on one side of the sheet as opposed to the still wet fibers on the other which can produce a tendency for the paper web to curl both in the cross machine and in the machine direction. What is needed is a shorter dryer section which dries both sides of the web simultaneously and which facilitates rapid clearing of broke from the dryer section. SUMMARY OF THE INVENTION The paper dryer section of this invention employs a single tier of all top felted dryers. The dryer rolls are preferably of increased diameter, 8-20 feet in diameter, as opposed to the usual 6 foot diameter. The single tier arrangement, together with the top felting, assists in the removal of broke. Air caps are employed over the dryer rolls to simultaneously dry both sides of the web to prevent curl and to increase drying rates. The air caps employ blown air at a temperature of 200-900 degrees Fahrenheit and air speeds of 8,000-40,000 feet per minute. The felt employed is foraminous with a permeability of between 300-1500 cubic feet per minute per square foot and is designed to withstand peak temperatures of up to 900 degrees Fahrenheit and average temperatures of between 500-600 degrees Fahrenheit. Either one, or more advantageously, two felt rolls or two vacuum rolls in a vacuum box are disposed between the dryer rolls to maximize the circumferential wrap of the web and, at the same time, support and transport the web between dryers. It is a feature of the present invention to provide a papermaking dryer apparatus which provides an increased rate of drying of a paper web. It is another feature of the present invention to provide a more compact papermaking dryer section. It is a further feature of the present invention to provide a papermaking dryer which prevents the formation of curl in the paper web being dried. It is an additional feature of the present invention to provide a dryer section of a papermaking machine in which the ready removal of broke is facilitated. It is yet another feature of the present invention to provide a dryer section of a papermaking machine which may be mounted directly to the mill floor wherein machine vibration and installation costs are reduced. Further objects, features and advantages of the invention will be apparent from the following detailed description when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic side-elevational view of the dryer section of this invention employing two reversing rolls. FIG. 2 is a somewhat schematic side-elevational view of the dryer section of this invention employing a single reversing roll. FIG. 3A is the wet end of an exemplary papermaking machine for supplying a web to the dryer section of FIG. 1. FIG. 3B is a schematic view of the dry end of an exemplary papermaking machine employing the dryer section of FIG. 1. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring more particularly to FIGS. 1-3B wherein like numbers refer to similar parts, a papermaking machine 20 is illustrated in FIGS. 3A-3B. The papermaking machine employs a dryer section 22. The dryer section is composed of dryer rolls 24 which are internally steam heated and will preferably have a diameter of eight to as large as twenty feet as opposed to conventional dryers of six feet in diameter. The dryer rolls rotate about axes 26, the axes lying in a single plane. Such an arrangement of dryer rolls is known as a single tier dryer section. A paper web 28 is wrapped onto the dryer rolls 24 by first a first felt 30, then a second felt 32, and finally a third felt 34 in sequence, as the paper web moves through the dryer section 22. Each dryer roll 24 has a dryer surface 36. The dryer surface 36 is cylindrical and thus, has a circular cross-section. The circular cross-section has an uppermost or zenith point 38 and a lowermost or nadir point 40 at the bottom of each dryer roll 24. The felts 30, 32, 34 wrap the dryer rolls 24 so the tops or zenith points 38 of the rolls are covered but the nadir 40 or bottom of the rolls are not overwrapped. This application of the felts is referred to as top felting. A top felted dryer section 22 has an advantage over bottom felted dryer systems in which the felts wrap the bottom or nadir points of the dryer rolls, in that broke may be much more easily cleared from the a top felted dryer section should a web break occur. A papermaking machine 20 such as illustrated in FIGS. 3A-3B can operate in the range of 6,500 feet per minute. Paper breaks, while being highly undesirable on papermaking machines, are an inevitable occurrence particularly when the machine is changing between various grades of paper or when extensive maintenance and felt changes have been made. The high speed of the papermaking machine leads to an accumulation of a considerable quantity of broke or paper within the papermaking machine when a break occurs before the break can be detected and the machines shut down. The result is that the broken paper web will often wrap around individual dryer rolls. With top felting, the felts can be slacked off from the dryer rolls 24 and any accumulated paper readily removed from and dropped down from the dryer rolls. This is in contrast to bottom felted single tier dryers where it is necessary to fish the broke out from between the felt and the dryers, the felts forming pockets about the dryers which can accumulate and retain broken paper. The disadvantage of single tier top felted dryers is that typically the paper web is dried from only a single side. This unidirectional drying of the paper web results in dimensional changes between the dryer side and the felt side of the web which, in turn, results in a permanent set or curling in the paper web which is an undesirable result. The dryer section 22 overcomes this problem by employing air caps 42 to dry the felt side of the web. The air caps 42 are hoods which overlie the upper portions 44 of the dryer rolls 24 and blow high velocity hot air through the felts to dry the upper surface of the web simultaneously and preferably at the same rate as the roll side of the paper is dried by the steam heat transmitted to the surface 36 of the dryer rolls 24. In order to allow the passage of air through the felts 30, 32, 34 the felts must be of a porous or foraminous nature. Thus, the felts employed in the dryer section 22 will have a porosity in the range of three-hundred to fifteen-hundred cubic feet per minute per square foot as that porosity is typically measured by those skilled in the art of the design and construction of papermaking felts. The air supplied by the air caps 42 may have a temperature range of two-hundred to one-thousand degrees Fahrenheit and be blown at a velocity of between eight-thousand and forty-thousand feet per minute. The high air temperatures require felts which can withstand up to one-thousand degrees Fahrenheit for brief periods of time and average temperatures in the range of five-hundred to six-hundred degrees Fahrenheit. Felts of this nature may be constructed of metal, high temperature plastics such as polyetheretherketone (PEEK), or other high temperature materials which can be formed into the necessary fibers. As shown in FIGS. 3A-3B, multiple felts 30, 32, 34 are employed. An exemplary transfer system, as illustrated in FIGS. 3A and 3B, is of the so-called lick-down web transfer wherein the paper web 28 is unbacked by felt over a short region 46 as it transits between the first felt 30 and the second felt 32 or the second felt 32 and the third felt 34. As shown in FIGS. 3A and 3B, the air caps 48 adjacent to the lick-down transfers 47 do not blow on the unbacked short region 46 so the unbacked web is not blown off the dryer surface 36. The web 28 is transferred between the multiple dryer rolls 24 of the single tier. Because only a single tier of dryers 24 is employed in the dryer section 22, reversing rolls 50 are used to transfer the paper web 28 from the surface 36 of one dryer roll to the surface 36 of an adjacent dryer roll. In order to maximize the amount of drying achieved per dryer roll 24 it is desirable that the web be wrapped about the maximum portion practical of the dryer surface 38 of each dryer roll 24. As shown in FIGS. 1 and 3A-3B the employment of two spaced apart reversing rolls 50 maximizes the portion 52 of the roll surface 36 which is wrapped by the felts 30, 32, 34. The dryer section 24 shown in FIGS. 1 and 3A-3B wraps a portion 52 comprising approximately eighty percent of the dryer roll's surface 36, in the case of an eight foot diameter dryer. As shown in FIG. 1, where dual reversing rolls 50 are employed it is desirable to support the web 28 as it moves around the reversing rolls 50 to prevent fluttering and thus paper breaks. A vacuum chamber 54 is formed by a rigid metal structure 58 located between gaps 56 between dryer rolls 24. The vacuum chamber 54 is formed by a metal cover 58 which is sealed against the moving dryer felts 30, 32, 34 to define an internal volume on which reduced pressure is drawn. The cover 58 is comprised of two side plates 60, one of which is shown in FIG. 1. The side plates are joined along the top by a top plate 62. Each side plate 60 has two clearance openings 64 which are smaller in diameter than the reversing rolls 50. The reversing rolls 50 preferably are formed with circumferential grooves which facilitate holding the paper web and the felts to the reversing roll 50. The reversing rolls 50 are rotatably mounted within the vacuum chamber 54. The openings 64 provide clearance for the side wall extensions of the shafts (not shown) on which the rolls 50 are mounted. The side plates 60 oppose each other and are perpendicular to the central axes 26 of the dryer roll 24. A hole (not shown) is cut through the side plate 60 which allows for the drawing of a vacuum on the vacuum chamber 54 by an external vacuum means (not shown). Each side plate 60 has an upper segment 66 which extends above the grooved rolls 50 and a downwardly extending tab 68 which blocks escaping air to the sides of the grooved rolls. A lower horizontal edge 70 of the tab 68 engages with the dryer felt 30, 32, 34 as it passes between the two grooved rollers 50. Stiffening ribs (not shown) may project inwardly from the inner perimeter of the side plates 60 to prevent excessive deflection of the plates by the application of vacuum. Two inclined flanges 72 extend from the top plate 62 between the side plates 60. Each inclined flange 72 extends upward of the top plate 62 and inward towards the center of the top plate 60, thereby forming an acute angle with the top plate 62. The net result of the grooved rollers 50 and the vacuum box 54 is to restrain the web and the backing felt from fluttering as it transfers from one dryer roll to the next whilst preventing paper breaks. Alternatively, a passive box could be employed. As shown in FIG. 2, an alternative dryer section 122 employs dryer rolls 124 and air caps 142. The dryer section 124 is similar to the dryer section 24 of FIG. 1, only a single turning roll 150 is employed to transfer the web 128 and felt 130 between dryer rolls 124. The result of employing a single turning roll reduces the complexity of the dryer section 122. However, the use of a single turning roll results in a wrapped portion 152 which is a somewhat smaller percentage of the total surface area 136 of the roll when compared to the wrapped percentage of the dryer section 22 of FIG. 1. An exemplary paper machine 20 employing the dryer section 22 is shown in FIGS. 3A-3B. The papermaking machine 20 illustrated can be used to produce twenty-eight pound newsprint with a wire width of four-hundred-and-twenty inches and operating at a speed of sixty-five-hundred feet-per-minute. The papermaking machine 20 employs a vertically oriented headbox 80 which has a slice 82 which injects a stream of pulp between a first forming wire 84 and a second forming wire 86 which comprises the twin wire former 88. The paper web 36 is transferred to a press section 90 where a single extended nip press 92 accomplishes the pressing function. The web 36 is then wrapped onto the first dryer felt 30 and transferred to the dryer section 22. After transiting the dryer section the web is calendered with high temperature soft nip calenders 94 and wound onto reels by a winder 96. In a preferred system, the twin wire former may be a Bel-Baie RCB type enclosed jet former obtainable from Beloit Corporation. The headbox used will preferably be the Concept IV-MH headbox employing consistency profiling, also available from Beloit Corporation. Press sections, high temperature soft nip calenders and reels are also available from Beloit Corporation. The papermaking machine 22 employing the dryer section 24 may be observed to be of compact design with relatively few dryer rolls as well as few rolls of any type. Because of the high cost of individual rolls, together with their bearings and support system, a papermaking machine such as illustrated in FIGS. 3A-3B will result in improved cost and reliability performance. It should be understood that the air temperature used in the dryer air caps may be varied between the wet end and the dry end of the dryer. It should also be understood that an exemplary air velocity of twenty-eight-thousand feet per minute and an air temperature of seven-hundred-fifty degrees may be employed. It should be understood that greater dryer surface for a given floorprint may be achieved by using larger dryers and that dryer technology used in the manufacturer of Yankee dryers assures that dryers as large as twenty feet can be constructed. It should also be understood that a further advantage of the dryer section 22 of this invention is that because all the dryers are in a single tier it is possible to mount the dryer section directly to the mill floor without the necessity of constructing basements under the dryer. This relatively simple and more rigid mounting will reduce dryer vibrations as well as reduce dryer installation costs. It should also be understood that although three dryer felts are shown, more or less felts could be used. The advantages of employing greater numbers of felts are threefold. One, the paper lengthens and shortens slightly as the drying process is accomplished and therefore the dryer rolls are required to run more rapidly as the paper progresses through the dryer section 22. The more drying felts, the more stages in which the paper speed can be increased. Secondly, changing felts prevents a single felt from impressing a pattern onto the surface of the web. Thirdly, it is to be understood that shorter felts are more easily changed. It is understood that the invention is not limited to the particular construction and arrangement of parts herein illustrated and described, but embraces such modified forms thereof as come within the scope of the following claims.
The paper dryer section has a single tier of all top felted dryer rolls seven to nine feet in diameter. Air caps are employed over the dryer rolls to simultaneously dry both sides of the web to prevent curl and to increase drying rates. The air caps employ blown air at a temperature of 200-1,000 degrees Fahrenheit and air speeds of 8,000-40,000 feet per minute. The felt employed is foraminous with a permeability of between 300-1,500 cubic feet per minute per square foot and is designed to withstand peak temperatures of up to 1,000 degrees Fahrenheit and average temperatures of between 500-600 degrees Fahrenheit. A single dryer roll, or more advantageously, two vacuum rolls in a vacuum box are disposed between the dryer rolls to maximize the circumferential wrap of the web and, at the same time, support and transport the web between dryers.
3
CROSS REFERENCE TO RELATED APPLICATION [0001] This application filed under 37 CFR 1.53(b) is a continuation of U.S. Ser. Number 10/449,279 filed on May 30, 2003. BACKGROUND OF THE INVENTION [0002] 1) Field of the Invention [0003] The present invention relates to a high loft having balanced properties and a method of making the same for the production of nonwoven fabric. In particular, the present invention relates to a lightweight, high loft nonwoven fabric in which properties in the machine direction and cross direction such as resiliency (measured in terms of improved loft), and improved tensile strength are more uniform. Additionally, a process for making the high loft nonwoven is unique in that a drafter machine is employed, thereby increasing the efficiency of the production process. [0004] 2) Prior Art [0005] High loft nonwoven fabrics are used in a wide variety of applications, for example, in indoor and outdoor furniture, bedding such as mattresses, and quilting. As such, there is always a need to improve the quality of nonwoven fabrics to enhance their function with existing uses, and to add their application to new uses. Moreover, from an economics standpoint, it is desirous to improve the process of producing nonwoven fabric in order to increase production rate. [0006] High loft, nonwoven fabrics are principally formed of a polyester blend having a low melt binder. The low melt binder is either a bicomponent fiber, or a low melting fiber having a lower melting temperature than the polyester fiber, or a latex resin applied to the fibers, either as a spray or a powder. [0007] Two principle characteristics of high loft nonwoven fabrics are product resiliency and tensile strength. Product resiliency refers to the capability of the fabric to return to its original shape after having been compressed. For example, it is desirable that a cushion, mattress, or similar item returns to its original form after use, such as after being sat upon by a person. Also, during shipping, the product is usually vacuumed down to reduce shipping volume. As such, it is important that the product returns to its original state upon unpacking. [0008] Tensile strength refers to the capacity of the fabric to resist a load applied in tension and is measured in the machine and cross directions. Machine direction refers to the direction in which the nonwoven material is manufactured and processed, and cross direction is transverse to the machine direction. [0009] Other important measures of quality include product uniformity, product compression recovery, and the amount of false loft exhibited by the product. Product uniformity refers to the degree of fiber alignment in both the machine and cross directions, such that the product possesses more uniform physical properties. Compression recovery and false loft are related to resiliency in that they affect fabric's ability to return to its original shape. For example, a fabric with false loft will have a high initial loft due to excessive voids within the fabric. Upon removal of an applied load, the fabric will be compressed into the voids and will not return to its original form. [0010] In a conventional process for making high loft nonwoven fabric, wherein low melt fibers are used as the binder, polyester fibers and low melt fibers are blended together in a hopper, for example, and deposited onto a moving conveyor belt forming a batt. The speed of the conveyor belt determines the thickness of the batt. Movement of the conveyor belt naturally orients the majority of the fibers in the machine direction. However if higher tensile strengths are desired, more orientation in the machine direction will provide this effect. For example, the fibers may be carded to align the fibers more uniformly in the machine direction to give higher tensile strengths. To provide tensile strength in the cross direction a cross lapper layers the fibers over the machine direction laid fibers to thicken and strengthen the web. The web is then passed through an oven having sufficient heat to melt the low melt fibers, causing them to bind to the other fibers, thereby strengthening and improving resiliency of the web. After leaving the oven, the properties of the web are set in a cooling zone and the batt is wound for shipping to customers. This is the conventional process for producing the highest quality high loft product. [0011] This conventional process is limited in that tensile strength of the web in the cross direction is higher than the tensile strength in the machine direction. Another drawback of the conventional process is that the low melt fibers typically constitute twenty percent (20%) or more of the web, by weight. These low melt fibers are more expensive than the polyester fibers, adding cost to the product. [0012] A further limitation of the conventional process is that the production rate is limited by the cross-lapper. That is, the faster the production rate, the more inconsistent the fibers are laid when cross lapped. Moreover, the cross lapper is incapable of cycling back and forth at a speed sufficient to keep up with the speed of the other production components. This is particularly a problem for lightweight, nonwoven fabrics wherein inconsistently laid fibers reduce the fabrics' quality and diminishes physical properties of the product. [0013] An alternative to using a low melt fiber as a binder in a conventional process for producing high loft nonwoven fabrics is to spray a latex resin onto the polyester fibers. The latex resin is applied in a spraying area sequentially located between the cross lapper and oven. Disadvantageously, the step of applying resin is also quite slow in comparison to the process speed of the remaining equipment, causing another process restriction point. Moreover, the latex resin causes the fabric to have a stiff feel. [0014] It is the object of the present invention to provide a process for producing high loft nonwoven fabric at a faster production rate than conventionally accomplished. It is also an object of this invention to provide a product and process for producing high loft nonwoven fabric having comparable and in most cases superior quality, particularly having uniformity in tensile strength in the machine and cross directions. Further, it is an object of this invention to provide a product for making high loft nonwoven fabric that has improved product uniformity, enhanced compression recovery, and a reduction in false loft. Still further, it is an object of this invention to provide a product and process that produces a high loft nonwoven fabric, containing a reduced amount of low melt fibers, that is comparable or superior to fabric produced by a conventional process. [0015] The present invention achieves these objectives in producing nonwoven fabric by adding a drafter within an existing high loft nonwoven process, between the cross lapper and oven. The drafter functions in its conventional sense, but its use in producing high loft nonwoven fabric is novel, thus producing novel products, and the benefits to product quality and increased production rate resulting therefrom was unexpected. [0016] Drafters are known to those skilled in the textile art for producing thin fabrics. Drafters are typically used in processes which include needle punching, wherein the needle punching strengthens the web. However, their use in producing lightweight, high loft nonwoven fabric, is not known. [0017] Applicant is aware of the following U.S. Patents concerning a process having a drafter for producing nonwoven fabric. [0018] U.S. Pat. No. 5,475,903, issued to Collins on Dec. 19, 1995, describes a hydroentangled, nonwoven fabric having comparable strength in the machine and cross directions. The process includes carding, cross lapping, drafting and hydroentaglement to create a thin fabric suitable for use in hospital gowns. The hydro entanglement step imparts comparable strengths to the fabric in the machine and cross directions. Since the process relates to manufacturing a thin fabric, there is no consideration of product resiliency. [0019] U.S. Pat. No. 5,252,386, issued to Hughes et al. on Oct. 12, 1993, describes a process for making an entangled nonwoven fabric having balanced strength properties in the machine and cross directions and improved fire retardancy. These characteristics are achieved by cross-stretching the entangled fabric after the fabric has been wetted with an aqueous-based fire retardant composition and drying the wetted fabric while maintaining it in its stretched state. [0020] Another example of a nonwoven fabric having comparable strength in the machine and cross directions is illustrated by U.S. Pat. No. 5,296,289, issued to Collins on Mar. 22, 1994. Collins discloses a spun bonded nonwoven web having spaced autogenous spot bonds, wherein spot bonds are distributed in a cornrow pattern to form a web having improved strength. [0021] Conventionally formed high loft nonwoven fabrics have limited use since their tensile strength in the machine direction is significantly less than that in cross direction. Moreover, improvement is also desired in other measures of product quality, such as fiber uniformity, resiliency, compression recovery, and reduction in false loft. [0022] Conventional processes for forming high loft nonwoven fabrics also have process components that limit production rate well below that of the remaining equipment. The cross lapper typically limits the rate of production in that it is incapable of obtaining the production speeds of the remaining equipment. [0023] Conventional processes that spray resin as a binder onto the web have a production rate much slower than those that utilize low melt fibers because the step of applying resin causes a process restriction point. Also the oven cure residence time to dry and cure the sprayed binder resin impedes the production process compared with using low melt fibers. Using low melt fibers, on the other hand, is often more expensive than spraying a binder resin. SUMMARY OF THE INVENTION [0024] The present invention relates to a product and process for making a lightweight, high loft nonwoven fabric. The process adds a drafter to a conventional nonwoven process in order to increase the production rate. Additionally, the invented process improves the quality of the manufactured fabric by increasing the tensile strength in the machine direction, providing balanced strength in the machine and cross directions, and enhancing resiliency of the fabric. [0025] Preferably, the invented process provides a fabric having tensile strength in the MD and CD that is at least 50% of one another, and more preferably at least 60% of one another (within 40% of one another). Most preferably the high loft nonwoven fabric has tensile strengths in the MD and CD that is at least 80% of one another (within 20% of one another). [0026] In the broadest sense, the present invention relates to a process for forming a high loft, nonwoven fabric in which the process includes the steps of providing a fiber, a binder, and a drafter for drafting the batt of fiber and binder. Preferably, the fiber is made of polyester and the binder is either a low melt binder fiber or a bicomponent fiber. More preferably, the weight of the fabric is no more than 2.0 oz/ft 2 , and most preferably the weight of the fabric is in the range of 0.25 oz/ft 2 to 1.8 oz/ft 2 . [0027] In the broadest sense, the present invention also relates to a process for forming a high loft nonwoven material in which the process includes the steps of providing natural and/or synthetic fibers, and low melt binder fibers. The natural and/or synthetic fibers and low melt fibers are mixed, optionally carded, cross lapped, drafted, heated and cooled to form the nonwoven material. Preferably, the nonwoven fabric has a tensile strength in a machine direction that is at least 50 percent or the tensile strength in a cross direction. [0028] In the broadest sense, the present invention also relates to a high loft, nonwoven fabric wherein the weight of the fabric is in the range of 0.25 oz/ft 2 to 1.8 oz/ft 2 , the tensile strengths in the CD and MD are within 40% of one another, and the loft recovery is 90% or more. BRIEF DESCRIPTION OF THE DRAWINGS [0029] The drawing of the present invention is used to help illustrate, describe, and convey the general concept of the overall invention. Accordingly, it is for illustrative purposes only and not meant to limit the scope of the invention and claims in any manner. [0030] FIG. 1 is a flow diagram of the invented process for producing high loft nonwoven fabric. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0031] The present invention is an improved product and process for producing lightweight, high loft nonwoven fabric. For purposes of this application, light-weight fabric is considered to be fabric having a weight of ≦2.0 oz/ft 2 and more preferably having a weight in the range of 0.25 oz/ft 2 to 1.8 oz/ft 2 . The present invention comprises a nonwoven batt having natural and/or synthetic fiber and a binder. [0032] The synthetic fiber can be polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or polypropylene terephthalate, or a mixture of these; polyamide such as nylon 6 or nylon 6 , 6 , or a mixture of these; polyolefin such as polyethylene or polypropylene, or a mixture of these; polyacrylic such as polyacrylonitrile, cellulose acetate, melamine, and rayon, or a mixture of these, or copolymers based on any of these. [0033] The natural fiber can be, for example, cotton, wool, flax, kenaf, hemp, silk, jute, asbestos, and ramie. Natural fibers are generally fibers from animals, minerals, or plants. Mixtures of various natural fibers are also within the scope of this invention. [0034] The binder can be a latex resin, a low melt polymer fiber or powder, or a bicomponent fiber. The binder is typically employed at about 5 to about 25 percent by weight of the nonwoven batt, to provide sufficient bonding and resiliency for various applications. Generally no more than 30% by weight of the nonwoven batt (fabric) is binder. Latex resin used as binders are well known and most are suitable for the present invention so long as they have adequate strength and durability and have no odor or safety concerns (fire or noxious gases) problems. Common low melt polymers include polyolefin, polyester, copolyester, and copolyolefin which can be in fiber form (preferable), powder form, or applied like a hot melt adhesive. The low melt fibers must have a lower melting point than the synthetic fibers. Bicomponent fibers are also known to those skilled in the art and include side-by-side and sheath-core arrangements wherein the high melt component is the core and the low melt component forms the sheath. Such bicomponent fibers may be based upon polyolefin/polyester, copolyester/polyester, polyester/polyester, polyolefin/polyolefin, and copolyolefin/polyolefin wherein the naming convention is the low melt component followed by the high melt component. [0035] Referring to the drawing, and in particular to FIG. 1 , the process 10 includes several blend hoppers 12 for supplying a desired blend of fibers or a single fiber type. The fibers are typically natural and/or synthetic and may have fire retardant properties, a silicon finish to provide a slick fiber, or other characteristics. From the hoppers 12 , the fibers are blended into a batt by being weighed, and then air laid onto a moving conveyor belt 14 , for example. The desired batt thickness and weight, measured in terms of ounces per square foot, is controlled by the conveyor belt speed. The batt fibers are then carded 16 to align the fibers uniformly in a web, oriented in the machine direction. Thereafter, the conveyor belt 14 moves the web to a cross lapper 18 where a predetermined number of layers are applied, back and forth, in cross direction to build-up the web to a desired weight and thickness and to provide tensile strength in the cross direction. Following the cross lapper 18 comes the drafter 20 , which pulls the web or batt in the machine direction to better balance the properties with the cross direction. [0036] The nonwoven web is then passed through an oven 22 having a series of heated zones 24 wherein the low melt binder is melted and cured according to standard practice. In lieu of using low melt fiber as a binder, a conventional process may spray latex resin onto the batt or web. In such an arrangement, the conveyor 14 carries the web to a spray area (not shown) sequentially positioned between the drafter 20 and oven 22 . Thereafter, the nonwoven web is passed through a cooling zone 26 , allowing the low melt binder to re-solidify to set the web properties. The web is wound up on a winding head 28 , and ready for use in furniture, mattresses, and other applications. [0037] The drafter 20 is of a conventional type, such as an Asselin Drafter. The drafter 20 includes several zones, wherein each zone includes multiple rollers. The rollers nip the web, compressing and pulling the web in the machine direction. The speed of each zone of rollers is the same as or progressively increased so that the web becomes attenuated or stretched during its passage therethrough. [0038] Notwithstanding the conventional nature of the drafter 20 , its application in producing lightweight, high loft nonwoven fabric surprisingly allows for the fabric to be processed at a significantly higher rate than with the conventional process. Moreover, use of the drafter unexpectedly and dramatically improves the quality of the fabric. In particular, use of the drafter improves fabric resiliency, increases tensile strength in the machine direction, and yields a fabric having more uniform tensile strength in the machine and cross directions. Other measures of quality, such as the amount of false loft, compression recovery and product uniformity also benefit from the operation of the drafter. Heretofore, the use of a drafter on high loft fabric was thought to be worthless because the tensile strength could be balanced by other means and it was thought that the drafter would easily pull apart the web or batt, since it is light weight and full of void areas to create loft. [0039] In particular, the drafter in compressing, nipping and pulling the web, tends to improve fiber uniformity, negating some of the effects of fiber misalignment caused by the cross lapper. The velocity of the web actually increases as it traverses through the drafter. Accordingly, the overall process rate in manufacturing high loft fabric can be increased. [0040] The use of the drafter also yields a more resilient fabric and removes false loft from the web by compressing and stretching the fibers. The amount of compression is set by the gap between the rollers and is also determined by the weight of the web. Although the rollers can be set to interferingly engage, it is preferred that the rollers are slightly gapped apart, such as for example from 0.5 mm to 40 mm, in order to avoid excessive compression of the web which may reduce the initial loft of the fabric. Notwithstanding and not to be construed as limiting, it is found that a gap between 0 to about 40 mm, depending on the weight of the web, provides significant improvement to the quality of lightweight, high loft nonwoven fabric. Test Procedures [0041] The properties of the webs were measured according to the following procedures: [0000] Web Strength [0042] The tensile strength of each web was measured according to the ASTM test method set forth in reference ASTM D91-93-Section 12, Tensile Strength, “Breaking Load” and “Specific Strength”. A 250 lb load cell for high loft products was used with the pounds at break recorded. [0000] Loft [0043] The loft under various loads was measured with a loft tester having a pressure foot with an area of 12 inch×12 inch. Two nonwoven 12 inch×12 inch sheets were cut and stacked in the tester. The pressure foot was lowered until it came into contact with the stack of nonwoven sheets. The thickness was then measured and reported as initial loft (L I inch). The pressure foot was applied to the fabric and stopped for 2 minutes, at each of the following loads, 5, 10, 15 and 20 lbs, and the thickness measured at each load. The pressure foot was then moved completely clear from the nonwoven stack. After allowing the sample to relax for 5 minutes, the thickness (L R inch) was measured. [0044] The percent loft recovery is: (L R /L I )×100 [0045] Test results illustrating the effect of including the drafter compared to the conventional process are shown in Tables 1-9. Fabrics made by the conventional process are identified as Control and fabrics that were made by the invented process are identified as Sample. The Tables show that use of the drafter enhances product resiliency, as measured by percent loft recovery, decreases false loft and allows for an increased production rate. In each experiment, testing was performed with zero gap between the rollers of the drafter. EXAMPLE 1 [0046] Referring to Table 1, the quality of a Control high loft nonwoven fabric and three Sample fabrics are compared. Each of the fabrics had a weight of 0.75 oz/ft 2 and a weight percent blend of: 20% 4 dpf (denier per filament) low melt binder fiber, 30% 25 dpf PET, and 50% 15 dpf PET. The Samples were processed with different number of layers, with the Control, First Sample, Second Sample and Third Sample respectively having 2, 2, 3 and 4 layers. In order to maintain the same weight (oz/ft 2 ), the process rate was adjusted, with the Control, First Sample, Second Sample, and Third Sample respectively processed at 1278 lbs/hr, 1775 lbs/hr, 1896 lbs/hr and 1896 lbs/hr. TABLE 1 Percent Loft Recovery for 0.75 oz/ft 2 Control and Samples Applied Load (lbs) Loft (inches) Percent Loft (%) Control Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1278 lbs/hr Weight: 0.75 oz/ft 2 Number of Laps: 2 Zero 1.75 100  5 1.39 79.4 10 1.18 67.4 15 1.03 58.9 20 0.93 53.1 Load removed 1.68 96.0 (% loft recovery) Sample 1 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1775 lbs/hr Weight: 0.75 oz/ft 2 Number of Laps: 2 Zero 1.55 100  5 1.3  83.9 10 1.14 73.5 15 1.03 66.5 20 0.94 60.6 Load removed 1.5  96.8 (% loft recovery) Sample 2 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1896 lbs/hr Weight: 0.75 oz/ft 2 Number of Laps: 3 Zero 1.51 100  5 1.24 82.1 10 1.08 71.5 15 0.97 64.2 20 0.88 58.3 Load removed 1.46 96.7 (% loft recovery) Sample 3 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1896 lbs/hr Weight: 0.75 oz/ft 2 Number of Laps: 4 Zero 1.61 100  5 1.31 81.4 10 1.08 67.1 15 0.98 60.9 20 0.87 54.0 Load removed 1.56 96.9 (% loft recovery) [0047] The percent loft recovery for the Samples ranged from 96.7% to 96.9% which is superior to the 96.0% recovery exhibited by the Control. This improvement in resiliency is advantageous is preserving the fabric's loft and shape during shipment and use. The testing also demonstrated that the invented process reduced the amount of false loft in the fabric. False loft is indicated by the percent of loft lost between the initial loft and the loft at the applied load. As shown in the Table 1, the Samples performed superior to the Control, exhibiting less false loft. Moreover, it is noted that the improvements in fabric resiliency and false loft was achieved at substantially higher production rates. [0048] Table 2 is the tensile strength of the Control and the three Sample fabrics identified in Table 1. TABLE 2 (Tensile Strength in pounds) Control Sample 1 Sample 2 Sample 3 MD 1.33 2.78 7.09 9.19 CD 5.30 4.44 5.52 4.57 [0049] Table 2 illustrates a great disparity between tensile strength in the cross direction and machine direction for the Control Sample, with strength in the machine direction being significantly less than that in the cross direction. In comparison, tensile strength in machine direction for each of the drafted Samples was substantially improved from that of the Control. Specifically, Sample 1, having the same number of laps as the Control, provides an increased tensile strength from of load of 1.33 lbs to 2.78 lbs. Samples 2 and 3 each demonstrate an even more dramatic increase in machine direction tensile strength. EXAMPLE 2 [0050] Referring to Table 3, a Control high loft, nonwoven fabric and two Sample fabrics are compared wherein each of the fabrics had a weight of 1.0 oz/ft 2 and a weight percent blend of: 20% 4 dpf low melt binder fiber, 30% 25 dpf PET, and 50% 15 dpf PET. The Samples were processed wiith different number of laps, with the Control, First Sample and Second Sample having 3, 3 and 4 laps, respectively. The process rate was adjusted in order to maintain the same weight (oz/ft 2 ), with the Control, First Sample and Second Sample respectively processed at 920 lbs/hr, 1050 lbs/hr and 1100 lbs/hr. TABLE 3 Percent Loft Recovery for 1.0 oz/ft 2 Control and Samples Applied Load (lbs) Loft (inches) Percent Loft (%) Control Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 920 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 3 Zero 2.82 100  5 2.14 75.9 10 1.75 62.1 15 1.43 50.7 20 1.3  46.1 Load removed 2.7  95.7 (% loft recovery) Sample 1 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1050 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 3 Zero 2.57 100  5 2.07 80.5 10 1.73 67.3 15 1.46 56.8 20 1.34 52.1 Load removed 2.47 96.1 (% loft recovery) Sample 2 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1100 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 4 Zero 2.98 100  5 2.37 75.9 10 1.97 62.1 15 1.7  50.7 20 1.52 46.1 Load removed 2.9  97.3 (% loft recovery) [0051] Again, the step of drafting improved the resiliency of the fabric, as measured by percent loft recovery. Here, the percent recovery for Samples 1 and 2 were respectively 96.1% and 97.3%, compared to a loft recovery of 95.7% for the Control. Also, the Samples had the same or less false loft than the Control. These improvements in fabric quality were obtained even at production rates higher than that of the Control. [0052] Table 4 is the tensile strength of the Control and Samples of Table 3. TABLE 4 (Tensile Strength in pounds) Control Sample 1 Sample 2 MD 3.0 7.0 10.25 CD 8.75 9.1 7.25 [0053] Table 4 illustrates that by adding the drafter to the nonwoven process, tensile strength in the machine direction was substantially improved while tensile strength in the cross direction remained relatively unchanged. As such, tensile strength in the machine and cross directions is more uniform. EXAMPLE 3 [0054] Because the drafter provides a more balanced fabric (with respect to certain physical properties), it is possible to lower the amount of binder and still achieve good tensile strength properties. Table 5 compares the Control having 20% binder and the Samples each of which had a weight of 1.0 oz/ft 2 and a weight percent blend of: 10% 4 dpf low melt binder fiber, 35% 25 dpf PET, and 55% 15 dpf PET. TABLE 5 Loft Recovery for 1.0 oz/ft 2 Control and 10% Low Melt Binder Fiber Samples Applied Load (lbs) Loft (inches) Percent Loft (%) Control Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 920 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 3 Zero 2.82 100  5 2.14 75.9 10 1.75 62.1 15 1.43 50.7 20 1.3  46.1 Load removed 2.7  95.7 (% loft recovery) Sample 1 (10% Low melt fiber) Blend (10% 4 dpf low melt, 35% 25 dpf PET, and 55% 15 dpf PET) Rate: 1050 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 3 Zero 2.41 100  5 1.76 73.0 10 1.43 59.3 15 1.25 51.9 20 1.11 46.1 Load removed 2.25 93.4 (% loft recovery) Sample 2 (10% Low melt fiber) Blend (10% 4 dpf low melt, 35% 25 dpf PET, and 55% 15 dpf PET) Rate: 1100 lbs/hr Weight: 1.0 oz/ft 2 Number of Laps: 4 Zero 2.71 100  5 2.05 75.6 10 1.69 62.4 15 1.43 52.8 20 1.3  48.0 Load removed 2.56 94.5 (% loft recovery) [0055] Due to the loser weight percent of binder fiber, the Samples had a lower percent loft recovery, respectively 93.4% and 94.5%, than that of the Control. Notwithstanding, the Samples exhibited more tensile strength uniformity in the machine and cross directions, as discussed in detail below. In many applications, the balanced tensile strengths and cost savings achieved by increased production rate and using less of the comparatively expensive low melt fibers are more important than the disadvantage of a reduction in loft recovery. [0056] The tensile strength for the Control and Samples of Table 5 are set forth in Table TABLE 6 (Tensile Strength in pounds) Control Sample 1 Sample 2 MD 3.3 6.2 4.1 CD 8.75 6.7 4.05 [0057] The drafted samples had a reduced weight percent of low melt fibers. Since low melt fibers are used bond the fibers, standard convention would dictate that decreasing the weight percent of these fibers would reduce the tensile strength of the fabric. Surprisingly, the drafted Samples had tensile strength in the machine direction that exceeded that of the control. [0058] Although the drafted Samples did decrease in tensile strength in the cross direction, the tensile strength in the cross and machine directions were now substantially balanced. Since the low melt fabrics do not exhibit a gross weakness in either direction, they can be applied to many applications, but at a lower cost than conventionally manufactured fabric. EXAMPLE 4 [0059] Table 7 shows the percent loft recovery for 1.25 oz/ft 2 Control and two Sample fabrics. TABLE 7 Percent Loft Recovery for 1.25 oz/ft 2 Control and Samples Applied Load (lbs) Loft (inches) Percent Loft (%) Control Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate 1385 lbs/hr Weight: 1.25 oz/ft 2 Number of Laps: 3 Zero 2.86 100  5 2.3  80.4 10 1.95 68.2 15 1.71 59.8 20 1.54 53.8 Load removed 2.74 95.8 (% loft recovery) Sample 1 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1700 lbs/hr Weight: 1.25 oz/ft 2 Number of Laps: 4 Zero 2.54 100  5 2.22 87.4 10 1.99 78.3 15 1.81 71.3 20 1.65 65.0 Load removed 2.46 96.9 (% loft recovery) Sample 2 Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1300 lbs/hr Weight: 1.25 oz/ft 2 Number of Laps: 5 Zero 2.72 100  5 2.42 89.0 10 2.2  80.9 15 2.0  73.5 20 1.86 68.4 Load removed 2.66 97.8 (% loft recovery) [0060] As with the previous examples, drafting improved the resiliency of the fabric, as measured by percent loft recovery. In this experiment, the percent recovery for Samples 1 and 2 were respectively 96.9% and 97.8%, compared to a loft recovery of 95.8% for the Control. Table 7 also shows that the drafted Samples have less false loft than the Control. These advantages in fabric quality are achieved even though the Samples were manufactured at a higher production rate than the Control. [0061] It is noted that the production rate of Sample 2 is less than that of the Control. However, this lower rate was due to the maximum operation capacity of the cross lapper, and not related to the use of the drafter enhanced process in manufacturing the Sample. As such, it is extrapolated that the quality of Sample 2 will be superior to that of the Control, even at higher production rates. [0062] Table 8 shows the tensile strength for the Control and Samples set forth in Table 7. TABLE 8 (Tensile Strength in pounds) Control Sample 1 Sample 2 MD 4.1 9.0 14.1 CD 12.4 13.0 16.5 [0063] Table 8 illustrates that by adding the drafter to the nonwoven process, tensile strength in the machine direction was substantially improved while tensile strength in the cross direction remained relatively unchanged. As such, tensile strengths in the machine and cross directions are more uniform. EXAMPLE 5 [0064] The percent loft recovery for the invented process was also compared to that of a conventional process which uses latex resin as a binder. It is known that typically latex resin produces superior loft recovery properties compared to a nonwoven high loft using a low melt binder fiber. The use of the drafter makes a fabric that is more uniform such that the loft recovery is similar even if you use a latex resin binder or a low melt binder fiber. The results are set forth in Table 9. TABLE 9 Percent Loft Recovery for 0.75 oz/ft 2 Samples and Resin Control Applied Load (lbs) Loft (inches) Percent Loft (%) Resin Control Blend (100% 15 dpf PET, Resin Add On 17.80%) Rate: 450 lbs/hr Weight: 0.75 oz/ft 2 Zero 1.51 100  5 1.19 82.1 10 0.99 65.4 15 0.83 54.8 20 0.73 48.5 Load removed 1.46 97.0 (% loft recovery) Sample Blend (20% 4 dpf low melt, 30% 25 dpf PET, and 50% 15 dpf PET) Rate: 1700 lbs/hr Weight: 0.75 oz/ft 2 Zero 1.51 100  5 1.24 82.1 10 1.08 71.5 15 0.97 64.2 20 0.88 58.3 Load removed 1.46 96.7 (% loft recovery) [0065] As shown in Table 9, the Sample exhibited comparable results in percent loft recovery to that of the Control, 96.7% to 97.0%. Notably, however, the production rate for the Sample was significantly faster than that for the Control: 1700 lbs/hr compared to 450 lbs/hr. [0066] From the foregoing, it is apparent that there has been provided, in accordance with the invention, an improved process for manufacturing light-weight, high loft, nonwoven fabric that fully satisfies the objects, aims and advantages set forth above. Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations would be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the invention.
The present invention relates to process for making a light-weight, high loft nonwoven fabric. The process adds a drafter to a conventional nonwoven process in order to increase the production rate. Additionally, the invented process improves the quality of the manufactured fabric by increasing the tensile strength in the machine direction, providing balanced strength in the machine and cross directions, and enhancing resiliency. The process blends polyester fiber with a low melt fiber or low melt bicomponent fiber to form a web. The web is optionally carded and cross lapped before being drafted. Thereafter, the web is heated in an oven having sufficient heat to melt the low melt fiber then cooled to set the properties.
3
TECHNICAL AREA [0001] This invention relates to the area of biomaterials involving resorbable or degradable, macroporous bioactive glass material which can be used either for the restoration of hard tissues or as the tissue engineering scaffold, as well as preparation methods for such materials. BACKGROUND TECHNOLOGY [0002] There has been a history of over 30 years in research on bioactive glass since 1971 when Dr. Larry Hench reported that such glass could bond together with bone tissues for the first time. Also, such glass material has been used for restoration of bone defects in clinical practice for over ten years, and such clinical applications have proven successful in that this glass can bring along not only the benefit of osteoconduction, but also the bioactivity to stimulate the growth of bone tissues. Many recent studies have revealed that the degradation products of bioactive glass can enhance the generation of growth factors, facilitate cellular proliferation and activate gene expression of osteoblasts. Moreover, bioactive glass is the only synthetic biomaterial so far that can both bond with bone tissues and soft tissues. These unique features of this glass have created a great potential for its clinical application as a type of medical device, and thereby, attracted great attention from both academia and the industrial sector. Despite its excellent biocompatibility and bioactivity, bioactive glass can be now produced only in a granular form for clinical application. For restoration of bone defects, macroporous and block scaffold materials with a particular mechanical strength are often needed to fill in and restore such defects. Even in the field of tissue engineering, which receives world-wide attention and evolves rapidly, macroporous bioactive scaffold materials are similarly demanded to serve as cell carriers. [0003] Research studies in the past have suggested that besides the composition of the material, its structure can directly influence its clinical applications as well. The macroporous and block scaffold materials with bioactivity whose pore sizes are in the range of 50-500 microns are most suitable to be used as materials either for the restoration of bone defects, or as cell scaffolds. Any macroporous biomaterial having a pore size within the said range can bring benefits to the housing and migration of cells or tissue in-growth, as well as to the bonding of such a material to living tissues, thereby achieving the goals of repairing defects in human tissues and reconstructing such tissues more effectively. [0004] Moreover, the subject of the biomaterials that are both resorbable and macroporous has now become an integral part of tissue engineering studies that have been rapidly developed in recent years, where scaffolds made of such macroporous materials can be adopted to serve as cell carriers so that cells can grow in the matrix materials and constitute the living tissues that contain genetic information of the cell bodies, and such tissues can be in turn, implanted into human bodies to restore tissues and organs with defects. Therefore, resorbable, macroporous bioactive glass scaffold materials possess wide-ranging potential for their applications as cell scaffolds either for restoration of defects in hard tissues, or for the purpose of in vitro culture of bone tissues. [0005] U.S. Pat. Nos. 5,676,720 and 5,811,302 to Ducheyne, et al, teach a hot-pressing approach using inorganic salts such as calcium carbonate and sodium bicarbonate as the pore-forming agents to prepare and manufacture macroporous bioactive glass scaffolds which have the compositions of CaO—SiO 2 —Na 2 O—P 2 O 5 , and which are designed to function as the cell scaffolds used for in vitro culture of bone tissues. Nevertheless, this hot-pressing approach if adopted would entail high production costs, and furthermore, controlling the composition of the finished products is difficult because the composition will be affected by the remnants that result after sintering the inorganic salts used as pore-forming agents. Additionally, Yuan, et al. have adopted oxydol as a foaming agent to prepare and manufacture 45S5 bioactive glass scaffolds under a temperature of 1000° C., with the scaffolds produced in this way being bioactivity and having the ability to bond together with bone tissues (J.Biomed.Mater.Res; 58:270-267,2001). But according to our testing results, the glasses will become substantially crystallized and their resorbability/degradability will decrease if they are sintered under a temperature of 1000° C. In addition, it is quite difficult to control the pore size and pore number of the materials when oxydol is used as the foaming agent. [0006] Mechanical strength is also an important factor for performance of macroporous bioactive glass scaffold materials, and relevant studies have suggested that any compressive strength below 1 MPa would result in the poor applicability of these scaffold materials, and thus, in the course of applying them either as cell scaffolds or for the purpose of restoration of bone injuries, such materials would be very prone to breakage or damage, therefore limiting the effectiveness of their application. So far, no report on the compressive strength standard data of macroporous bioactive glass scaffolds has been found in previous patent and published documents and as a result, gives rise to the purpose of this invention to determine proper technical control measures to keep the compressive strength of the manufactured bioactive glass scaffold within a certain range to meet the requirements of various applications. SUMMARY OF THE INVENTION [0007] The purpose of this invention is to develop, through the optimization of technology and process, a new type of macroporous bioactive glass scaffold with interconnected pores, which features excellent bioactivity, biodegradability, controllable pore size and porosity. Such a scaffold would serve as a means to repair defects in hard tissues and be applied in the in vitro culture of bone tissues, and its strength can be maintained within a range of 1-16 MPa in order to meet demands arising from the development of the new-generation biological materials and their clinical applications. [0008] This invention has been designed to use glass powders as raw material, into which organic pore forming agents will be added, and the mixture will be processed by either the dry pressing molding method or gelation-casting method, and then the resulting products will be obtained by sintering under appropriate temperatures. In this way, a macroporous bioactive glass scaffold can be obtained with various porosities, pore sizes and pore structures, as well as different degrees of compressive strength and degradability. The chemical composition of such scaffolds shall be expressed as CaO 24-45%, SiO 2 34-50%, Na 2 O0-25%, P 2 O 5 5-17%, MgO 0-5 and CaF 2 0-1%. Additionally, the approaches provided in this invention can be adopted to prepare the said scaffold in different shapes. The crystallizations of calcium phosphate and/or calcium silicate can be formed inside the bioactive glass scaffolds by way of technical control, whereby both the degradability and mechanical strength of the macroporous materials can be controlled as demanded. [0009] As designed in this invention, the macroporous bioactive glass scaffold materials exhibit excellent biological activity, and can release soluble silicon ions with precipitation of bone-like hydroxyl-apatite crystallites on their surface in just a few hours after being immersed into simulated body fluids (SBF). In addition, the macroporous bioactive glass in this invention is resorbable, as shown by in vitro solubility experiments, and such glass demonstrates a degradation rate of approximately 2-30% after being immersed in simulated body fluids (SBF) for 5 days. As such, it can be concluded that the macroporous bioactive glass scaffold materials in this invention do not only have desirable biointerfaces and chemical characteristics, but also demonstrate excellent resorbability/degradability. [0010] Another feature of this invention is manifested in controlling technical conditions to create materials that can have both a relatively higher porosity (40-80%) with suitable pore size (50-600 microns), and exhibit a proper mechanical strength (with the compressive strength at 1-16 MPa). BRIEF DESCRIPTION OF THE DRAWINGS [0011] FIG. 1 is a photograph of the prepared macroporous bioactive glass. [0012] FIG. 2 is an optical microscope picture displaying cross-sections of the macroporous bioactive glass. [0013] FIG. 3 shows XRD displays for the macroporous bioactive glass materials prepared under different temperatures; these illustrations show that different levels of crystallization of calcium silicate or calcium phosphate can be found on the surface of the materials prepared under different temperatures; (a) bioactive glass powder before sintering, (b) bioactive glass scaffolds prepared by sintering at 800° C., (c) bioactive glass scaffolds prepared by sintering at 850° C. [0014] FIG. 4 (A) is an SEM picture of the macroporous bioactive glass material of this invention before being immersed in SBF (i.e. simulated body fluids); 4 (B) is an SEM picture of the material immersed SBF for 1 day; 4 (C) is an SEM picture of the material when immersed in SBF for over 3 days; these pictures show that substantial hydroxyapatite crystalline can form on the surface of the material when immersed in SBF for 1 day. [0015] FIG. 5 is a Fourier Transform Infrared spectrometry (FTIR) spectra of the macroporous bioactive glass materials before being immersed in SBF, as well as after being immersed in SBF for 0 hours, 6 hours, 1 day, 3 days and 7 days respectively; the resulting analysis reveals that the hydroxyl-apatite peak can be observed when such material has been immersed in SBF for only 6 hours. DETAILED DESCRIPTION OF THE INVENTION [0016] The implementation of this invention is detailed as below: [0000] 1. Preparation of Materials: [0017] The bioactive glass powder in this invention is prepared using the melting method. The inorganic materials applied in the present invention are all of analytical purity. Specifically, these chemical reagents are weighed and evenly mixed in line with requirements for proper composition results, and then melted in temperatures ranging from 1380° C. to 1480° C. to produce glass powders with a granularity varying from 40 to 300 μam after cooling, crushing and sieving procedures. Furthermore, such glass powders are then used as the main raw material to prepare a variety of the macroporous bioactive glass scaffold substances by way of different processing technologies. The pore forming agents specified in the present invention can be organic or polymer materials such as polyethylene glycol, polyvinyl alcohol, paraffin and polystyrene-divinylbenzene, etc., whose granularity can fall in the range of 50-600 microns. Thus, the pore forming agent within a certain granularity range (20-70% in mass percent) can be blended with the said bioactive glass powders and the resulting mixture can be molded by adopting either of the following two approaches: [0018] First, the dry pressing molding approach, in which 1-5% polyvinyl alcohol (concentration at 5-10%) is added to the said mixture as the adhesive, which is stirred, and then dry-pressed into a steel mold (pressure at 2-20 Mpa) to produce a pellet of the macroporous material, which is then sintered (temperature at 750-900° C.) for 1-5 hours to obtain final product. [0019] Second, the gelation-casting approach, in which an aqueous solution is prepared as per the following mass percent concentrations: 20% acrylamide, 2% N, N′-methylene-bis-acrylamide cross-linking agents and 5-10% polyacrylic acid dispersant agents. Next, the aforementioned mixture and the aqueous solution (volume percent at 30-60%) is combined and mixed, and ammonium persulfate (1-5% in mass percent) and N, N, N′, N′-tetramethyl ethylene diamine (1-5% in mass percent) is added. Then, the above-mentioned materials are stirred to produce a slurry with fine fluidity and homogeneity, which is then poured into plastic or plaster molds for gelation-casting. Later the cross-linking reaction of monomers is induced under temperatures ranging from 30° C. to 80° C. for 1-10 hours, and pellets of the macroporous material are obtained after a few hours of drying at 100° C. The pellets are processed first at the temperature of 400° C. to remove organics, and then sintered at 750-900° C. to obtain the macroporous material of the present invention. [0000] 2. Performance Evaluation [0000] 2.1. The Mechanical Strength of the Macroporous Material: [0020] An array of samples obtained in this invention was tested for their respective compressive strengths using the Autograph AG-I Shimadzu Computer-Controlled Precision Universal Tester made by the Shimadzu Corporation. The testing speed designated for these samples was 5.0 mm/min. This test revealed that the compressive strength of the macroporous material obtained in this invention can be well controlled within the scope of 1-16 MPa. [0000] 2.2. The Porosity of the Macroporous Materials [0021] The Archimedes Method was used to carry out a test with a part of the samples mentioned above to determine their porosities, and a Scanning Electron Microscope (SEM) was used to observe their pore shapes and distribution. This test demonstrated that the porosity of the macroporous material obtained in this invention can be well controlled within a range of 40-80%. [0000] 2.3 Bioactivity Evaluation [0022] A test of in vitro solution bioactivity was carried out with the macroporous materials obtained in the present invention, after being washed in de-ionized water and acetone successively, and then air dried afterwards. The solution applied was simulated body fluids (SBF). The ion and ionic group concentrations in this SBF are the same as those in human plasma. This SBF's composition is as below: NaCl: 7.996 g/L NaHCO 3 : 0.350 g/L KCl: 0.224 g/L K 2 HPO 4 •3H 2 O: 0.228 g/L MgCl 2 •6H 2 O: 0.305 g/L HCl: 1 mol/L CaCl 2 : 0.278 g/L Na 2 SO 4 : 0.071 g/L NH 2 C(CH 2 OH) 3 : 6.057 g/L [0023] The test was carried out with macroporous material immersed in SBF in the following conditions: 0.15 g of macroporous material, 30.0 ml/day SBF, 37° C. in a temperature-controlled water-bath. After the macroporous material was immersed in SBF for a period of 1, 3 or 7 days respectively, samples were taken out and washed using ion water, and then underwent the SEM, Fourier Transform Infrared spectrometry (FTIR) and XRD tests. The respective results of the tests can be seen in FIGS. 3, 4 and 5 . The relevant bioactivity experiment results have shown that the macroporous glass scaffold materials obtained in the present invention can induce the formation of bone-like hydroxyapatite on their surface, indicating ideal bioactivity of these materials. [0000] 2.4 Degradability Evaluation [0024] A bioactivity experimental test was conducted on the macroporous materials in this invention after being washed in de-ionized water and acetone successively, and then dried. Evaluation of both degradation speed and degradability of the macroporous materials according to the content of SiO 2 substances that are released at different time points after the materials have been immersed in SBF was conducted. For example, where PEG is used as the pore forming agent, the macroporous bioactive glass scaffolds (porosity at 40%) obtained after the processes of dry pressing molding and calcination (temperature at 850° C.) exhibit a degradability of 10-20% when the scaffold has been immersed in SBF for 5 days. IMPLEMENTATION EXAMPLE 1 [0000] The raw materials used in this example are the same as those described above. [0025] SiO 2 , Na 2 CO 3 , CaCO 3 and P 2 O 5 (all of analytical purity) are mixed proportionally, and the mixture is melted into homogenous fused masses at the temperature of 1420° C. and then cooled, crushed and sieved to obtain bioactive glass powder with a particle diameter ranging from 40-300 microns. The composition of the bioactive glass powder is expressed as CaO 24.5%, SiO 2 45%, Na 2 O 24.5% and P 2 O 5 6%. Next, the bioactive glass powder (150-200 microns in granularity) is mixed with the polyethylene glycol powder (200-300 microns in granularity) at a mass percent of 60:40. Polyvinyl alcohol solution (6%), which serves as the adhesive, is added and the solution is mixed. The mixture is then dry-pressed under a pressure of 14 MPa, and the pellets of the macroporous materials are stripped from the mold. The pellets are first processed at 400° C. to remove organics, and then sintered at 850° C. for 2 hours to obtain the said macroporous materials with a compressive strength at approx. 1.25 MPa and a porosity at about 56%. The XRD indicates the existence of both the Ca 4 P 2 O 9 and CaSiO 3 , as shown in FIG. 2 (C). [0026] Finally, the said macroporous materials are immersed in simulated body fluids (SBF) for periods of 6 hours and 1, 3, and 7 days respectively, and evaluated as to both bioactivity and resorbability/degradability. Results in FIGS. 4 and 5 demonstrate that the macroporous glass material of this invention has strong bioactivity, as a bone-like apatite layer is soon formed on the surface of such materials after they are immersed in SBF. After this material has been immersed in SBF for 5 days, its degradation rate can be up to a level of 14%, suggesting that the macroporous bioactive glass material in this invention has ideal degradability, and can therefore be expected to be successfully applied for the restoration of injured hard tissues and as the cell scaffold for in vitro culture of bone tissue. IMPLEMENTATION EXAMPLE 2 [0027] SiO 2 , CaCO 3 , Ca 3 (PO4) 2 , MgCO 3 ,CaF 2 (all of analytical purity) are mixed proportionally, melted into a homogenous fused masses at the temperature of 1450° C., and then cooled, crushed and sieved to obtain bioactive glass powder (particle diameter ranging from 40-300 microns). The composition of the bioactive glass powder is CaO 40.5%, SiO 2 39.2%, MgO 4.5%, P 2 O 5 15.5% and CaF 2 0.3%. [0028] Next, the bioactive glass powder is blended with polyvinyl alcohol powder (300-600 microns in granularity) at a mass percent of 50:50 to obtain a solid mixture. An aqueous solution composed of 20% acrylamide, 2% N,N′-Methylene-bis-acrylamide and 8% polyacrylic acid is prepared, and 10 grams of the said solid mixture is blended with the aqueous solution at a volume percent (ratio) of 50:50, with several drops of ammonium persulfates (3% in mass percent) and several drops of N, N, N′,N′-tetramethyl ethylene diamine (3% in mass percent) added and stirred to produce a slurry with fine fluidity, which is poured into molds for gelation-casting. The cross-linking reaction of monomers of the material is induced for 3 hours at 60° C. In this way, pellets of the macroporous material are obtained by stripping them from the mold after the gelation-casts have been dried at 100° C. for 12 hours. Subsequently, the pellets are processed at 400° C. to remove organics, and then sintered at 850° C. for 2 hours to produce the macroporous materials that feature a compressive strength at about 6.1 MPa and porosity at approx. 55%. This material demonstrated degradability is 78% (calculated based on the mass percent of Si releasing) after being immersed in Simulated Body Fluids for 3 days. IMPLEMENTATION EXAMPLE 3 [0029] The raw materials and the preparation methods of the bioactive glass powder used in this example are the same as those in Implementation Example 2. [0030] The bioactive glass powder (granularity at 150-200 microns) is blended with PEG powder (granularity at 200-300 microns) at the mass ratio of 40:60. Polyvinyl alcohol solution (concentration at 6%) is added to serve as the adhesive and mixed. This mixture is dry-pressed under a pressure of 14 MPa, and pellets of the macroporous materials are obtained by removal from the mold. The pellets are first processed at 400° C. to remove organics, and then sintered at 800° C. to obtain the said macroporous materials with a compressive strength at approx. 1.5 MPa and porosity at about 65%. After being immersed in Simulated Body Fluids for 3 days, the degradation rate of the macroporous glass material is 38% (calculated based on the mass percent of Si releasing). [0031] It is understood and contemplated that equivalents and substitutions for certain elements and steps set forth above may be obvious to those skilled in the art, and therefore the true scope and definition of the invention is to be as set forth in the following claims.
A resorbable, macroporous bioactive glass scaffold comprising approximately 24-45% CaO, 34-50% SiO 2 , 0-25% Na 2 O, 5-17% P 2 O 5 , 0-5% MgO and 0-1% CaF 2 by mass percent, produced by mixing with pore forming agents and specified heat treatments.
2
BACKGROUND OF THE INVENTION [0001] The subject matter disclosed herein relates to belts or ropes used, for example, in elevator systems. More specifically, the subject disclosure relates to fault detection (e.g. of corrosion, fatigue, wear, etc.) of belts or ropes used for elevator suspension and/or driving. [0002] Elevator systems utilize ropes or belts operably connected to an elevator car, and routed over one or more pulleys, also known as sheaves, to propel the elevator car along a hoistway. Coated steel belts in particular include a plurality of wires located at least partially within a jacket material. The plurality of wires is often arranged into one or more strands and the strands are then arranged into one or more cords. In an exemplary belt construction, a plurality of cords is typically arranged equally spaced within a jacket in a longitudinal direction. [0003] During normal elevator operation, coated steel belts and ropes are subject to various failures due to fatigue, wear and corrosion over the time of their service which could progressively lead to a catastrophic consequence. It is desirable to have an online health monitoring system for early warning of structural compromise at low cost. The prevalent technology for real time health monitoring of ferromagnetic rope is magnetic flux leakage (MFL) based inspection which could provide adequate detection of minor rope damage but the system is complex, bulky and costly to elevator industry. Resistance based inspection (RBI) is a low cost and popular method for steel cord reinforced belt inspection. However, it lacks of sensitivity for early warning and ability to detect all the common failure modes of the ropes and belts. Dynamic measurement of extremely low resistance multi-strand cords subject to electromagnetic interference or “noise” and/or thermal or mechanical variations presents major challenges relative to interference resistance and signal to noise ratio of the system. A method of continuous monitoring elevator for early warning of wire rope or steel belt damage with low cost is highly desirable. BRIEF DESCRIPTION OF THE INVENTION [0004] According to one aspect of the invention, a method of fault detection of a belt or rope includes interconnecting a plurality of cords of the belt or rope, the cords including a plurality of wires, to form a bridge circuit. The bridge circuit is subjected to an excitation voltage and outputs a signal voltage, the bridge circuit structure suppressing environmental noise to increase signal to noise ratio of the signal voltage. The signal voltage is monitored to detect a fault condition of the rope. [0005] According to this or other aspects of the invention, the method includes comparing a profile of the measured electrical impedance to a baseline electrical impedance profile and determining a fault condition of the belt or rope via the comparison. [0006] According to this or other aspects of the invention, each leg of the bridge circuit includes at least one cord of the belt or rope. [0007] According to this or other aspects of the invention, each leg of the bridge circuit includes two or more cords of the belt or rope. [0008] According to this or other aspects of the invention, fault conditions include wire breakage, fretting and/or birdcaging. [0009] According to this or other aspects of the invention, the method further includes switching the interconnection of the plurality of cords via a switching mechanism operably connected to the plurality of cords. [0010] According to this or other aspects of the invention, the belt or rope is a coated belt or rope. [0011] According to this or other aspects of the invention, at least one leg of the bridge circuit is a fixed resistor. [0012] According to this or other aspects of the invention, two legs of the bridge circuit each comprise at least one cord and two legs of the bridge circuit each comprise a fixed resistor. [0013] According to another aspect of the invention, an elevator system includes an elevator car and one or more sheaves. A belt or rope having a plurality of wires arranged into a plurality of cords for supporting and/or driving the elevator car is routed across the one or more sheaves and is operably connected to the elevator car. The plurality of cords are interconnected to form a bridge circuit. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIG. 1 is a schematic of an exemplary elevator system; [0015] FIG. 2 is a schematic of another exemplary elevator system; [0016] FIG. 3 is a cross-sectional view of an embodiment of an elevator belt; [0017] FIG. 4 is a cross-sectional view of an embodiment of a cord or rope; [0018] FIG. 5 is a schematic of an embodiment of an elevator belt fault detection unit; and [0019] FIG. 6 is schematic circuit diagram for elevator belt fault detection; [0020] FIG. 7 is a schematic of another embodiment of an elevator belt fault detection unit; [0021] FIG. 8 is another schematic circuit diagram for elevator fault detection; [0022] FIG. 9 is yet another embodiment of an elevator belt fault detection unit. [0023] FIG. 10 is still another embodiment of an elevator belt fault detection unit; [0024] FIG. 11 is a schematic circuit diagram of the embodiment of FIG. 10 ; [0025] FIG. 12 is another embodiment of an elevator belt fault detection unit; [0026] FIG. 13 is a schematic circuit diagram of the embodiment of FIG. 12 ; [0027] FIG. 14 is still another embodiment of an elevator belt fault detection unit; and [0028] FIG. 15 is a schematic circuit diagram of the embodiment of FIG. 14 ; [0029] The detailed description explains the invention, together with advantages and features, by way of examples with reference to the drawings. DETAILED DESCRIPTION OF THE INVENTION [0030] Shown in FIGS. 1 and 2 are schematics of exemplary traction elevator systems 10 . Features of the elevator system 10 that are not required for an understanding of the present invention (such as the guide rails, safeties, etc.) are not discussed herein. The elevator system 10 includes an elevator car 12 operatively suspended or supported in a hoistway 14 with one or more belts 16 or ropes. The one or more belts 16 interact with one or more sheaves 18 to be routed around various components of the elevator system 10 . The one or more belts 16 could also be connected to a counterweight 22 , which is used to help balance the elevator system 10 and reduce the difference in belt tension on both sides of the traction sheave during operation. It is to be appreciated that while the embodiments herein are described as applied to coated steel belts, it is to be appreciated that the disclosure herein may similarly be applied to steel ropes, either coated or uncoated. [0031] The sheaves 18 each have a diameter 20 , which may be the same or different than the diameters of the other sheaves 18 in the elevator system 10 . At least one of the sheaves 18 could be a drive sheave. A drive sheave is driven by a machine (not shown). Movement of the drive sheave by the machine drives, moves and/or propels (through traction) the one or more belts 16 that are routed around the drive sheave. [0032] At least one of the sheaves 18 could be a diverter, deflector or idler sheave. Diverter, deflector or idler sheaves are not driven by a machine, but help guide the one or more belts 16 around the various components of the elevator system 10 . Further, one or more of the sheaves 18 , such as the diverter, deflector or idler sheaves, may have a convex shape or crown along its axis of rotation to assist in keeping the one or more belts 16 centered, or in a desired position, along the sheaves 18 . [0033] In some embodiments, the elevator system 10 could use two or more belts 16 for suspending and/or driving the elevator car 12 . In addition, the elevator system 10 could have various configurations such that either both sides of the one or more belts 16 engage the one or more sheaves 18 (such as shown in the exemplary elevator systems in FIG. 1 or 2 ) or only one side of the one or more belts 16 engages the one or more sheaves 18 . [0034] FIG. 1 illustrates an elevator system 10 in which the elevator car 12 includes a sheave 18 around which the belt 16 is routed to support the elevator car 12 . Similarly, the counterweight 22 includes a sheave 18 around which the belt 16 is routed to support the counterweight 22 . Each end 24 a and 24 b of the belt 16 is terminated at a fixed location such as a support 26 or other fixed location of the elevator system 10 . FIG. 2 illustrates an embodiment of an elevator system 10 in which, as in FIG. 1 , the elevator car 12 includes a sheave 18 around which the belt 16 is routed to support the elevator car 12 . In this embodiment, however, a first end 24 a of the belt 16 is terminated at the support 26 , while a second end 24 b of the belt 16 is terminated at the counterweight 22 and is movable with the counterweight 22 . [0035] FIG. 3 provides a schematic of a belt construction or design. Each belt 16 is constructed of a plurality of wires 28 (e.g. twisted into one or more strands 30 and/or cords 32 as shown in FIG. 4 ) in a jacket 34 . As seen in FIG. 3 , the belt 16 has an aspect ratio greater than one (i.e. belt width is greater than belt thickness). The belts 16 are constructed to have sufficient flexibility when passing over the one or more sheaves 18 to provide low bending stresses, meet belt life requirements and have smooth operation, while being sufficiently strong to be capable of meeting strength requirements for suspending and/or driving the elevator car 12 . The jacket 34 could be any suitable material, including a single material, multiple materials, two or more layers using the same or dissimilar materials, and/or a film. In one arrangement, the jacket 26 could be a polymer, such as an elastomer, applied to the cords 32 using, for example, an extrusion or a mold wheel process. In another arrangement, the jacket 34 could be a woven fabric that engages and/or integrates the cords 32 . As an additional arrangement, the jacket 34 could be one or more of the previously mentioned alternatives in combination. [0036] The jacket 34 can substantially retain the cords 32 therein. The phrase substantially retain means that the jacket 34 has sufficient engagement with the cords 32 to transfer torque from the machine 50 through the jacket 34 to the cords 32 to drive movement of the elevator car 12 . The jacket 34 could completely envelop the cords 32 (such as shown in FIG. 3 ), substantially envelop the cords 32 , or at least partially envelop the cords 32 . [0037] Referring to FIG. 5 , a fault detection unit 52 is electrically connected to a plurality of cords 32 of the belt 16 . The fault detection unit 52 is connected to a terminated portion of the belt 16 , for example, at an end 24 a and/or 24 b of the belt 16 located at the support 26 (shown in FIG. 1 ). The cords 32 are electrically connected to the fault detection unit 52 in a Wheatstone bridge configuration. In one embodiment, as shown in FIG. 5 , each cord 32 a, 32 b, 32 c and 32 d of a four-cord 32 arrangement forms each leg of the Wheatstone bridge. Cord ends 32 A and 32 B are connected are connected via input leads 54 , while cord ends 32 C and 32 D are connected via input leads 54 . Other ends of cords 32 a and 32 b , referred to as 32 A′ and 32 B′ are connected via output lead 56 , while ends of cords 32 c and 32 d, referred to as 32 C′ and 32 D′ are also connected by an output lead 56 . The resulting bridge circuit 58 is shown in FIG. 6 . Each leg 60 of the bridge circuit 58 is an LCR circuit allowing for measurement of complex impedance of the legs 60 or alternatively resistance of the legs 60 . An excitation voltage is applied across the bridge circuit 58 via the input leads 54 from the fault detection unit 52 in the form of an AC voltage, or alternatively a DC voltage source, and the bridge circuit 58 outputs a signal voltage via output leads 56 to the fault detection unit 52 . The fault detection unit 52 compares the excitation voltage to the signal voltage and evaluates an electrical impedance and/or electrical resistance of the belt 16 . The measurements are dynamic such that changes in complex impedance or electrical resistance are evaluated by the detection unit 52 and are indicative of wear, fretting and wire breakage in the cords 32 of the belt 16 . Configuring the cords 32 as a bridge circuit 58 suppresses noise from electromagnetic interference (EMI), temperature variation along a length of the cords 32 , and tensile load variation along each cord 32 . The connection scheme increases the total resistance of the circuit 58 and reduced the interrogating current through the cords 32 , thus improving signal to noise ratio. Further, since the cords 32 are all interconnected in the circuit 58 , all of the cords 32 are monitored simultaneously, thus reducing a number of required measurement channels. [0038] In another embodiment, as shown in FIG. 7 , the belt 16 includes 8 cords 32 , with adjacent cords 32 arranged in cord-pairs 64 A, 64 B, 64 C and 64 D. The configuration of FIG. 7 is utilized when, for example, the first end 24 a of the belt 16 is fixed and the second end 24 b is not fixed, as in the elevator system 10 of FIG. 2 . In this embodiment, the individual cords 32 of each cord-pair 64 A, 64 B, 64 C, 64 D are connected at the second end 24 b by jumper wires 66 . At the first end 24 a, the cord pairs 64 A, 64 B, 64 C, 64 D are interconnected to form the bridge circuit 58 . For example, as shown in FIG. 7 and FIG. 8 , cord-pair 64 A is connected to cord-pair 64 B, cord-pair 64 B is connected to cord-pair 64 C, cord-pair 64 C is connected to cord-pair 64 D, and cord-pair 64 D is connected to cord-pair 64 A. As in the embodiment of FIG. 6 , voltage is applied across the bridge circuit 58 via the input leads 54 and output leads 56 from the fault detection unit 52 measures an electrical impedance and/or electrical resistance of the belt 16 . Specifically, an output voltage at the output leads 56 indicates a difference in impedance of cord-pairs 64 A and 64 D from cord-pairs 64 B and 64 C, or inner cords 32 of the belt 16 compared to outer cords 32 of the belt 16 . While the cords 32 of cord-pairs 64 A, 64 B, 64 C and 64 D are illustrated as connected external to the jacket 34 , in some embodiments, the cords 32 are connected internal to the jacket 34 . Further, while embodiments of belts 16 having 4 or 8 cords 32 are illustrated, it is to be appreciated that in other embodiments, belts 16 having any number of cords 32 four or greater may be utilized, with select cords 32 connected as bridge circuit 58 at any one time. [0039] In another embodiment, as shown in FIG. 9 , the cords 32 are connected to a switch array 68 including one or more relays or other switching elements. In this embodiment, the cords 32 are selectably connected fault detection unit 52 . In belts 16 having greater than 4 cords 32 , this allows for selection of cords 32 or multiples of cords 32 for assessment. Further, with the selective connection of a single cord 32 , the fault detection unit 52 may assess the condition of the single cord 32 via, for example, a traditional resistance-based inspection process. [0040] Referring now to FIGS. 10-15 , a combination of cords 32 and fixed resistors 70 may be used to define the bridge circuit 58 . As shown in FIGS. 10 and 11 , two cords, in this embodiment 32 c and 32 d are used in combination with two resistors 70 , for example, two low inductance resistors 70 , to form the bridge circuit 58 . Output leads 56 are connected between cords 32 and resistors 70 and the fault detection unit 52 essentially compares the complex impedance of the cords 32 c and 32 d to the impedance of the fixed resistors 70 . The impedance of the fixed resistors 70 is stable, while the impedance of cords 32 c and 32 d is variable, so change in impedance of the cords 32 c, 32 d is more easily detectable. In some embodiments, the resistor 70 legs are low inductance and may also be temperature matched utilizing thermocouples and heaters (not shown). Further, the resistors 70 are matched to the cord impedance within 0.5 to 10× of the cord impedance. [0041] In another embodiment, as shown in FIGS. 12 and 13 , cord pairs 64 A and 64 B are connected to form two legs of the bridge circuit 58 , while resistors 70 for the other two legs. The behavior of this bridge circuit 58 is similar to that of the circuit in FIGS. 10-11 , but with higher levels of cord impedance. Additional cords 32 may be connected in series to form legs 64 A and 64 B. [0042] Referring to FIGS. 14 and 15 , in some embodiments, the cords 32 and resistors 70 are interconnected such that the bridge circuit 58 is formed with cords 32 at opposing legs, and likewise resistors 70 at opposing legs, as opposed to at adjacent legs as in other embodiments. In this embodiment, an increase in complex impedance in the cords 32 will unbalance the bridge in opposite directions, resulting in approximately double the measurable signal at the fault detection unit 52 . Thus a smaller change in impedance in the cords 32 is detectable. [0043] While the invention has been described in detail in connection with only a limited number of embodiments, it should be readily understood that the invention is not limited to such disclosed embodiments. Rather, the invention can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the invention. Additionally, while various embodiments of the invention have been described, it is to be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims.
A method of fault detection of a belt or rope includes interconnecting a plurality of cords of the belt or rope, the cords including a plurality of wires, to form a bridge circuit. A fault detection bridge circuit is subjected to a voltage excitation and outputs a voltage which is indicative of the belt or rope damage but remaining insensitive to other environmental noises.
3
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention concerns wall thickness measurements in general. More specifically it concerns a method and apparatus for measuring wall thickness of metallic material. It is also well adapted for making combined measurements of wall conditions in pipelines and the like. 2. Description of the Prior Art Magnetic methods have been used heretofore for finding anomalies of pipes or pipelines. But, they have not been found quantitatively accurate, and they often fail to provide a true qualitative representation of accurate wall conditions. It has been found that magnetic permeability differences between the steel pipe and surrounding medium, become a primary problem when sensor pads bounce and vibrate from the pipe wall as a result of passing weld joints and other obstructions. Also, magnetic fields induced into the pipe by current conducting brushes or permanent magnets are often unstable. Consequently, it is an object of this invention to provide a method for measuring wall thickness of metallic materials which method uses a pulsed magnetic reluctance coil rather than passive sensor coils or diodes in the presence of a steady state magnetic field. In addition, this method provides for determining the distance between such pulsed coil and the metallic material in order that the inductance measured may be compensated to provide accurate indication of wall thickness. SUMMARY OF THE INVENTION Briefly, the invention concerns a magnetic method for measuring wall thickness of metallic material which comprises the steps of applying a pulse of energy to a magnetic reluctance coil having said metallic material in the proximity of said coil, and measuring the inductance of said pulsed coil. It also comprises determining the distance between said pulsed coil and said metallic material, whereby said inductance is a measure of said wall thickness. Again briefly, the invention relates to a pipeline wall condition monitor. And, it concerns a magnetic method for finding anomalies. The method comprises applying a pulsed magnetic field to said pipeline wall, and measuring the permeability of the magnetic circuit of said field. It also comprises measuring the length of the flux path of said magnetic circuit. Again briefly, the invention concerns a pipeline wall condition monitor which comprises in combination, means for magnetically pulsing said pipeline wall to measure the permeability thereof, and means for determining the distance of said pulsing means from said wall in order to correct for variations thereof. Again briefly, the invention concerns a combined magnetic and acoustic wall thickness and condition measuring apparatus. It comprises in combination a pulsed magnetic reluctance means for measuring said wall thickness, and ultrasonic means for measuring the distance of said magnetic means from said wall. Once more briefly, the invention concerns a combined magnetic and acoustic wall thickness and condition measuring apparatus. It comprises in combination a reluctance coil having the axis thereof transverse to said wall and adapted for having a small gap between the coil and said wall in order to include said wall in the magnetic field of the coil. And, it comprises first circuit means for pulsing said reluctance coil and for determining the permeability of said magnetic circuit. It also comprises an ultrasonic transducer mounted in a fixed position relative to said reluctance coil, and acoustic reflecting means for directing ultrasonic energy both perpendicular to said wall and at an angle of incidence greater than the critical angle of refraction of said wall. It also comprises second circuit means for pulsing said transducer and for measuring reflected ultrasonic energy from both said perpendicular and angled energy paths. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other objects and benefits of the invention will be more fully set forth below in connection with the best mode contemplated by the inventor of carrying out the invention and in connection with which there are illustrations provided in the drawings, wherein: FIG. 1 is a schematic cross-sectional showing which illustrates apparatus according to the invention as it would be used for making measurements in a pipe; FIG. 2 is a schematic circuit diagram illustrating a system including electrical circuits that might be employed with a plural instrument measuring system for use in a pipe or pipeline; FIGS. 3-6 are illustrations showing oscilloscope traces of signals generated under particular conditions in accordance with the invention; and FIG. 7 is a graph showing inductance as the ordinate and the thickness of a wall as the abscissa, of the graph. There are two curves shown, one for the measurement with the wall thickness variation on the same side of the wall as the measuring coil, and the other for the measurement with the thickness variation on the other side from the measuring coil. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic indication of the elements used in an acoustic wall thickness and condition measuring apparatus that is combined with a magnetic measurement. It will be appreciated that apparatus according to this invention could be employed for detecting and identifying pits which might be external or internal relative to the pipe of a pipeline, an offshore platform riser, a storage tank bottom or any other inaccessible steel or iron structure. Also, as will appear more fully hereafter, this inspection device could be used as a single unit or in multiples (not shown), depending upon the area and configuration of the structure that is to be inspected. For a pipeline instrument, multiple units or devices would be arranged around the periphery of the pipe in order to allow electronic stepping from one device to another so as to cover the entire wall of the pipe. Such an arrangement of the units would be similar to that indicated in a patent assigned to the same assignee as this application; i.e. U.S. Pat. No. 4,022,055 issued May 10, 1977. With reference to FIG. 1, there is a pipe wall 11 which has an internal pit 12 that may have been caused by corrosion or the like, and the presence of which is to be determined. An instrument 15 is schematically shown. It has mounted thereon a reluctance coil 16 that may be mounted in a block of supporting material 19 in a manner such that the axis of coil 16 is transverse to the wall 11 of the pipe. Also, there may be a thin surface of wear-resistant material 20 which bears against the inside surface of the pipe 11 as the instrument is used when surveying pipe wall conditions. Mounted in a fixed position relative to the reluctance coil 16, there is an ultrasonic transducer 23 that has acoustic material lenses 24 and 25 one on each face of transducer 23 in order to focus the acoustic energy pulses. Such pulses are generated by the transducer 23 when it is electrically pulsed in a manner that is known to those skilled in the art, e.g. as generally described in the above mentioned U.S. Pat. No. 4,022,055. The acoustic pulses are focused into columnar form for transmitting them along the identical paths (shown by dashed lines) 28 and 29, respectively. Also mounted on the instrument 15 there are a pair of acoustic reflectors 32 and 33 that have the reflecting surfaces of each set at desired angles so that the column 29 of acoustic energy will be reflected at a right angle or transverse path relative to the pipe wall 11. And, the reflecting surface of the reflector 33 has an angle such that its column of acoustic energy (path 28) will be directed at an angle of incidence relative to the pipewall 11 which is greater than the critical angle of refraction of the wall. This provides for operating conditions similar to those described in the above noted U.S. Pat. No. 4,022,055 so that any reflected acoustic energy will indicate the presence of a pit or other anomaly such as the pit 12. Such reflected acoustic energy returns along the acoustic path 28 indicated, and generates a signal at the transducer 23 which indicates the presence of the anomaly. In the absence of such anomaly no reflected acoustic energy will return because of the angle of incidence indicated. At the other face of the transducer 23, the acoustic energy pulses are transmitted so as to reflect from the reflector 32 and be directed at right angles to the surface of the pipe 11. Consequently, there will be reflected energy returned from both the inside and from the outside of the pipe wall 11. Such acoustic signals will then provide a measure of the thickness of the wall 11 as well as a measure of the distance from the instrument to the inside surface of the pipe wall 11. It will be understood that the instrument 15 includes portions 36 and 37 thereof which each have a wear-resistant surface layer 38 and 39, respectively. These surface layers bear against the inside surface of the wall 11 during normal operations. FIG. 2 illustrates schematic circuits that are suitable for pulsing each of the reluctance coil 16 and the acoustic transducer 23. It may be noted that FIG. 2 also illustrates a plurality of similar circuits which would be employed when the instrument surveying a pipe or pipeline includes a plurality of the instruments 15. These instruments 15 would be positioned around the entire inner periphery of the pipewall 11 in a manner similar to that described in the U.S. Pat. No. 4,022,055. In connection with each instrument 15, the reluctance coil 16 is pulsed by having a silicon controlled rectifier 42 connected in series therewith. It should be noted that hereafter the common designation SCR will be used to stand for the terms silicon controlled rectifier. In the circuit illustrated in FIG. 2, the SCR 42 has a circuit connection from its cathode leading to one end of the coil 16. And, its anode is connected via a resistor 43 to a voltage source 44 that is indicated by the plus V caption. There is a capacitor 47 that is charged through the resistor 43 from the source 44. It has one side thereof grounded as indicated. When the coil 16 is to be pulsed, the SCR 42 will be triggered via a resistor 48 and buffer 49. The buffer 49 acts to pass on a trigger signal which will originate from a selector network 52. Then the signal at a point 53 will be amplified by an amplifier 54 after which it may be transformed by an analog to digital converter 57 if desired. It will be understood that the discharge of capacitor 47 takes place through the SCR 42 and the coil 16 in series therewith on the way back to ground via a resistor 58. The transducer 23 will be pulsed at or near the time of pulsing of the reluctance coil 16 in order to provide for the distance measurement of the wall 11 from the coil 16. And, the circuit for pulsing the transducer 23 is similar to that for the coil 16. Thus, there is a voltage source terminal 61 with a resistor 62 connected between it and one terminal of a capacitor 63., the other terminal of which is grounded. Another SCR 66 has its control electrode connected via a resistor 67 to another buffer 68. Buffer 68 is connected to the selector network 52 where trigger signal for the transducer 23 also originates. In this case, when the SCR 66 discharges it goes via a resistor 71 and an inductance 72 both in parallel with the transducer 23. Consequently, this discharge current will pulse the transducer as desired. That acoustic pulse generating signal and the reflected return acoustic signals received by the transducer 23 thereafter, will all be amplified by an amplifier 75 which may have its output connected to an analog/digital converter 76. It is to be expected that normally the SCR 66 would be triggered first so that the other SCR 42 could be triggered at the time of the arrival of the ultrasonic reflected energies back to the transducer 23. In such manner, a measurement of the distance of the instrument 15 and, particularly, the coil 16 from the wall 11 of the pipe that is being surveyed, will be made at the time when the magnetic reluctance is being measured. Consequently, the accuracy of the reluctance measurement may be verified or a compensating adjustment may be applied to the pulsed magnetic signal from the coil 16. FIGS. 3, 4, 5 and 6 illustrate pulses that were recorded from an oscilloscope when a reluctance coil and resistor were energized in a laboratory simulation of the FIG. 2 circuit involving the pulsed magnetic coil 16. The trace A in each case represents the applied voltage pulse that is generated when the SCR is triggered and the trace B in each case indicates the IR voltage of the reluctance circuit. The vertical oscillograph scale in each case, is such that it represents one volt per vertical division, each of which represents one centimeter in the case of the trace A. And, in the case of the trace B in each case, the scale is such that the IR voltage of the reluctance circuit is represented by the vertical divisions (one centimeter) each of which represent two milli-volts per vertical division. The time base of the oscillographs is ten micro seconds per horizontal division which again represent one centimeter each. And, the signal repetition rate is at ten kilo-Hertz. It is to be noted that the FIG. 3 oscillograph was made with a coil, e.g. coil 16, over a full thickness of material simulating the wall 11. In the actual simulation the full thickness was 0.117 inch. FIG. 4 illustrates another simulation with the same scales and time base. This case employed a depression or pit that was 5/8 inch across and was located on the opposite side of the simulated wall from the coil and had a depth such that the wall was 0.060 inch thick. Similarly, FIGS. 5 and 6 illustrate additional simulations which were made with the thickness reduced more in each case. Thus, in FIG. 5 the same scales and time base were employed with the pit being 5/8 inch across and again located on the opposite side of the simulated wall with the depth such that the wall was 0.040 inch thick. And in FIG. 6 the only change was to make the depth of the pit such that the wall was 0.025 inch thick. It may be noted that in the simulations illustrated in FIGS. 4, 5 and 6, all three were carried out with the coil located on the opposite side of the material being tested from the pit. In other words, the pit was on the other side of the wall from the reluctance coil. As a result, while it was expected that a pit or reduction in thickness of the wall would cause a reduction in the inductance of the coil, the opposite effect was discovered. It appears that a possible explanation for this phenomenon is that the lines of magnetic flux may be concentrated in the thinner metal section which causes an increase in the flux density near the coil center. Furthermore, it was found that when the pits that were being measured were located on the same side of the material wall as the coil, then the inductance was reduced instead of being increased and thus a manner of determining which side of the wall a pit was located on, has been discovered. This situation is illustrated in FIG. 7 where the graph shows two curves 81 and 82. These were made from measurements of the inductance (on the ordinate of the graph) against the thickness of the plate (on the abscissa of the graph). These curves meet at a point 85 which represents the full thickness of the plate being measured. The curve 81 shows the inductance values when the points that determined the curve were measured with the reduced thicknesses made by a simulated pit in each case, located on the opposite side of the plate from the coil that was employed to make the measurements. On the other hand, the curve 82 shows the values of inductance that were found when the same thickness reductions were tested but with the simulated pit located on the same side as the coil. Therefore, it may be noted that not only may a pit be identified but its location as to whether it is on the same side of the wall being measured or the opposite side thereof, will be indicated by the signals generated. It will be appreciated that a method according to this invention may be carried out by various and different types of apparatus and the method has the benefits indicated above that make it more accurate and reliable than the previous magnetic surveying methods. Thus, a method, according to this invention, includes the step of applying a pulse of energy to a magnetic reluctance coil that is located with the metallic material in proximity to the coil. And, it includes the step of measuring the inductance of the pulsed coil. The latter is carried out and thereafter, or coextensively therewith, the method includes the step of determining the distance between the pulsed coil and the metallic material. The latter is carried out by employing the transducer and ultrasonic distance measuring technique indicated above. A mathematical explanation of the magnetic method employed may be clarified by the following explanation. Thus, the self-induced emf E s is an indication of the quantity of permeable material in the proximity of a pulsed reluctance coil. And, it is related to the permeability, μ, by the following formulae: ##EQU1## where φ=magnetic flux i=current N=number of turns 1=length of the flux path (magnetic circuit) A=cross-sectional area of the flux path μ=permeability The foregoing equations show that a predictable dφ/dt requires a known 1/μ ratio and when μ is very small as in the case for media other than steel, 1 must be kept small also. The permeabilities of oil, water or gas are several orders of magnitude smaller than that of steel. While the foregoing explanations have been set forth in considerable detail in accordance with the applicable statutes, this is not to be taken as in any way limiting the invention but merely as being descriptive thereof.
A pulsed magnetic procedure and apparatus for measuring wall thickness. It is especially applicable to pipelines. It includes pulsing a magnetic reluctance coil that is located close to the wall, and measuring the inductance of the pulsed coil. Also the distance of the coil from the wall is accurately determined so that the inductance is a measure of the wall thickness. Apparatus may include the combination of an ultrasonic transducer mounted fixed relative to the magnetic pulse coil and arranged so that ultrasonic energy pulses are directed toward the wall. In this manner reflected ultrasonic pulses will provide a measure of the distance. In addition, by proper angle thereof, ultrasonic pulses may also determine the presence of any anomaly.
6
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a one-way clutch used for torque transmission, back stop or overrunning in an automatic variable speed device to be used for an automobile etc., and more particularly to a lubricating device for leading lubricating oil into the inside of a one-way clutch having clutch members such as sprags or rollers. 2. Related Background Art In a one-way clutch effective to transmit rotary power in one direction only and free running in another direction, clutch members such as sprags or rollers are disposed between inner and outer rings and both end surfaces of the clutch members are guided by side plates. The clutch members engage with the inner and outer rings when the rotary power is transmitted and slip therebetween during free running. Such a conventional one-way clutch is shown in FIGS. 27 to 32. FIG. 27 shows a one-way clutch where lubricating oil is supplied to clutch members from the inner ring side, FIG. 28 shows the assembly of the one-way clutch, FIG. 29 shows a longitudinal cross section of FIG. 28, and FIG. 30 shows details of the roller arrangement. FIG. 31 shows a one-way clutch where lubricating oil is supplied to clutch members from the outer ring, and FIG. 32 shows an application of a one-way clutch. In FIG. 27, a conventional one-way clutch 1, where lubricating oil is supplied from inner ring to clutch members, comprises inner ring 2 and outer ring 3, and rollers 4 are disposed between the inner and outer rings. At the inner peripheral surface of outer ring 3, a cam surface 3a is formed in association with each roller 4 to constitute cam structure 5 together with the roller 4 so that the inner ring 2 can rotate relative to outer ring 3 only in one direction. At one side surface of outer ring 3, a step 3b is formed, to which a first side plate 6 fits to effect centering of the first side plate 6. The first side plate 6 covers first end surfaces of rollers 4 and parts of the first side plate 6 are folded to form folded pieces 6a, which penetrate between inner ring 2 and outer ring 3. The front end 6b of each piece 6a projects from the other side of the outer ring. At the other side surface of outer ring 3 a second side plate 7 is provided which covers the other end surfaces of rollers 4. The second side plate 7 has small holes 7a through which folded pieces 6a of the first side plate 6 project, and the front end 6b of each piece 6a is caulked at the outer surface of the second side plate 7 so as to effect centering of the second side plate 7 and to fix both side plates 6 and 7 to outer ring 3. Inner ring 2 has a groove 2a at its inner peripheral surface and lubricating oil filled in groove 2a is supplied to rollers 4 through a lubricating oil hole 2b by centrifugal force. As shown in FIGS. 28 and 30, centering blocks (pad bearings) 8 are provided between outer ring 3 and inner ring 2. Each centering block 8 comprises a slide part 8a, which slidingly contacts inner ring 2, folded parts 8b engaging with a recess 3c formed at the inner peripheral surface of outer ring 3 and supported by folded pieces 6a, and supporting parts 8c connecting slide part 8a and folding parts 8b. Folding parts 8b of centering block 8 are supported by folded pieces 6a so as to be fixed to recess 3c of outer ring 3. FIG. 31 shows a conventional one-way clutch 9 where lubricating oil is supplied to the clutch members from outer ring side, with parts corresponding to those in one-way clutch 1 being assigned the same reference numbers. The difference from the one-way clutch where lubricating oil is supplied from inner ring is that instead of the hole 2b and the groove 2a of inner ring 2, a lubricating hole 3c is provided in outer ring 3, and the lubricating oil is supplied through the hole 3c to rollers 4. The application of one-way clutch 1 is shown in FIG. 32, in which inner ring 2 is welded to a plate 100. In one-way clutches 1, 9, since rollers 4 slide during free running, heating and friction become large unless sufficient lubrication is provided. The use of a lubricating hole 2c or 3c as previously described leads to a number of practical problems. For example, the presence of the hole leads to stress concentration which can cause damage and reduce the service life of the clutch. Peeling off or scratching of the edge of the hole can occur when the clutch is engaged with the hole being subjected to heavy surface pressure by a clutch member. Although the clutch structure may be reinforced by increasing the thicknesses of the inner and outer rings, this causes the clutch to become undesirably heavy and bulky. As still another problem, the forming of the aforementioned lubricating hole requires a complex and expensive operation. SUMMARY OF THE INVENTION Basically speaking, the present invention overcomes such problems of the conventional one-way clutches through the use of a novel arrangement in which lubricating oil is guided to the clutch members without the use of a lubricating hole in one of the inner and outer race track surfaces. For example, in a first preferred form, a one-way clutch according to the present invention includes a centering block having a sliding portion sliding on the track surface of one of the inner and outer clutch rings and a pair of spaced radially extending supporting portions, a side plate attached to one of the inner and outer rings and covering corresponding end surfaces of the clutch members, the side plate having a hole therethrough in alignment with a space between the supporting portions of the centering block, and means for introducing lubricating oil into said space through the hole of the side plate. In another preferred form of the invention, a side plate of a one-way clutch is provided with means including an axially outwardly protruding inner peripheral portion of the side plate for catching lubricating oil flowing outwardly in a radial direction under centrifugal force and for directing the lubricating oil between the track surfaces of the inner and outer clutch rings. In still another preferred form of the invention, a one-way clutch is provided with a side plate having at least one axially outwardly protruded and radially inwardly open embossment for catching lubricating oil flowing outwardly in a radial direction under centrifugal force and for directing the oil between the track surfaces of the inner and outer clutch rings. In yet another preferred form of the invention, a one-way clutch is provided with a side plate having a hole therethrough in communication with a space between the track surfaces of the inner and outer clutch rings. An oil catcher is attached to the side plate and has a wall extending circumferentially of the side plate and outwardly along an axis of the side plate to define an oil catchment space for catching lubricating oil flowing outwardly in a radial direction under centrifugal force and to guide the lubricating oil into the hole of the side plate. The above and other preferred forms of the invention, and additional features and advantages thereof are more fully explained in the detailed description hereinafter. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an enlarged fragmentary cross-sectional view of a first embodiment of a one-way clutch of this invention, where lubricating oil is supplied to clutch members from the inner ring side; FIG. 2 is a cross-sectional view of the one-way clutch according to the first embodiment; FIG. 3 is a front view of the one-way clutch of the first embodiment; FIG. 4 is an enlarged fragmentary cross-sectional view of a second embodiment of this invention; FIG. 5 is a cross-sectional view of the second embodiment; FIG. 6 is a front view of the second embodiment; 15, FIG. 7 is an enlarged fragmentary cross-sectional view of a third embodiment; FIG. 8 is a cross-sectional view showing a second side plate and oil catcher of the third embodiment in more detail; FIG. 9 is a front view of the one-way clutch of the third embodiment; FIG. 10 shows details in the region of a centering block; FIG. 11 is a front view of a modification of the third embodiment; FIG. 12 is a detailed view showing a stop ring mounted on an outer ring; FIGS. 13A and 13B are cross-sectional and front views, respectively, showing a triangle shape member provided on a side plate; FIG. 14 is an enlarged fragmentary cross-sectional view of a fourth embodiment of the one-way clutch, where lubricating oil is supplied to clutch members from the outer ring side; FIG. 15 is an enlarged fragmentary cross-sectional view of a fifth embodiment; FIG. 16 is an enlarged fragmentary plan view as seen in arrow direction B of FIG. 15; FIG. 17 is an enlarged fragmentary cross-sectional view of the second side plate and oil catcher of a sixth embodiment; FIGS. 18 and 19 are enlarged fragmentary cross-sectional views of one-way clutches providing a pipe; FIG. 20 to FIG. 23 show an embodiment where two oil catchers are provided for supplying lubricating oil from the outer ring and inner ring, respectively; FIG. 24 shows a modification of an oil catcher shown in the third embodiment; FIG. 25 is an enlarged view showing details of the embodiment of FIG. 24; FIG. 26 is cross-sectional view taken along line E--E of FIG. 25; FIG. 27 is an enlarged fragmentary cross-sectional view of a conventional one-way clutch where a lubricating hole is provided through the inner ring; FIG. 28 is a front view, partly cut away, of the one-way clutch of FIG. 27; FIG. 29 is longitudinal cross-sectional view of the one-way clutch in FIG. 28; FIG. 30 shows details of the roller arrangement; FIG. 31 is an enlarged fragmentary cross-sectional view of a conventional one-way clutch where a lubricating hole is provided in the outer ring; and FIG. 32 shows a conventional application of a one-way clutch. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1 to 3 show a first embodiment of the invention, in which a one-way clutch 10 has lubricating oil supplied to the clutch members from the inner ring side. In FIG. 1, one-way clutch 10 comprises inner ring 11 and outer ring 12, and rollers 13 disposed between the inner and outer rings. A cam surface 12a is formed at the inner peripheral surface of outer ring 12 for each roller 13. Each cam surface 12a and associated roller 13 form a cam structure 14, so that inner ring 11 can rotate in only one direction relative to outer ring 12. At one side surface of outer ring 12, a step 12b is formed, and a first side plate 15 is mounted on step 12b, thus centering side plate 15. Side plate 15 covers first end surfaces of rollers 13, and parts of the plate 15 are folded to form folded portions which penetrate between inner ring 11 and outer ring 12. A front end portion 15b of each folded portion 15a projects out past the other side of outer ring 12. At the other side of outer ring 12, a second side plate 16, which covers the other end surfaces of rollers 13, is provided. Second side plate 16 has holes 16a through which folded portions 15a project, and each front end portion 15b is caulked at the surface of side plate 16 so as to center second side plate 16 and fix both side plates 15 and 16 to outer ring 12. As best seen in FIG. 1, the inner peripheral end portion of second side plate 16 projects outwardly along the rotating axis (horizontal in FIG. 1) of one-way clutch 10 to form a bulging portion 16b. Thus, a lubricating oil path is formed such that lubricating oil flowing outwardly in a radial direction by centrifugal force is received by bulging portion 16b and supplied to rollers 13. FIGS. 4 to 6 show a second embodiment, in which a second side plate 17 has bulging portions arranged at circumferential intervals, taking the strength of second side plate and action of one-way clutch 10 into consideration. Other portions are similar to the first embodiment. As will be appreciated from FIGS. 4 and 5, plural portions of the inner peripheral edge of second side plate 17 are press worked to project outwardly along the rotating axis of one-way clutch 10 to form bulging portions 17b. Consequently, as in the first embodiment, due to centrifugal force, the lubricating oil flowing outwardly in the radial direction is received by bulging portions 17b to supply the oil to rollers 13. FIGS. 7 to 10 show a third embodiment. Instead of providing bulging portions on the second side plate, an oil catcher 19 for receiving lubricating oil is provided in the third embodiment. There is no difference in the elements other than second side plate and catcher from the second embodiment. In a second side plate 18, as shown in FIG. 9, six penetrating holes 18a are equiangularly spaced to penetrate from one side to the other side of the second side plate. As shown in FIG. 10, such a penetrating hole 18a communicates with the inside of a centering block 8. Fitted to this hole 18a, is an outer peripheral groove 19b provided on a tubular projection 19a of oil catcher 19, so as to fix oil catcher 19 to second side plate 18. Oil catcher 19 is made of elastic material such as plastic, and it is possible to push projection 19a into penetrating hole 18a. Oil catcher 19 projects outwardly along the rotating axis of one-way clutch 10. The inner peripheral portion of oil catcher 19 is circular and the outer peripheral portion is of substantially hexagon shape with the apexes positioned at holes 18a. Between oil catcher 19 and second side plate 18, a lubricating oil path is formed, which communicates with the inside of centering block 8 in one-way clutch 10 through penetrating hole 19c of projections 19a. According to the above structure, lubricating oil flowing outwardly in the radial direction by centrifugal force is received by oil catcher 19 and the oil is collected at the tubular projection 19a at the apex of hexagon shaped oil catcher 19, so that the oil is supplied to the inside of centering block 8 through penetrating hole 19c. In this embodiment, oil catcher 19 is mounted on second side plate 18, but it is possible to mount oil catcher 19 on first side plate 15. Further, as shown in FIG. 11, for reducing the possibility of chipping the ends 15b of folded portions 15a of first side plate 15, the outer periphery of the oil catcher, designated 20 in this modification, made substantially circular, so that only tubular projections 20a project outwardly in the radial direction. FIG. 12 shows an embodiment in which a projection 21 is provided along the whole periphery of outer ring 12 of one-way clutch 10, extending outwardly along the rotating axis of clutch 10. A key groove 21a is formed on projection 21, and an annular stop ring 22 fits in this groove 21a to form a trough, which receives lubricating oil flowing outwardly in the radial direction. The oil is supplied to the inside of the clutch 10 through penetrating hole 23a of a second side plate 23. Referring to FIG. 13, substantially triangular shaped embossments 24a may be equiangularly spaced on a second side plate 24, and through substantially triangular apertures 24b formed at embossments 24a lubricating oil is supplied to one-way clutch 10. Further, a groove 11a extending radially outwardly can be provided on one side of inner ring 11 at a position corresponding to embossment 24a so as to make lubricating oil flow into aperture 24b more smoothly. Explanation will now be made of an embodiment where lubricating oil is supplied to a one-way clutch 30 from the outer ring side. FIG. 14 shows a fourth embodiment, which differs from the first embodiment in the structure of the second side plate. The second side plate 31 has a bulging portion 31a projected outwardly along the rotating axis of one-way clutch 30. Consequently, lubricating oil supplied from an unillustrated external device is received by bulging portion 31a of second side plate 31 to supply the lubricating oil to rollers 13. FIGS. 15 and 16 show a fifth embodiment, which is similar to the fourth embodiment, but with a different second side plate and outer ring. Plural portions at the outer periphery of second side plate 32 are projected outwardly along the rotating axis of one-way clutch 30 to form bulging portions 32a. In an outer ring 33, a groove 33a extending radially from outer periphery to inner periphery is provided at a position corresponding to bulging portion 32a. FIG. 16 shows one-way clutch 30 seen in the arrow direction B in FIG. 15. With the provision of groove 33a, lubricating oil coming from the lubricating path provided from an unillustrated external device is received more smoothly at the bulging portion 32a and efficiently supplied to rollers 13. FIG. 17 shows a sixth embodiment of the invention, in which, instead of providing the bulging portion at the second side plate, an oil catcher is mounted for receiving lubricating oil. The sixth embodiment differs from the third embodiment in that the oil catcher opens outwardly in the radial direction. As in the third embodiment, second side plate 18 has penetrating holes 18a penetrating from one side to the other side in the manner shown in FIG. 17. To each penetrating hole 18a a tubular projection 34a of oil catcher 34 fits, whereby oil catcher 34 is fixed to second side plate 18. Lubricating oil flowing from an unillustrated external device is received by the oil catcher and supplied to rollers 13 through holes 18a. According to the invention as shown in FIGS. 18 and 19, a pipe communicating with the one-way clutch can be provided to supply lubricating oil to rollers 13. In FIG. 18, a second side plate 35 provides a penetrating hole 35a to which a pipe 36 fits so that lubricating oil coming from an unillustrated external device can be supplied to rollers 13 through pipe 36. Further as shown in FIG. 19, an externally projecting tubular projection 37a may be provided on a second side plate 37, and a pipe 38 may be mounted to projection 37a so that lubricating oil coming from the unillustrated external device is supplied to rollers 13 through pipe 38. FIGS. 20 to 23 show arrangements in which lubricating oil is provided from the outer and inner ring sides, in substantially a combination of the third and sixth embodiments. As shown in FIGS. 20 and 21, a notch 19a is provided at the portion of oil catcher 19 receiving lubricating oil flowing by centrifugal force An oil catcher 34 receiving lubricating oil is mounted on notch 19a. FIGS. 22 and 23 show similar structure in which oil catchers 20 and 34 are provided. FIGS. 24 through 26 show a modification of oil catcher 20 of the third embodiment shown in FIG. 11. In FIG. 24, oil catcher 120 mounted on penetrating hole 18a of second side plate 18 has weir 120b provided in the vicinity of tubular projection 120a for leading lubricating oil to penetrating hole 18a. As oil catcher 120 receives lubricating oil flowing from the rotating elements around the one-way clutch, the received oil has momentum in a circumferential direction and rotates within the catcher 120 as shown by arrow C. Consequently, for leading the lubricating oil rotating within oil catcher 120 to penetrating hole a, weir 120b is provided behind penetrating hole 18a relative to the rotating direction of the lubricating oil so that as shown by arrow D, lubricating oil impinges on weir 120b and then flows easily into penetrating hole 18a. FIG. 26 is a cross-sectional view along line E--E in FIGS. 25. Lubricating oil impinges on weir 120b, as shown by arrow F, to flow into penetrating hole 18a. The lubricating device of the one-way clutch of the present invention is, of course, not limited to the above-described embodiments, and various changes and modifications may be made without departing from the spirit and principles of the invention, as will be readily appreciated by those skilled in the art. It will also be appreciated that because it is not necessary to provide a lubricating hole in the inner or outer ring in the present invention, it is possible to reduce the weight of the one-way clutch and to reduce the cost. Moreover, the invention allows the mounting position of the one-way clutch to be selected with a greater degree of freedom, being unrestricted by the location of such a lubricating hole.
A one-way clutch incorporates an arrangement to lead lubricating oil to the torque transmitting members without the use of a penetrating hole in the inner ring or outer ring of the clutch. Instead, a guide arrangement is provided externally of the track surfaces of the inner and outer rings for leading the lubricating oil from outside the one-way clutch to the torque transmitting members, e.g. rollers or sprags. In a clutch having a centering block for supporting the inner and outer rings, the guide arrangement may lead the lubricating oil into the centering block.
5
CROSS-REFERENCE TO RELATED APPLICATION [0001] Pursuant to 35 U.S.C. §119(a), this application claims the benefit of earlier filing date and right of priority to Korean Application No. 10-2014-0087645, filed on Jul. 11, 2014, the contents of which is incorporated by reference herein in its entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present disclosure relates to a magnetic switch. [0004] 2. Background of the Invention [0005] A magnet switch is a device used for switching (opening or closing) power of an electric line, and is extensively utilized for industrial, household, and vehicle purposes. In particular, a magnetic switch for a vehicle is used to supply and cut off DC power provided from a storage battery of a vehicle such as a hybrid vehicle, a fuel cell vehicle, or a golf cart. [0006] Such a magnetic switch is closed and a current flows when a stationary contact arm and a movable contact arm are brought into contact with each other, and in particular, in order to control an arc generated when DC power having a high voltage is cut off, a permanent magnet is used. The magnetic switch employs a breaking mechanism in which a permanent magnet is appropriately disposed in the vicinity of a stationary contact arm and a movable contact arm where an arc is generated, and an arc is controlled and cooled to be extinguished using a force determined according to strength and a direction of magnetic flux generated in the permanent magnet, a current direction, and an elongated length of an arc. Here, an arc extinguishing unit and a motor magnet may be damaged by the generated arc, and thus, in order to enhance operational reliability of a magnetic switch, it is required to extinguish the arc and protect the magnetic switch against the arc. The present invention provides enhancement of operational reliability of a high voltage DC switch, and the foregoing requirements are satisfied by using a protecting device formed of a resin material. [0007] FIG. 2 is a view illustrating a related art magnetic switch 100 . As illustrated in FIG. 2 , the related art magnetic switch includes a moving unit 140 movable with a contact, a gas sealing unit for hermetically sealing an arc-extinguishing gas filling space for arc extinguishment, and a magnetic driving unit providing driving force to drive the moving unit 140 . Here, the moving unit includes a shaft 141 , a cylindrical movable core 145 connected to a lower portion of the shaft 141 such that the cylindrical movable core 145 can be linearly movable together with the shaft 141 , and disposed to be movable linearly by a magnetic pull from the magnetic driving unit, and a movable contact arm 150 connected to an upper end portion of the shaft 141 to form an electrical contact portion. A fixed core 143 is provided in a position facing the movable core 145 and surrounds the shaft 141 , and the fixed core 143 , the movable core 145 , the second barrier 118 , and the like, form a circuit providing a path along which magnetic flux moves. [0008] The gas sealing unit is provided in the vicinity of an upper portion of the moving unit to form an arc extinguishing gas chamber in which an arc extinguishing gas of the magnetic switch is airtightly installed (or sealed), and includes a tubular insulating member, a pair of fixed electrodes 121 penetrating through the insulating member to connect the interior and exterior of the insulating member and airtightly coupled to the insulating member, a tubular airtight member provided between the insulating member and a second barrier 118 (to be described hereinafter) to airtightly seal the insulating member and the second barrier 18 and having a step, and a cylinder 160 formed of a non-magnetic material and installed to airtightly surround the movable core 145 and the fixed core 143 . Here, a DC power source side and a load side are connected to the pair of fixed electrodes 121 electrically, for example, through an electric line. [0009] The magnetic driving unit for switching the magnetic switch by driving the movable core 145 and the movable contact arm 150 (to be described hereinafter) by generating a magnetic pull includes a magnetizing coil 131 and the second barrier 118 . Here, the magnetizing coil 131 is a driving coil provided in a lower portion of the magnetic switch. When a current is applied, the magnetizing coil 131 is magnetized, and when an application of a current is cut off, the magnetizing coil is demagnetized. The magnetizing coil 131 provides driving force to the moving unit for switching (or opening and closing) a contact by generating a magnetic pull in the magnetic switch. The second barrier 118 is installed above the magnetic coil 133 , and when the magnetic coil 133 is magnetized, the second barrier 118 forms part of a movement path of magnetic flux, together with the movable core 145 and the fixed core 143 . When the magnetic coil 133 is magnetized, a lower yoke forms a movement path of magnetic flux, together with the second barrier 118 , the movable core 145 , and the fixed core 143 . [0010] In FIG. 2 , a bobbin 131 may allow the magnetizing coil 133 to be wound therearound, and supports the magnetizing coil 133 . A return spring 183 is installed above the shaft 141 , and when the magnetizing coil 133 is demagnetized, the return spring 183 provides elastic force to return the movable core 145 to the original position, that is, to a position spaced apart from the fixed core 143 . In FIG. 2 , a contact spring is a spring for maintaining contact pressure between contacts when the movable contact arm 150 is in an ON position of the magnetic switch in which the movable contact arm 150 is in contact with the fixed electrode 121 . In FIG. 1 , a housing 110 accommodates the magnetic switch according to the related art. [0011] An operation of the magnetic switch according to the related art configured as described above will be described. When the magnetizing coil 133 is magnetized upon receiving a current, magnetic flux generated by the magnetic coil 133 may move along a movement path of the magnetic flux formed in the movable core 145 , the fixed core 143 , the second barrier 118 , and the lower yoke (not shown), forming a closed circuit of magnetic flux, and at this time, the movable core 145 linearly moves to be brought into contact with the fixed core 143 , and at the same time, the shaft 141 connected to be moved together with the movable core 145 moves upwardly. Then, the movable contact arm 150 installed in eh upper end portion of the shaft 141 is brought into contact with the fixed electrode 121 and the DC power source side and the load side are connected to enter an ON state in which DC power is supplied. [0012] When a current supplied to the magnetizing coil 133 is cut off, the magnetizing coil 133 is demagnetized, and as the magnetizing coil 133 is demagnetized, the movable core 145 is returned to the original position spaced apart from the fixed core 143 , by the return spring 183 . Accordingly, the shaft 141 connected to be moved together with the movable core 145 moves downwardly. Then, the movable contact arm 150 installed in the upper end portion of the shaft 141 is separated from the fixed electrode 121 , entering an OFF state in which the DC power source side and the load side are separated and supply of the DC power is cut off. [0013] When power is applied through a coil terminal, magnetic force is formed in a coil assembly and the movable core 245 moves to push up the shaft in a direction toward the fixed core. Here, short-circuit performance (operational performance) of the magnetic switch is determined by compressive force of the two types of springs when the magnetic switch is turned on, and, in general, since a load of the contact spring 181 is considerably large, compared with the return spring 183 , short-circuit performance of the magnetic switch relies on maximum compressive force of the contact spring. Compressive force of a spring is proportional to a maximum compression distance, and is determined by a distance between the fixed core and the movable core 245 and a distance between the fixed contact arm and the movable contact arm. [0014] In general, short-circuit performance according to current capacity of a magnetic switch is determined according to maximum compressive force of the contact spring 181 . In the related art, maximum compressive force of a spring is proportional to a compression distance of the spring, it is not easy to enhance compressive force of the spring in a limited space such as in the related art. SUMMARY OF THE INVENTION [0015] Therefore, an aspect of the detailed description is to provide a magnetic switch having short-circuit performance enhanced by changing a shape of a movable core. [0016] To achieve these and other advantages and in accordance with the purpose of this specification, as embodied and broadly described herein, a magnetic switch may include: a housing; a cylinder coupled to an inner side of the housing; a stationary contact arm coupled to the housing; a movable contact arm positioned to be movable within the housing and brought into contact with the stationary contact arm or separated therefrom; a coil assembly installed within the housing and configured to form a magnetic field when a current is applied thereto; a movable shaft coupled to the movable contact arm in an upper portion thereof; a fixed core inserted into the cylinder and surrounding the movable shaft; and movable cores fixed to the movable shaft and configured to press the movable shaft by a magnetic field formed by the coil assembly to move the movable shaft, wherein the movable cores include protrusion portions extending toward the movable shaft and fixed to the movable shaft and body portions configured to move in contact with an inner diameter of the cylinder, and the fixed core has an accommodation portion for accommodating the protrusion portions. [0017] The protrusion portion and the body portion may be provided as separate members. [0018] The magnetic switch may further include: a contact spring configured to provide elastic force to the movable shaft such that the movable contact arm moves in a direction in which the movable contact arm is brought into contact with the stationary contact arm; and a return spring configured to provide elastic force to the movable shaft such that movable contact arm moves in a direction in which the movable contact arm is separated from the stationary contact arm. [0019] The protrusion portions may press a lower end of the movable shaft, and as the movable shaft is pressed by the protrusion portion, the movable shaft may be guided by the fixed core so as to be moved. [0020] Outer surfaces of the protrusion portions may be in contact with an inner surface of the accommodation portion and guided to be moved. [0021] After a current is applied to the coil assembly, the body portion and the protrusion portion may press the movable shaft together to move the movable shaft, and thereafter, the protrusion portion may be spaced apart from the body portion by a predetermined distance to further press the movable shaft and move within the accommodation portion. [0022] Further scope of applicability of the present application will become more apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS [0023] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments and together with the description serve to explain the principles of the invention. [0024] In the drawings: [0025] FIG. 1 is a perspective view of the related art magnetic switch. [0026] FIG. 2 is a cross-sectional view of the related art magnetic switch. [0027] FIG. 3 is a cross-sectional view of a magnetic switch according to an embodiment of the present disclosure. [0028] FIG. 4 is a cross-sectional view of a moving unit according to an embodiment of the present disclosure. [0029] FIG. 5 is a cross-sectional view of a moving unit according to another embodiment of the present disclosure. [0030] FIG. 6 is a cross-sectional view of the moving unit according to the embodiment of FIG. 5 . [0031] FIG. 7 is an exploded perspective view of the moving unit according to the embodiment of FIG. 5 . DETAILED DESCRIPTION OF THE INVENTION [0032] Description will now be given in detail of the exemplary embodiments, with reference to the accompanying drawings. For the sake of brief description with reference to the drawings, the same or equivalent components will be provided with the same reference numbers, and description thereof will not be repeated. [0033] Hereinafter, a magnetic switch according to an embodiment of the present disclosure will be described in detail with reference to the accompanying drawings. Parts of the magnetic switch similar to those of the related art will be briefly described within a range required for describing the characteristics of the present disclosure. [0034] FIG. 3 is a cross-sectional view of a magnetic switch 200 according to an embodiment of the present disclosure. As illustrated in FIG. 3 , a movable shaft 241 is positioned to be movable within a housing 210 , and a movable contact arm 250 is coupled to an upper portion of the movable shaft 241 . Accordingly, when movable cores 245 - 1 and 245 - 2 presses the movable shaft 241 and moves the movable shaft 241 , the movable shaft 241 and the movable contact arm 250 move together and the movable contact arm 250 is brought into contact with the stationary contact arm 220 . [0035] The movable cores 245 - 1 and 245 - 2 are positioned within a cylinder 260 , and when a current is applied to a coil assembly, generated magnetic force is transferred to the movable cores 245 - 1 and 245 - 2 . Upon receiving the magnetic force, the movable cores 245 - 1 and 245 - 2 press the movable shaft 241 to move it. [0036] The movable cores 245 - 1 and 245 - 2 include body portions 245 a and 245 b and protrusion portions 246 a and 246 b, respectively. The protrusion portion 246 a or 246 b protrudes toward the fixed core 243 . The body portions 245 a and 245 b may be in contact with an inner side of the cylinder 260 and movable by a magnetic force. The protrusion portion 246 a or 246 b is fixed to a lower end of the movable shaft 241 by welding. The protrusion portions 246 a and 246 b of the movable cores 245 - 1 and 245 - 2 may be integrally manufactured with the movable cores 245 - a and 245 - 2 , or the protrusion portions 246 a and 246 b may be assembled, as separate components, to the body portions 245 a and 245 b of the movable cores 245 - 1 and 245 - 2 , respectively. As described hereinafter, the body portion 245 a or 245 b and the protrusion portion 246 a or 246 b may move together to press the movable shaft 241 , and thereafter, the protrusion portion 246 a or 246 b may be separated from the body portions 245 a and 245 by a predetermined distance, respectively, to further press the movable shaft 241 . [0037] The fixed core 243 is fixed to the cylinder 260 and has a hole formed in a length direction to guide and move the movable shaft 241 as described hereinafter. [0038] The fixed core 243 may include an accommodation portion 244 . The accommodation portion 244 , a space for accommodating the protrusion portion 246 a or 246 b, may be provided to be larger than the protrusion portion 246 a or 246 b. An outer side of the protrusion portion 246 a or 246 b may be in contact with an inner side of the accommodation portion 244 . A depth of the accommodation portion 244 may be greater than or equal to a length of the protrusion portion 246 a or 246 b such that the protrusion portion 246 a or 246 b may sufficiently move to the inner side of the accommodation portion 244 so as to be accommodated therein. [0039] Referring to FIG. 3 , a contact spring 281 and a return spring 283 are positioned above the movable shaft 241 . The contact spring 281 applies elastic force to the movable shaft 241 such that the movable contact arm 250 is brought into contact with the stationary contact arm 220 , and maintains contact pressure between contacts when the movable contact arm 250 and the stationary contact arm 220 are in a position where they are in contact. The contact spring 281 is pressed between the movable contact arm 250 and a first rib of the movable shaft 241 so as to be elastically deformed. [0040] The return spring 283 applies elastic force to the movable shaft 241 such that the movable contact arm 250 is separated from the stationary contact arm 220 . The return spring 283 is pressed between a second rib (not shown) of a first barrier 217 and a washer positioned in the movable shaft 241 so as to be elastically deformed. [0041] The magnetic switch includes the housing 210 , and the housing 210 may include a first housing 211 and a second housing 212 . [0042] The first housing 211 is positioned in an upper portion of the magnetic switch, coupled to the first barrier 217 , and divide the upper portion of the magnetic switch into an arc extinguishing region in which the stationary contact arm 220 and the movable contact arm 250 come into contact and the other remaining region. The first housing 211 may be formed of a ceramic material for an insulation purpose. A pair of stationary contact arms 220 penetrate through an upper surface of the first housing 211 and airtightly coupled to the first housing 211 . [0043] The second housing 212 is positioned in a lower portion of the magnetic switch and may be coupled to a second barrier 218 . The cylinder 260 is coupled to an actuator region formed by the second housing 212 and the second barrier 218 , and a coil assembly is installed around the cylinder 260 . [0044] Hereinafter, an operation of an embodiment of the magnetic switch according to the present disclosure will be described in detail. [0045] First, in a state in which a current is not applied to the coil assembly 230 , only elastic force of the return spring acts on the movable shaft 241 . Thus, the movable shaft 241 is maintained in a state of having moved downwardly, and accordingly, the movable contact arm 250 is separated from the stationary contact arm 220 . [0046] Meanwhile, when a current is applied to the coil assembly 230 so the coil 233 is magnetized, magnetic flux is generated by the movable core 245 - 1 or 245 - 2 , the fixed core 243 , and the second barrier 218 , forming a closed circuit of magnetic flux, and accordingly, the movable core 245 - 1 or 245 - 2 moves. The movable core 245 - 1 or 245 - 2 presses the movable shaft 241 . The movable cores 245 - 1 and 245 - 2 include the body portions 245 a and 245 b and the protrusion portions 246 a and 246 b, and as illustrated in FIGS. 4 through 6 , the movable core 245 - 1 or 245 - 2 presses the movable shaft 241 . [0047] In FIG. 4 , the movable core 245 - 2 in which the protrusion 246 b and the body portion 245 b are integrated is illustrated, illustrating an embodiment in which the movable core 245 - 2 presses the movable shaft 241 . Here, pressing starts to compress the contact spring 281 . [0048] In FIG. 5 , the movable core 245 - 1 in which the protrusion portion 246 a and the body portion 245 a are separated is illustrated, illustrating another embodiment in which the movable core 245 - 1 presses the movable shaft 241 . Here, pressing starts to compress the contact spring 281 . [0049] In FIG. 6 , the protrusion portion 246 a and the body portion 245 a press the movable shaft 241 so the movable shaft 241 is moved upwardly. Here, the body portion 245 a moves to a position as close as possible to the fixed core 243 , in a state of pressing the movable shaft 241 . The contact spring 281 is more compressed than that of FIG. 5 . [0050] FIG. 7 is an exploded perspective view illustrating the movable contact arm 250 , the first barrier 217 , the movable shaft 241 , and the movable core 245 - 1 or 245 - 2 . These components are assembled and exploded as illustrated. [0051] The protrusion portion 246 a may be separated from the body portion by a predetermined distance to further press the movable shaft 241 . The contact spring 281 is compressed as much as possible to enhance short-circuit performance of the fixed contact arm 220 and the movable contact arm 250 . The protrusion portion may be coupled to the body portion by a spring, and the protrusion portion may be separated from the body portion to further press the movable shaft, and here, a control unit for controlling this operation may be further provided. [0052] When a current supplied to the magnetic coil 233 is cut off, the movable core 245 - 1 or 245 - 2 is returned to the original position spaced apart from the fixed core 243 by the return spring 283 . Then, an OFF state is entered in which the movable contact arm 250 installed in an upper end portion of the movable shaft is separated from the fixed contact arm 220 . [0053] According to an embodiment of the present invention, the movable cores 245 - 1 and 245 - 2 include the protrusion portions 246 a and 246 b, respectively, the fixed core 243 includes the accommodation portion, and the protrusion portions 246 a and 246 b of the movable cores 245 - 1 and 245 - 2 press the movable shaft within the accommodation portion and are moved, whereby a maximum compression distance of the contact spring 281 increases and short-circuit performance of the magnetic switch may be enhanced. [0054] The foregoing embodiments and advantages are merely exemplary and are not to be considered as limiting the present disclosure. The present teachings can be readily applied to other types of apparatuses. This description is intended to be illustrative, and not to limit the scope of the claims. Many alternatives, modifications, and variations will be apparent to those skilled in the art. The features, structures, methods, and other characteristics of the exemplary embodiments described herein may be combined in various ways to obtain additional and/or alternative exemplary embodiments. [0055] As the present features may be embodied in several forms without departing from the characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be considered broadly within its scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalents of such metes and bounds are therefore intended to be embraced by the appended claims.
A magnetic switch includes: a housing; a cylinder coupled to an inner side of the housing; a stationary contact arm coupled to the housing; a movable contact arm positioned to be movable within the housing and brought into contact with the stationary contact arm or separated therefrom; a coil assembly installed within the housing and configured to form a magnetic field when a current is applied thereto; a movable shaft coupled to the movable contact arm in an upper portion thereof; a fixed core inserted into the cylinder and surrounding the movable shaft; and movable cores fixed to the movable shaft and configured to press the movable shaft by a magnetic field formed by the coil assembly to move the movable shaft.
7
The invention was supported by the U.S. Environmental Protection Agency, and the U.S. Government has certain rights in the invention. This is a divisional copending U.S. application Ser. No. 444,517 filed Dec. 1, 1989 now U.S. Pat. No. 5,050,425. BACKGROUND OF THE INVENTION This invention relates to techniques for testing earth samples and, more particularly, to an apparatus and method for measuring volatile constituents in a sample of ground water or soil mixed with water. The leakage of underground storage tanks, and other types of pollution which introduce hydrocarbons and other volatile contaminants into the ground, has become a serious problem in many places. Recent federal, state and local regulations have or will soon require that investigations be conducted to determine whether underground gasoline storage tanks have leaked. An integral part of these investigations is determining whether soil or ground water in the vicinity of tanks have been contaminated. This is generally accomplished by the use of soil/gas surveying, drilling to collect soil samples, and construction of monitoring wells to collect ground water samples. Of significance are the more soluble and easier to detect components of gasoline, such as benzene, toluene, ethylbenzene and the xylenes. Samples are generally analyzed in the laboratory by gas chromatography or gas chromatography/mass spectrometry for volatiles and semi-volatiles using a number of known methods. Given the relatively high costs for these analyses, field screening can be conducted to select samples for laboratory evaluation. Also, field screening is used to guide investigations in terms of the depth and lateral extent of drilling. Additionally, field screening may be employed in guiding remediation by excavation. An evaluation of some existing field screening techniques, particularly those using so-called "headspace sampling", are described in "Use Of Headspace Sampling Techniques In The Field To Quantify Levels Of Gasoline Contamination In Soil And Ground Water", G. A. Robbins et al., Proc. of NWWA/API, Nov. 1987. Headspace sampling techniques involve placing a consistent volume or weight of ground water or soil mixed with water in a container, sealing the container, agitating, allowing time to permit volatile constituents to be released into the air headspace of the container, and then using a detector to measure the volatile constituent in the headspace. Existing headspace sampling techniques have various disadvantages and limitations, and it is among the objects of the invention to provide an improved headspace sampling apparatus and method. SUMMARY OF THE INVENTION The present invention is directed to an apparatus and method for measuring the presence of a volatile constituent of a sample of ground water or soil mixed with water. In accordance with an embodiment of the apparatus of the invention, a valve system is provided, and has a plurality of branches. A reclosable and collapsible bag, preferably of the polyethylene freezer bag type, is provided for receiving the sample. The bag has a hole in a wall thereof, preferably near the top of the bag. Means are provided for air-tight coupling a first of the branches of the valve system to the bag via the hole. A detector of the volatile constituent is coupleable to a second of the branches of the valve system. The valve system is operative, in one position thereof, to close off the first branch so as to isolate the bag, and in another position thereof, to couple the first and second branches so that the detector can communicate with the bag. In the preferred embodiment of the invention, the valve system has a third branch coupled to ambient air, and the valve system is operative in said "one" position thereof to couple the second and third branches and close off the first branch, and is operative in said "another" position thereof to couple the first and second branches and close off the third branch. An embodiment of the method of the invention includes the following steps: coupling a reclosable and collapsible polyethylene bag to the first branch by connecting the branch to a hole in a wall of the bag; introducing the sample into the bag through the reclosable opening thereof, and sealing the reclosable opening of the bag; with the valve system in its "another" position, pumping air into the bag by attaching an air pump to the second branch; with the valve system in its "one" position, agitating the bag and its contents to induce the release of the volatile constituent into the air headspace above the sample; with the valve system in its "one" position and the third branch in ambient air, coupling the detector to the second branch; switching the valve system to its "another" position so that the detector communicates with the headspace in the bag; and reading the detector to obtain a measure of the volatile constituent in the headspace. The apparatus and method hereof have substantial advantages over techniques which employ no valve or other types of valves which employ a glass or rigid plastic container for receiving the sample. The reclosable and collapsible polyethylene bag used in the present invention has a readily testable and reliable seal which is easy to open and close. The bag is inexpensive and conveniently disposable. This is in contrast to other containers which must be carefully cleaned before reuse in order to ensure against contamination of subsequently tested samples. A further important advantage is the collapsibility of the bag which maintains the equalization of pressure in the bag headspace at about atmospheric pressure. Also, the valve system permits the detector to communicate with ambient air while it is being connected and before it is switched to communication with the headspace air. These features facilitates more reliable and consistent testing, and avoid curtailment of the detector instrument's flow rate. A still further benefit of the bag used herein is its flexibility, which permits disaggregation of the sample by squeezing the bag. Further features and advantages of the invention will become more readily apparent from the following detailed description when taken in conjunction with the accompanying drawing. BRIEF DESCRIPTION OF THE DRAWING The drawing shows a schematic diagram of an apparatus in accordance with an embodiment of the invention and which can be used to practice an embodiment of the method of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, there is shown a diagram of a reclosable bag sampling system in accordance with an embodiment of the invention. A reclosable polyethylene freezer bag 120 (such as of the type made and sold by Dow Chemical as "Ziploc") is connected to a three-way valve system 150. In an operating embodiment, the reclosable polyethylene bag 120 was a one-quart bag, and the three-way valve system 150 was a so-called 3-way ball valve of a type sold by Imperial Eastman, Inc., No. 108-HD. The valve 150 has three branches labeled 1, 2, and 3, respectively, one manually adjustable position that can be referred to as position A, and a second manually adjustable position that can be referred to as position B. In position A, the branch 2 is coupled to the branch 1 (i.e., these branches are permitted to communicate with each other), and the branch 3 is closed off. In position B, the branch 2 is coupled to the branch 3, and the branch 1 is closed off. In the present embodiment, the bag 120 is connected to the valve system through a hole in the bag which can be made with a standard hole punch. A connector fitting, for example a 1/8 inch NPT connector fitting 131 coupled to the valve branch 3, is inserted through the hole, and the fitting is sealed to the bag using gaskets 135, 136 and the nuts 137, 138 on respective sides of the hole. Other suitable seals can also be employed. Using a hand pump on branch 2, and with the valve in the B position, the bag 120 can be filled until just taut and tested for leakage. If bag leakage is observed, a different bag is attached. If proven leak-tight, the reclosable seam of the bag 120 is opened. A sample (e.g. an aqueous sample or a soil sample mixed with distilled water) can then be introduced into the bag through the opening. A volumetric flask can be used for liquid samples, and a predetermined volume (e.g. using a spoon) or weight can be used for soil samples. The bag is then sealed and inflated until just taut, again using a hand pump with the valve in the B position. The bag is isolated, by placing the valve in position A (which closes off branch 3) and then agitated. This can be done by hand, using a rocking motion. The agitation tends to release vapor into the headspace, either directly from an aqueous sample in which it was initially contained, or from soil into water and then into the headspace. The flexibility of the bag also has the advantage of permitting disaggregation of the sample by hand, if desired, by squeezing the bag and its contents. This will accelerate the release of vapors from the sample. After a sample is agitated, headspace concentration measurement can be implemented by coupling a detector to branch 2 and, at the desired time or times, moving the valve to position B. The 3-way valve is seen to allow the detector to draw ambient air prior to sample measurement (i.e., via branch 1), and permits rapid switching to the headspace of the bag (i.e., by switching to valve position B) in a manner that does not curtail the instrument's flow rate. The vapors evolved in the headspace can be measured in a manner not affected by inducing a vacuum while the detection instrument draws air from the bag; i.e., as the air is drawn out of the bag into the sampling instrument, the bag collapses and thus maintains an internal pressure of about one atmosphere. In one example, tests were conducted using a flame ionization detector ("FID") that was calibrated with a methane in air standard. In another example, tests were conducted using a photoionization detector ("PID") that was calibrated with an isobutylene in air standard. It will be understood, however, that any suitable type of detector can be employed. Following each analysis the bag and its contents should be properly disposed. If appropriate, the gaskets can be re-used. For example, it has been found that buna-n gaskets used as a seal on the bag can be re-used without sample carry-over. The valve system can be purged by pumping air through the system. The effectiveness of purging can be checked by connecting the valve system to the measuring instrument. Consider measuring the concentration of a single volatile constituent in a sample of air that is contained within a chemically inert and collapsible bag. The bag is connected to a PID or FID, as described above. As the instrument withdraws air from the bag during sampling, the bag collapses and maintains a constant internal pressure. Therefore, the concentration measured may be equated to the actual concentration by C.sub.mi =R.sub.i C.sub.i, (1) where C mi equals the measured vapor concentration for a constituent i, C i equals the actual vapor concentration, and R i is a response factor. The response factor will depend on the instrument's sensitivity to constituent i relative to a calibration gas and to a given set of calibration conditions. Pertinent calibration conditions would include the condition of the instrument and its detector, whether the instrument's response is being affected by quenching, and whether the actual concentration levels are within the linear range of the instrument. If measurements are performed on a series of air samples containing a single constituent i, Equation (1) predicts that measured and actual concentrations will be linearly related providing R i remains constant. Expanding Equation (1) for the case where multiple vapor constituents are present in the bag results in ##EQU1## where C mT is the measured total concentration, C T is the actual total concentration, and n is the total number of constituents. Equation (2) predicts that measured and actual total concentrations will be linearly proportional among samples, if the following conditions hold. The R i value for each constituent remains constant among samples, and either a constituent's concentration varies, or the concentration of all constituents vary in proportion (i.e., C i /C T remains constant for each constituent) from sample to sample. Next, consider sealing a water sample, containing a single, dissolved, volatile constituent, into a bag inflated with clean air. With time, the constituent will volatilize into the headspace. If the sample is well agitated and the volume of headspace remains constant, the measured headspace concentration at any time may be described by a first order transfer function expressed as C.sub.mi (t)=R.sub.i C.sub.i (t)=R.sub.i C.sub.ie [1-exp(-k.sub.i t)](3) where C mi (t) and C i (t) are the measured and actual vapor concentrations at time t, respectively, C ie is the actual equilibrium headspace concentration, and k i is an effective mass transfer coefficient [see Tchobanoglous et al., 1985]. Equation (3) predicts an exponential achievement of an equilibrium concentration with time that depends on the magnitude of the mass transfer coefficient. The mass transfer coefficient is a function of the individual constituent, temperature, degree of sample agitation, and the contact area between the water and the headspace. Mass transfer coefficients for commonly found volatile contaminants tend to be relatively large [see Mackay et al., 1975]. In well-agitated headspace vessels, vapor concentration equilibrium has been reported to occur within minutes [see, for example, Drozd et al., 1978; Leighton et al., 1981; Griffith et al., 1988]. The equilibrium headspace concentration in Equation (3) may be related to the equilibrium water concentration by Henry's law, expressed as C.sub.ie =H.sub.i C.sub.iwe (4) where H i is a dimensionless Henry's law constant and C iwe is the equilibrium concentration in the water, expressed in the same dimensional units are the vapor concentration. Based on mass continuity and the previously developed equations, the measured equilibrium headspace concentration may be related to the initial dissolved concentration of the constituent by C.sub.mie =R.sub.i C.sub.ie =R.sub.i H.sub.i C.sub.iwe =[R.sub.i /(1/H.sub.i +V.sub.hs /V.sub.w)]C.sub.iwo (5) where V hs is the volume of headspace, V w is the volume of water sample added to the bag, and C iwo is the initial concentration of the dissolved volatile constituent. Various forms of Equation (5) have been used in conducting head-space analysis in gas chromatography [see, for example, Stolyarov, 1981 or Gossett, 1987]. The equation indicates that for a single volatile constituent the measured headspace concentration will be linearly proportional to the initial water concentration. In order for this linearity to hold with respect to a series of samples, R i , H i and V hs /V w must remain constant. Because H i is a function of temperature and water quality factors (e.g., salinity), these conditions must be kept constant to maintain linearity. However, Equation (5) predicts that the magnitude of non-linear effects will depend on the magnitude of 1/H i relative to V hs /V w , the sensitivity of H i to temperature and water quality variations, and the degree to which these conditions vary among samples. The preceding equations can be readily expanded by summation to treat multiple constituents, as in the case of expanding Equation (1) to Equation (2). Linearity between total equilibrium headspace concentration and total aqueous concentration will depend on the same factors mentioned previously. In addition, it will depend on the achievement of equilibrium headspace concentrations by all constituents at the time of measurement. The effectiveness of partitioning aromatic compounds from soil into the headspace of VOA vial by agitation in water has previously been demonstrated [see Griffith et al., 1988]. Once constituents were partitioned from the soil, headspace equilibrium was shown to be described by the preceding theory for water-headspace partitioning. For a single constituent i, equilibrium partitioning among the three phases may be described by m.sub.iso =m.sub.ise +m.sub.iwe =m.sub.ie (6) where m iso is the mass originally on the soil sample, and m ise , m iwe , and m ie are the masses at equilibrium distributed among the soil, water and headspace, respectively. By performing appropriate substitutions of concentration and volume terms for mass terms, and by incorporating the previously cited equations, Equation (6) may be re-expressed as C.sub.mie =R.sub.i C.sub.ie =R.sub.i {[M.sub.s /V.sub.w ]/[((K.sub.isw +1)/H.sub.i)+V.sub.hs /V.sub.w ]}C.sub.is (7) where M s is the mass of soil added to the bag, K isw is a soil/water partition coefficient for constituent i, and C is is the concentration of the constituent on the soil on a mass/mass basis. As with the other equations, providing that the terms to the left of C is are kept constant among samples, the measured headspace concentration is predicted to be a linear function of the soil concentration. As in the previous developments, Equation 7 can be readily expanded for the multiple constituent case. Again, linearity between measured total headspace and total soil concentration will depend on the extent to which the parameters previously cited remain constant from sample to sample. For further details, reference can be made to "A field Screening Method For Gasoline Contamination Using A Polyethylene Bag Sampling System", G. Robbins et al., Fall 1989 GWMR. It will be understood that the interpretation of the detector measurements, and the underlying theory thereof are known in the art and are not, of themselves, inventive features hereof. The invention has been described with reference to a particular preferred embodiment, but variations within the spirit and scope of the invention will occur to those skilled in the art. For example, it will be understood that other valve systems can be employed which achieve the same functions as those described herein or which have additional branches for separate connection of air pump and detector.
The disclosure is directed to an apparatus and method for measuring the presence of a volatile constituent of a sample of ground water or soil mixed with water. In an embodiment of the apparatus, a valve system is provided, and has a plurality of branches. A recloseable and collapsible bag, preferably of the polyethylene freezer bag type, is provided for receiving the sample. The bag has a hole in a wall thereof, preferably near the top ofthe bag. A first of the branches of the valve system is air-tight coupled to the bag via the hole. A detector of the volatile constituent is coupleable to a second of the branches of the valve system. The valve system is operative, in one position thereof, to close off the first branch so as to isolate the bag, and in another position thereof, to couple the first and second branches so that the detector can communicate with the bag.
6
FIELD OF THE INVENTION This invention relates to the processing of copper beryllium alloys. More specifically, this invention relates to reducing the amount of geometric distortion currently observed during the precipitation hardening of formed parts in the conventional processing of copper beryllium alloys. BACKGROUND OF THE INVENTION The prior art reveals various methods for decreasing the distortion which results during the precipitation hardening of formed parts produced from copper beryllium alloys. Unfortunately, these prior art methods are minimally effective and often fail to control the resultant distortion to a commercially acceptable degree. Additionally, the prior art methods yield inconsistent non-reproducible results. These alloys are used in electrical connectors where consistent dimensional and mechanical properties in the finished product are important. Basically, all prior art methods for producing formed parts from copper beryllium alloys include the combination of the following sequence of processing events: preparing a copper beryllium melt; casting the melt; hot working the cast copper beryllium; solution annealing the copper beryllium; cold working the solution annealed copper beryllium; forming the copper beryllium; and age-hardening the formed copper beryllium. As mentioned above, various methods have been developed in an attempt to control the distortion experienced in this processing sequence. In this connection, reference is made to the methods disclosed in Goldstein U.S. Pat. No. 4,425,168, McClelland U.S. Pat. No. 4,394,185, Wickle U.S. Pat. No. 4,179,314, Shapiro U.S. Pat. No. 3,882,712, Britton U.S. Pat No. 3,658,601, the article entitled "Residual Stresses in Copper-2% Beryllium Alloy Strips", authored by K. E. Amin and S. Ganesh, Experimental Mechanics, December 1981, page 474, and the article entitled "A Technique For Predicting Distortion And Evaluating Stress Relief In Metal Forming Operations", authored by K. E. Amin and R. M. Rusnak, Journal of Metals, February 1981. The methods disclosed in these prior art sources are only partially successful in eliminating distortions in finished products. Amin and Ganesh have correctly identified residual stresses as one of the sources of distortion. Amin and Ganesh have also shown that a high rolling reduction of copper beryllium strip results in tensile residual stresses near the surface of the strip and compressive residual stresses at the center of the strip while low rolling reductions result in the opposite location of these stresses within the strip. The McClelland and the Britton patents comprehend the importance of relieving residual stresses prior to the forming operation by the incorporation of a pre-aging technique. However, they fail to realize that in a thermal treatment such as their pre-aging technique two reactions occur simultaneously. On the one hand thermal treatments such as pre-aging promote the nucleation and growth of the precipitates formed during precipitation hardening. On the other hand these treatments also reduce the magnitude of the existing cold working and residual stress patterns that affect the precipitation hardening. The recognition of these competing mechanisms is critical in the development of reproducible softening and hardening techniques and the effects thereof on the reproducibility of the formed parts. All thermal treatments must utilize those combinations of times and temperature which relieve or decrease the magnitude of residual stresses before the formation of precipitates become dominant. None of the prior art teachings recognize that the rates at which the nucleation and growth of precipitates occur are different when the metal matrix is aged under tensile residual stresses as opposed to compressive residual stresses. The realization of the existence of these differential zones of nucleation and growth is critical in the development of a process for producing distortion free copper beryllium products since consistent and reproducible mechanical and dimensional properties can only be obtained from the aging process in coils of strip, wire and the like, and parts formed therefrom by combinations of thermal and mechanical treatments that yield consistent and reproducible stress and precipitate patterns. The possible existence of these patterns of undissolved precipitates or precipitate nuclei has not heretofore been considered. Furthermore, to date there has been no application of the effects of light and heavy reductions to the controlling and leveling out of residual stresses within the alloy or to the modification of precipitate patterns left after an incomplete solution anneal. SUMMARY OF THE INVENTION With the foregoing in mind it is a principal object of this invention to provide a process for relieving the magnitude of residual stresses in copper beryllium alloys before the formation of precipitates becomes the dominant mechanism. Another object of this invention is to provide a process for imposing on regions of compressive or tensile residual stress those tensile or compressive stresses that are of the opposite type. Yet another object of this invention is to provide a process for ensuring an even distribution of precipitates throughout the alloy. Still another object of this invention is to provide a process which will result in a copper beryllium alloy wich exhibits an increased proportional limit in tandem with an increased elongation. A further object of this invention is to provide a process for the virtual elimination of the non-reproducible distortion which is currently experienced during the production of formed parts from copper beryllium alloys. These and other objects of the present invention may be achieved by including in the prior art process for producing formed parts from a copper beryllium alloy the additional improved steps of: subjecting the alloy to a heavy rolling reduction of at least 45% during the final cold rolling pass, solution annealing the alloy, subjecting the alloy to a low rolling reduction of from 5% to 15%, once again solution annealing the alloy, precipitation hardening the alloy in a salt bath heating medium at a temperature of from 300° to 800° for a period of up to 180 minutes, and when possible reversing the direction of coiling during each of the various steps of the process. To the accomplishment of the foregoing and related ends the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed. DESCRIPTION OF PREFERRED EMBODIMENT In copper beryllium alloys abnormally large strain or coherency stress fields develop during precipitation hardening. The applicants have found that these coherency stress fields may interact with the residual stress patterns that exist at the start of the thermal aging process to create unexpectedly strong effects on the dimensional changes which occur in the parts during the age hardening treatment. Residual stresses, both compressive and tensile, are created in wire and strip during the various forming operations such as rolling, coiling, uncoiling, and the like. In an attempt to better understand the effects of these various forming operations and the resultant stresses which these operations impart into the alloy, tests were conducted in which segments of copper beryllium strip were bent around an anvil of a specific radius of curvature and then aged. Upon aging, the angle formed by the bent strip was found to change. The effects of altering the radius of the anvil, the angle of the bend, the side of the strip being put under compression, the thickness of the strip, and the thermal treatment given the strip prior to aging, were all studied and the results statistically evaluated. The evaluations revealed that on aging, the amount of shrinkage in regions that were under compressive residual stress was greater than the amount of shrinkage that occurred in regions that were under tensile residual stress. These observations when combined with the well documented fact that large shrinkages occur in formed copper beryllium parts during aging due to the nucleation and growth of precipitates led the applicants to the conclusion that upon thermal aging the rate of nucleation and growth of precipitates in regions that are under compressive residual stress is greater than the rate that exists in regions that are under tensile residual stress. Therefore, during the aging of a formed part which contains various regions of compressive and tensile residual stresses, the formation of precipitates will proceed at different rates in each of these types of regions resulting in different amounts of shrinkage from region to region and thus will create distortion. Conventional processing steps to aging (i.e., cold rolling, drawing, coiling and the like) produce residual stress patterns. Since residual stress patterns exist before aging and since these patterns affect precipitate nucleation and growth, precipitation patterns must be created by aging. In these precipitation patterns the original compressive stress regions would have more precipitates than the original tensile stress regions and the greater the difference in the number of precipitates in such regions, the greater would be the difference in the rates of work hardening. Similarly it is to be expected that subsequent to a solution anneal there will be more undissolved precipitates and precipitate nuclei in regions that were originally under compressive residual stress than in regions that were under tensile residual stress. Additionally, since the distribution of residual stresses within the alloy directly affects the distribution of precipitates upon thermal treatment, an even distribution of the residual stresses which are imparted by the various forming operations of the process such as coiling would be most desirable. Evidence of the existence of precipitate patterns was supported by data obtained from tests performed on coils of copper beryllium wire. During these tests, it was observed that in the coils of wire some portions of the coils had abnormally high rates of work hardening. The existence of these portions of the wire which had abnormally high rates of work hardening could only be explained by variations in the amount of precipitates that existed along the length of the wire. These tests also revealed that when coils drawn from the same original rod were given a severe cold reduction, annealed, given a slight cold reduction, and then annealed again, there were no portions that revealed high work hardening rates either before or after aging. This meant that the distribution of precipitates was more even within the alloy and that the periodic pattern of regions, in which large amounts of precipitates dominated, no longer existed. These test results can be explained as follows: after the heavy reduction and the first anneal there were fewer undissolved precipitates and precipitate nuclei left on the outside of the wire than on the inside. After the light reduction and the second anneal there were fewer undissolved precipitates and precipitate nuclei left on the inside of the wire than on the outside. By successively combining the light and heavy reductions and their respective anneals a relatively homogeneous distribution of undissolved precipitates and nuclei was achieved within the wire. This was confirmed by a statistical analysis of the mechanical properties of wire which had been given the aforementioned light and heavy reductions and double anneals. These wires exhibited much less deviation than wire which was simply given one anneal and revealed no abnormal values as is commonly found in wire given only one anneal. In an attempt to further understand and develop methods for controlling the detrimental effects of the precipitate patterns additional tests were conducted. In one of these tests two contiguous segments of 25 alloy wire were given a severe cold reduction, annealed, given a slight cold reduction, and then annealed. The segments were then drawn into the quarter-hard condition and separate lengths were aged in either an air atmosphere furnace or a salt bath at 600° F. prior to being water quenched. The tensile data obtained from these specimens is shown below: TABLE I______________________________________Time Proportional Limit (KSI) Elongation (Percent)(Minutes) Furnace Salt Furnace Salt______________________________________0 74.2 10.12 76.9 73.1 9.8 22.05 85.8 79.0 8.3 17.510 108.0 98.4 6.3 12.815 132.9 131.5 1.8 8.22 and 15* 118.5 6.6______________________________________ *Two minutes in the salt bath followed by a water quench and 15 additiona minutes in the salt bath. Analysis of these results shows that the furnace aging was totally ineffective in improving the elongation of the wire. However, for the wire that was quickly heated in the salt bath, two minutes was long enough to decrease the residual stresses and the cold work put in the wire by the quarter-hard reduction with the result that the elongation was more than doubled from 10.1 to 22.0. After two minutes, however, the precipitation phenomena became dominant and strengths began to increase and elongations began to drop. After ten minutes in the salt bath, the wire revealed more elongation than it had originally shown before aging and a 32.7% increase in the proportional limit. Therefore, clearly a hardening treatment of four to eight minutes in a 600° F. molten salt bath will increase the formability of the wire as well as the strength of the wire. Similar decreases in the proportional limit were observed in specimens treated in a salt bath at 500° F. for less than 15 minutes and at 700° F. for less than 45 seconds. The consistent and striking variations in the data of Table I were not found in wire that had been given the standard wire drawing treatment. Therefore, the results of Table I can only be attained by adopting the present invention for the processing of copper beryllium alloys, (i.e., a severe cold reduction, an anneal, a light cold reduction, an anneal). This process controls residual stress and precipitation patterns enabling the results shown in Table I and also the reduction of the distortion which results from such patterns upon aging. Since many commercially available grades of copper beryllium alloys contain cobalt beryllides, the effects of these beryllides on this invention must be considered. The effects of cobalt beryllides on the physical properties of a copper beryllium alloy are well known. Specifically, it is known that the size and distribution of these cobalt beryllide precipitates have an appreciable effect on the rate of cold working. Therefore, cobalt beryllides must also have an effect on the combinations of time and temperature that are needed to stress relieve the alloy. Thus, it will be appreciated that in the application of this invention times and temperatures may have to be adjusted to accommodate the particular size and distribution of cobalt beryllides in the alloy which one is processing. In summary, the invention will conform to the four basic approaches which are designed to minimize the non-reproducible distortion which results from the aging process and produce a copper beryllium alloy with improved elongations in tandem with increased proportional limits. These four basic approaches are as follows: (1) utilize combinations of time and temperature which relieve or decrease the magnitude of residual stresses before the formation of precipitates becomes dominant; (2) before aging, provide for a more even distribution of residual stresses by imposing on regions of compressive or tensile residual stresses those tensile or compressive stresses that are of the opposite type; (3) utilize those combinations of reductions and annealing that minimize the differences in the magnitudes of the precipitate patterns left from the original cold rolling operations; (4) during the age hardening process utilize a salt bath treatment with those combinations of time and temperature that give increased elongations in conjunction with increased proportional limits. These four approaches when integrated into the prior art process of producing formed parts from copper beryllium alloys manifest themselves in a series of mechanical and thermal processes. Specifically, in order to minimize all previous precipitation patterns within the alloy and provide an even distribution of precipitates and nuclei a double anneal process is employed. The double anneal process comprises the steps of subjecting the alloy on the final cold rolling pass to a minimum cold reduction of 45% followed by a solution anneal, a light cold reduction of between 5% and 15%, and another solution anneal. When precipitation hardening the alloy, either before or after the forming operation, a molten salt bath heating medium in combination with specific times and temperatures must be employed in order to attain increased elongations in tandem with increased proportional limits. Such combinations of times and temperatures ±25° F. which have been found effective are 400° F. for a period of from two to three hours, 500° F. for a period of from thirty to sixty minutes, 600° F. for a period of from four to eight minutes, and 700° F. for a period of from one to three minutes. The imposition on regions of compressive or tensile residual stress of those stresses of the opposite type is generally accomplished by reversing the sides of the strip during the various coiling operations of the process. Such reversing will decrease the magnitude of the resultant stresses and tend to equalize them over the entire thickness of the strip. Similarly, it will be appreciated that this concept is also applicable to wire and may be implemented simply by reversing the direction of winding at each of the reeling operations. In processes which include an operation such as slitting prior to forming it will be necessary to stress relieve the alloy both before and after such an operation so as to avoid the detrimental effects of the stresses imparted into the alloy by the operation. The stress relief process will require a salt bath heating medium in combination with specific times and temperatures that relieve the magnitude of residual stresses before the formation of precipitates becomes dominant. Such combinations of times and temperatures ±25° F. which have been found effective are 500° F. for a period of from twelve to twenty minutes, 600° F. for a period of from sixty to ninety seconds, and 700° F. for a period of from thirty to fifty seconds. It should be noted that the incorporation of the stress relief anneals may require a light rolling reduction of up to 15% subsequent to the last stress relief anneal so as to impart some stiffness and the ability to be precipitation hardened into the alloy and thus facilitate its handling and feeding in subsequent operations. It will be appreciated that this invention is wholly applicable to all processes for producing formed parts from copper beryllium alloy rod, wire, sheet, or the like which include the cold working or cold reduction of the alloy. Cold working may be accomplished by various methods such as rolling, stretching, or drawing. It will be appreciated that the combinations of times and temperatures set forth in this invention simply represent guidelines and that in light of the teachings of this invention one skilled in the art may derive a variety of functional times and temperatures. Additionally, the optimum combination of times and temperatures will be a function of numerous variables such as strip or wire configuration, heat sources, alloy composition, line speed, etc. It will also be appreciated that this invention may be easily modified to incorporate additional processing steps such as machining, broaching, or the like. Additionally, it will be appreciated that one skilled in the art may easily adapt the invention so as to produce a finished part which exhibits a particular set of physical properties. Finally, it will be appreciated that the application of only a portion of this invention will yield beneficial results; however, optimum results will be achieved by incorporating all portions of the invention.
This invention provides a novel method for the production of formed parts from copper beryllium alloys. More specifically, this invention provides a process for the virtual elimination of the non-reproducible distortion which is currently experienced during the precipitation hardening of parts formed from copper beryllium alloys. To this end the process comprises a series of mechanical and thermal treatments which minimize or eliminate non-reproducible distortion by relieving or decreasing the magnitude of residual stresses throughout the various steps of the process before the formation of precipitates becomes dominant and by providing a more even patterned distribution of precipitates in the matrix of the alloy both prior to and after a thermal aging process. Additionally, the implementation of this process in conjunction with a precipitation hardening treatment utilizing a molten salt bath heating medium results in an alloy which exhibits an increased elongation in tandem with an increased proportional limit.
2
TECHNICAL FIELD OF INVENTION [0001] The present invention relates to an electro-hydraulic process control system in sub-sea production installations for well fluids, including oil or gas production and injection of gas or water. The invention also refers to a method for operating the process control means of the electro-hydraulic process control system. [0002] The expression “process control” as used in this application should be understood to include production control such as performed by Christmas tree actuators and down hole safety valves, as well as control of process equipment such as separators and pressure boost equipment. It is common practice in sub-sea engineering to integrate emergency shut down systems and production control systems. Thus, “process control” is considered to encompass some or all of these and other relevant types of control or process management in this application. BACKGROUND OF THE INVENTION AND PRIOR ART [0003] The remote control of sub-sea valve actuators for Christmas Trees (XTs) and manifold systems have evolved from simple concepts in the seventies to extensive and complex electro-hydraulic systems with offset distance capacity currently passing the 160 km limit. Traditionally hydraulic control power is generated at a host facility, based on a floating or semi-submerged unit or land based, and transmitted to the sub-sea facility at two different pressures: typically at 207 bars for the XT actuators, and pressures up to (and exceeding) 700 bars for the down hole safety valves (DHSV). Sub-sea hydraulic power units (HPU) located at the sub-sea production facility has been considered many times, but only a few and relatively insignificant installations of this type were ever made. [0004] Process control systems are characterized by infrequent actuation and corresponding low average hydraulic power consumption, thus by means of accumulators located at the sub-sea facility it has been possible to use small bore tubing (typically ⅜″ to ¾″ tubing size) for the hydraulic power transmission. It has only exceptionally and infrequently been considered beneficial to deviate from this design practice as even a minor loss in reliability of the control system can be of great significance to cash flow and intervention efforts. [0005] For most sub-sea process control systems, internal leakage from directional control valves (DCV) has been the dominant source of fluid consumption while actuation of the valves often accounts for less than 15% of the total fluid consumption. [0006] Two courses of development initiates a revision of the current design practice: Offsets up to 600 km are seriously considered for sub-sea tieback to the beach, essentially for transfer of dry gas products; New processing facilities, especially fast acting process control valves, require high power levels on a near continuous basis. [0009] Sub-sea hydraulic control valves are typically configured in one of two major categories, i.e. open loop and closed loop, the former based on dumping used fluid to sea and the latter based on returning the used fluid to the host HPU for re-use. Recent installations in environmentally sensitive areas have demonstrated the undesirable feature of open loop systems, since both corrosion inhibitor substances and dye additives are difficult to achieve in Green environmental (environment-friendly) class and tend to be offered in Yellow class, or even Red class. [0010] Hydraulic control systems being part of the sub-sea production control use either water based fluids (mostly a mixture of distilled water and glycol plus additives) or mineral based/synthetic fluids. For extreme offset distances, the inherently low viscosity of the water based fluids and corresponding moderate transmission losses tend to dominate. Water based fluids can be used in both open loop systems and closed loop systems, whereas mineral oil can not be discharged to the environment. [0011] In order to provide the required power for high flow or long offset scenarios, by means of an economically justifiable umbilical (and one that can be laid full length in a single campaign), the power transmission has to be electrical, otherwise umbilical content will grow out of all reasonable proportions. [0012] Traditionally the following objections have been raised against the few sub-sea HPU and thus locally closed hydraulic loop concepts proposed: 1. Leakage of process gas from the production tubing will migrate into the hydraulic control line to the DHSVs and from there contaminate the entire hydraulic control system, any attempt at boosting a fluid contaminated with gas by means of a pump intended for single phase operation would be futile (compressibility and possibly eventually even free gas phase); 2. Leakage of minor quantities of fluid to the environment will eventually deplete the local HPU reservoir and constitute an operational problem; 3. Wet make/break electrical connectors are unreliable; 4. Electrical squirrel cage motors are unreliable as used in a sub-sea environment; 5. Fixed displacement pumps have limited operating time, typically maximum 12 000 hours under ideal conditions of clean fluid and good lubrication, and will require frequent interventions and thus loss of regularity in operation; 6. Rotor-dynamic pumps, e.g. centrifugal pumps, typically provide low pressure and high flow, the opposite of what is required for an HPU intended for production control purposes. [0019] Thirty years of sub-sea oil and gas field developments and operations have basically demonstrated validity of these objections. However, recent developments have brought about many changes, the sum of which requires revision of the overall conclusion that sub-sea HPUs have no place in commercial sub-sea developments. With reference to the objections referred above the following changes have taken place: 1. DHSV actuators have improved considerably with respect to leakage. Nevertheless, leakage cannot be ignored as a factor, and the objection remains valid. A viable system requires system features to handle minor leakages of gas from the DHSVs; 2. A control system of absolutely no external leakage is unlikely, although environmentally significant leakages are rare. Replacement of lost fluid is required for high regularity operation; 3. Wet make/break connectors for 12 kV have been in operation for some time with good results and 36 kV systems have been qualified. High voltage (HV) wet make/break connectors have become a commercially viable component; 4. Electrical squirrel cage motors have been in operation for some time for 2 MW systems and 9-10 kV stator voltage. The motor issue is eliminated from the HPU discussion, which requires typically <15 kW of power for most applications; 5. Fixed displacement pumps for 2 MW power are being developed, but for less pressure than required for an HPU for control purposes; 6. Rotor-dynamic pumps for unprocessed well fluids (multiphase), produced water and even sea water, have been qualified for ratings up to 2 MW and operated for extended periods of time on fluids with significant particulate contamination. [0026] Thus it may be fairly stated that with state-of-the-art components related to a sub-sea HPU the gas leakage and the pump unit remain as the only issues in relation to achievement of a reliable sub-sea HPU for control purposes. [0027] All electric control systems have been proposed and developed for production control and are under development for XT actuators and fast acting Production control valves (PCVs). However, there are major objections to all-electric control systems that will most likely slow down their introduction into the market place: 1. An electro-hydraulic actuator design for fail close operation is relatively complex and reliability will be an issue; 2. There are few, if any, convincing design for a fail close actuator for the DHSVs; 3. In the event that horizontal XT design is pursued, the XT cannot be retrieved without prior retrieval of the tubing, a major workover operation of high cost, both in rig cost and deferred production, thus focusing even more on reliability. SUMMARY OF THE INVENTION [0031] The present invention thus has for an object to provide an electro-hydraulic process control system, in which supply of operating power and actuator response is secured at long offset distances between the sub-sea and host facilities of a sub-sea production installation. [0032] Another object of the invention is to provide an electro-hydraulic process control system for a sub-sea production installation, in which hydraulic fluid quality is actively controlled at sub-sea level. [0033] Yet another object of the invention is to provide an electro-hydraulic process control system, in which emergency shut down availability is enhanced and secured also at long offset distances between the sub-sea and host facilities of a sub-sea production installation. [0034] Still another object of the invention is to provide an electro-hydraulic process control system in which the emergency shut down availability can be tested during continued operation of a sub-sea production installation. [0035] A further object of the invention is to provide a control process, the steps of which are dedicated for securing operating power and actuator response at long offset distances between the sub-sea and host facilities of a sub-sea production installation. [0036] These and other objects are met in an electro-hydraulic process control system and method as specified in the appended claims. [0037] Briefly, the present invention provides an electro-hydraulic process control system in a sub-sea production installation, comprising: a top-side hydraulic power unit, driven and controlled to generate and supply hydraulic power to process control means of the sub-sea production installation at a steady-state operation mode; a sub-sea hydraulic power unit, driven and controlled to generate and supply hydraulic power to the process control means at a transient-state operation mode; an umbilical cord, comprising small bore tubing feeding hydraulic power from the top-side hydraulic power unit to the process control means, and cables feeding high voltage electric power for operation of the sub-sea hydraulic power unit, and means for controlling the sub-sea hydraulic power unit between a stand-by mode and an operative mode. [0042] A significant feature of the invention is that the top-side hydraulic power unit is operable for providing the steady-state power represented by directional control valve leakage, and the sub-sea hydraulic power unit is operable for providing the transient-state power required to operate process and safety valves of the process control means. [0043] To this purpose, the sub-sea hydraulic power unit comprises a pump driven by an electric motor powered by alternating current which is stepped down from the higher voltage supplied through the umbilical. [0044] More specifically, the pump is operable and controlled in the transient-state operation mode to boost the pressure of hydraulic fluid returning from the process control means into a pressure required for operating the process and safety valves of the process control means. [0045] In a preferred embodiment, hydraulic fluid is accumulated at operating pressure in a medium pressure accumulator bank, hydraulic fluid at return pressure is accumulated in a low pressure accumulator bank, and the pump being operable for charging the medium pressure accumulator bank with hydraulic fluid from the low pressure accumulator bank. [0046] Advantageously, the process control system of the invention comprises a check valve through the operation of which hydraulic fluid supplied through the umbilical is returned through the umbilical to the top-side hydraulic power unit in a fluid circulation mode, at a pressure independent of the control system operating pressure. [0047] Likewise preferred, the components of the sub-sea hydraulic power unit are contained in a pressure vessel from which hydraulic fluid in circulation mode is returned to the top-side hydraulic power unit by means of selectively operated directional control valves and via first and second return flow lines. [0048] Thus, the first return flow line exits the pressure vessel from a bottom region thereof, extracting hydraulic fluid and particulate matter deposited in the pressure vessel, and the second return flow line exits the pressure vessel from a top region thereof, extracting hydraulic fluid and gaseous matter eventually accumulated in the pressure vessel. [0049] In order to accelerate the hydraulic fluid extracted from the pressure-vessel's bottom and top regions, respectively, the first and second return flow lines advantageously connect to an eductor, which is powered by the hydraulic pressure supplied through the umbilical. [0050] A redundant emergency shut down system is achieved according to the invention through providing at least two sets of directional control valves connected in series, each set including at least two directional control valves connecting in parallel the supply line and the return line, powering the directional control valves electrically through the umbilical and controlling the valves into a normally closed position. [0051] In this way, the directional control valves of the emergency shut down system are controllable individually or in pairs into an open position, enabling operational test of all valves in the system without loss of production in the sub-sea production or processing installation. [0052] Through the above-cited measures, the present invention also introduces a new method for operating the process control means in an electro-hydraulic process control system in a sub-sea production installation. The new method comprises the steps of: feeding hydraulic power, via an umbilical, from a top-side hydraulic power unit for operating the process control means in a steady-state operation mode of the process control system; feeding high voltage electric power, via the umbilical, for operating a sub-sea hydraulic power unit, and controlling the sub-sea hydraulic power unit between a stand-by mode and an operative mode for operating the process control means, in a transition operation mode of the process control system. [0056] Preferably, the method further comprises the step of boosting, by said sub-sea hydraulic power unit, the pressure in hydraulic fluid returning from the process control means into a higher pressure required for operating process and safety valves of the process control system. [0057] Boosting the pressure of hydraulic fluid is achieved, according to the invention, by stepping down the high voltage electric power supplied via the umbilical, to a low voltage alternating current suitable for powering an electric motor and pump of the sub-sea hydraulic power unit. [0058] The method advantageously also comprises the further step of separating, in a circulation mode, the flow of hydraulic fluid supplied via the umbilical from the flow of hydraulic fluid required to operate the process control means. [0059] Likewise preferred, the method further comprises the step of extracting contaminants from the hydraulic fluid, at sub-sea level, in the circulation mode. [0060] Quality control of hydraulic fluid may be achieved through the steps of depositing particulate contaminants at a bottom region of a pressure vessel and accumulating gaseous contaminants in a top region of said pressure vessel, and selectively extracting hydraulic fluid with particulate or gaseous contaminants from said pressure vessel. [0061] The process of extracting contaminants may be further enhanced through the step of accelerating the return flow of hydraulic fluid by means of an eductor. [0062] Testing the availability of the emergency shut down system, under continued production of the sub-sea production installation, is achievable through the provision of a redundant emergency shut down system by the introduction of multiple emergency shut down valves, electrically controlled into a normally closed position and individually operable into an open position for test purposes. SHORT DESCRIPTION OF THE DRAWINGS [0063] The invention is further explained below with reference made to the drawings, wherein [0064] FIG. 1 is a diagrammatic illustration of a set up of a sub-sea production installation; [0065] FIG. 2 is a schematic of an electro-hydraulic power system; [0066] FIG. 3 is a diagrammatic illustration of the canister circuitry associated with the return side of the hydraulic system; [0067] FIG. 4 is a detail of the ESD circuitry, [0068] FIG. 5 illustrates a detail for enhancement of fluid circulation, and [0069] FIG. 6 is diagrammatic view of the structural layout of a sub-sea HPU embodiment according to the present invention. DETAILED DESCRIPTION OF THE INVENTION [0070] The invention is described in the following with reference to the drawings. Note that the drawings and the circuitry depicted are deliberately simplified, leaving out a number of details for clarity, e.g. electrical control and instrumentation, filters and auxiliary valves. Also some of the symbols used are simplified for the same reason. The simplifications do not, however, significantly impair the description of key, new features. [0071] With reference to FIG. 1 , a set up for production of well fluids may typically comprise a top-side installation communicating with one or more sea floor wells via production flow lines connecting the land-based facility to the well heads. Production is controlled through the Christmas tree (XT) structure, situated on the wellhead and controlled for administrating the flow of fluids from the well. Actuating and control power for production and safety valves incorporated in the XT-structure is supplied via a controls umbilical, connecting a process control module on the host facility to the XT. The process control system typically comprises electrical and hydraulic power units and control equipment, supplying control and actuating power to the sub-sea installations via pipes that are bundled into, and shielded by, the umbilical cord. [0072] Naturally, for the purpose of this invention, the topside installations may be hosted on a land-based or a semi-submerged facility. Also naturally, in FIG. 1 the offset or tieback distance between the sub-sea installation and the host facility is grossly understated for illustrating purposes. [0073] The invention features a system of circulation of hydraulic fluid to a remote, sub-sea HPU 11 and back to a topside HPU 1 on the host facility, such that any gas migrating from the DHSVs through the XT-tubing to the control module will be brought back to the sub-sea HPU and returned to the host facility HPU by means of the return line R in a closed system. Even small-bore lines (typically ½″ for long offsets) in the umbilical have capacity to remove significant quantities of contamination. [0074] With reference specifically to FIG. 2 , the basic components of the invention are the top-side hydraulic pump 1 driven by a standard industrial electrical motor (not shown) and an accumulator bank 2 supplying hydraulic power at typically 207 bar through the small bore supply conduit P included in the umbilical 3 . A sub-sea HPU 11 located typically at a central structure at the production site comprises a canister 110 to protect components of the sub-sea HPU from the environment, a medium pressure (typically 207 bars plus environmental pressure) accumulator bank 4 , a low pressure accumulator bank 5 operating at a pressure higher than the environmental pressure, a set of DCVs 6 which distribute flow of hydraulic power to end consumers at operating pressure, a manifold for collection of return fluid from end consumers 10 , and a system of ESD valves 9 , a booster unit 7 comprising a pump and motor to boost pressure from the return pressure to operating pressure, a DCV 8 to facilitate fluid circulation at reduced pressure, and return line R. [0075] In normal steady state operation mode, i.e. when the natural DCV internal leakage (normally minute) is the only fluid consumption, the hydraulic power supply is provided by means of the supply line P with the sub-sea booster unit 7 in standby mode. This mode of operation is totally time dominant with at least 95% of the time, and for a typical system substantially more. [0076] In the transient mode, i.e. operation of valves, the fluid consumption is temporarily relatively high, the fluid supply from the supply line P is insufficient and assistance from the booster 7 is required. This situation is also typical of sub-sea process plants which include fast acting production control valves (PCVs). The booster 7 is used to charge the medium pressure accumulator bank 4 from the low pressure accumulator bank 5 . The booster motor is typically a squirrel cage unit running off the high voltage AC electrical power supply via a step down transformer, typically stepping the 3 phase, 5-60 Hz power down from 3-24 kV to 220 volts. [0077] For long tieback distances it may be advantageous to transfer electrical power to the booster motor and sub-sea electronics at low frequencies, or even extreme low frequencies down to 1 Hz. In practice, a power supply of AC-voltage at about 5 Hz has proven feasible at longer distances. Although resulting in lower rotational speed and capacity that requires up-sizing of the sub-sea HPU-motors and pumps, the reduced load on equipment also extends its life span and would still be a cost-effective option at long distances where cost of equipment is a less discriminating factor than is weight, e.g. [0078] A squirrel cage motor operating on any voltage lower than 1 kV may be wound for operation in a water-based or mineral oil-based hydraulic fluid, using common insulation materials (windings have been successfully designed for up to 9 kV). It may be practical to accept an increased size stator design in order to use a cable for the stator windings, rather than a varnish-insulated wire for extra electrical robustness. Design and fabrication of such motors represent common knowledge to those familiar with this type of technology. [0079] Controlling the sub-sea HPU 11 from standby mode to operative mode is performed by means of a pressure sensor connected to the medium pressure accumulator bank 4 , the sensor reporting via the communication system that the accumulator bank pressure is falling below a preset value, such as 185 bar, e.g., as the result of actuators being moved. A command for activating the sub-sea HPU 11 with booster unit 7 is then generated from a top-side control computer, shifting the sub-sea HPU 11 from standby mode to operative mode, thus transferring the power supply from line supply via the umbilical and top-side HPU 1 only, to a combined power supply from the top-side HPU 1 and the sub-sea HPU 11 . [0080] Typically the booster unit would be based on tilting pad bearings (not shown) for long life, although with this type of intermittent operation, actual operating time for a ten year period will not be very high compared to calendar time. With 5% transient operation, the annular active operation is some 400 hours, negligible in terms of wear. For operation of fast acting PCVs the active operation time of the booster assembly would obviously be much higher. [0081] Although the invention is perfectly applicable also in an open hydraulic system wherein used hydraulic fluid is discharged to the sea, a special case of steady state operation, referred to in the following as circulation mode, is advantageously facilitated by means of the check valve 15 . In this mode the medium pressure accumulator bank 4 provides the minor fluid consumption required to compensate for the DCV leakage. This frees both supply line P and return line R for circulation of fluid, and thus also for fluid quality control. [0082] Whereas FIG. 2 illustrates high level features of the invention, FIG. 3 illustrates essential features related to the circulation mode that are simplified or omitted for clarity in FIG. 2 . The canister 110 contains the accumulator banks 4 and 5 ( 5 not shown in FIG. 3 ) as well as the booster assembly 7 , all DCVs and other components of the sub-sea HPU. The canister has typically a cylindrical section and a hemispherical cap at top and bottom. The pressure in the canister is adjusted to provide for sufficient flow return fluid and is thus to be considered a pressure vessel. ROV-operated (remotely operated vehicle) HV-connectors and hydraulic stab connectors required to provide power and fluid are standard sub-sea components used extensively in sub-sea control systems. These provide wet connections as required. The canister has the very important function of accumulating contamination, particulate contamination at the bottom and any free gas at the top. Free gas is only expected for rare cases of serious seal failures in the DHSVs. It is important to remove both types of contamination. It is also important to remove fluid that has absorbed gas although not necessarily in a free state, but enough to influence the bulk modulus in a significant way. In FIG. 3 both types of contamination are visualized by gross exaggeration for purposes of illustration, no such level of contamination is likely to ever occur. For cases where a mineral oil/synthetic oil is used as control fluid, it is also important to remove oil contaminated by ingress of water from parts of the installation, whether in free phase or dissolved in the oil. [0083] DCVs 12 and 13 facilitate a selection of removing gas or particulate contamination by circulation. The particulate contamination is in a worst case NAS 1648 class 12, as systems of this type are invariably designed for achieving class 6, but it is common knowledge that they often operate at class 8 or even worse. Thus particles to be removed are small and travel easily in the circulation fluid. [0084] FIG. 5 illustrates in a simplified way a device for enhancement of circulation in the isolated mode without using moving parts. R 1 and R 2 , as per selection, feed contaminated fluid into an eductor which is operated by means of the energy in the P line. The return line R pressure is enhanced and simultaneously the contaminated fluid is effectively injected into the return line R. Considerable pressure increase is available without pressurizing the canister volume. Eductors are commodity items. [0085] Alternatively, though not shown in the drawings, a closed loop embodiment may additionally comprise a hydraulic circuit connecting the manifold from end consumers 10 to the return line R, downstream of the eductor of FIG. 5 , and controlling the return flow to the top-side HPU externally of the sub-sea HPU circuits via a check valve dedicated for this purpose. [0086] The check valve 15 is normally not permitted in design of sub-sea production control system, as the primary ESD mode is to bleed hydraulic fluid back from the sub-sea control modules, thus closing all fail-close safety valves. [0087] For very long offset control systems this traditional ESD mode of operation will not provide sufficient ESD response, and new mechanisms are required. Thus, as ESD has to be readdressed and be based on spring charged DCVs for bleed down of fluid pressure, the check valve is considered acceptable, thus facilitating the circulation mode. [0088] This approach raises the issue of ESD availability, normally expressed as the safety integrity level (SIL), which simply states the probability of success (in any mode of operation at any time) of achieving ESD on command. This functionality is critical and the probability of success is required to be very high. [0089] The ESD system 9 suggested in FIG. 4 will achieve the required functionality for ESD. Four standard DCVs 21 are connected as shown to ascertain ESD on command. No single failure of a DCV can prevent ESD and no single failure of a DCV can prevent production. The suggested type of redundancy can be expanded, but the suggested arrangement is sufficient to achieve very high SIL value. [0090] Investigations have demonstrated that this type of circuit improves the ESD availability as compared to a single valve by a factor ranging from 10-25, depending on assumptions made for common mode failure. Improvement factor of 10 would correspond to a 5% common mode factor and an improvement factor of 25 would correspond to a common mode factor of 2%. By careful design it is possible to approach the 2% level, thus providing a very high availability of the shutdown function. Thus the traditional ESD mode, i.e. bleed down from the host end, is no longer required. Also, it is no longer feasible. [0091] FMECA (failure mode and effect consequence analysis) and reliability analysis show that the current valve configuration ( FIG. 4 ) has a PFD (probability of failure to perform its safety function on demand) of 1.6 E-06 (0.00015%). Consequently, the system will comply with SIL 3 requirements, which is the typical safety integrity level specified for ESD systems. [0092] The DCVs are held open by means of dedicated electrical lines (low voltage DC) included in the umbilical. The dedicated electrical lines are wired directly to the ESD panel on the host facility. [0093] Under normal operation, an ESD on the host facility will cut all power to the sub-sea installation. This will instantly de-energize the solenoids of the ESD valves as well as shut down all functionality of the control module. The hydraulic pressure will bleed down and shut down all production valves. For test purposes, it will be possible to cut the power to the DCV solenoids using the dedicated control lines, while maintaining the power to the control system, thus simulating an ESD under full monitoring power of the control system. [0094] Testing of the ESD valves is an important feature. This can be achieved by supplying power to each solenoid individually or in pairs, i.e. to one DCV in each branch ( FIG. 4 ). This configuration will enable operation of all valves in the ESD circuit, without actually initiating a shutdown of the sub-sea production system. [0095] Proper valve functioning could be monitored by an inductive device in the DCV body, detecting the presence or absence of the DCV slide in the end position. Similarly, the same effect could be obtained by mounting a strain measurement device at the base of the DCV return spring. This will enable monitoring of the spring force, which is a function of the DCV slide position. [0096] Testing and monitoring the operation of the ESD system 9 (see FIG. 4 ), is achieved by including a flow-measuring device between the accumulator bank 4 and the schematically shown ESD valve system 9 (see FIG. 2 ). Any flow detected in this tubing is an indication of flow through the ESD valves. As this will be a very fast acting detection system, it will be possible to open the ESD valves, detect flow and close the ESD valves 21 before a decrease in supply pressure of the hydraulic system is experienced. It is therefore possible to test the ESD system without interrupting the production. [0097] The possibility for testing the individual valves in the ESD system 9 enables repair or replacement of an HPU with a faulty valve at convenience, thus further improving the availability of the ESD system. [0098] Operation of DHSVs requires substantially higher pressures than the XT valves. This pressure is provided by means of standard pressure intensifiers as per now commonplace in sub-sea production control systems. [0099] The structural layout of a sub-sea HPU 11 embodiment according to the invention is schematically illustrated in FIG. 6 . The canister/pressure vessel 110 is supported by a funnel support 46 , resting on the sea floor. Housed in the canister 110 are the accumulator banks 4 , 5 , the pump and motor/transformer assembly 7 , the selectively operated DCVs 12 , 13 for the return flow at circulation/contamination removal mode, as well as the electrically controlled valves 21 of the ESD-system. For clarity, the internal hydraulic and electric circuits explained with reference to FIGS. 2-5 are omitted from FIG. 6 . Reference number 43 designates a hydraulic jumper containing the hydraulic power supply line P and return line R, the jumper 43 connecting the sub-sea HPU 11 with an umbilical termination assembly (UTA), not shown in the layout, via ROV-operated hydraulic stab connectors 42 and the ROV-operated isolation valves 41 . Likewise, reference number 44 designates an electric jumper connecting the sub-sea HPU 11 with the UTA, via the ROV-operated electric stab connector 45 . [0100] Through the structural and operational means and measures provided above, the present invention also introduces a method for operating the process control means in an electro-hydraulic process control system in a sub-sea production installation, the method comprising the steps which are apparent from the above disclosure. Modifications to the disclosed embodiment are possible while still taking advantage of the presented solution, the scope of which is defined through the appending claims.
A hybrid process control system including electrical transmission of power to a sub-sea hydraulic power unit, which in turn provides hydraulic power for control of hydraulic actuators. A circulation system using small bore tubing in the umbilical cord in combination with a traditional topside hydraulic power unit provides for active control of hydraulic fluid quality with respect to contamination caused by the sub-sea hydraulic actuators, especially process gas from down hole safety valves. Thus, a more economical power transmission is achieved without reduction of fluid quality, which is essential to system integrity and reliability. Also, a significant enhancement of power transmission without a dramatic increase in the size of hydraulic supply and return lines is achieved. Fluid environmental issues are reduced to a negligible aspect.
4
BACKGROUND OF THE INVENTION The present invention arose in the coal mining equipment industry. As schematically shown in FIG. 1, when a coal-carrying conveyor belt rips transversally or separates at a seam, usually the severed ends move away from one another several feet in the moments of trauma following the accident. In overcoming the problem represented by a broken belt laden with coal, generally it is essential that an in situ repair be undertaken and performed, even if the repair will be good only long enough to let the coal on the belt be conveyed out. Then, a replacement or more permanent repair can be made under less stressful and awkward conditions. Sometimes it is possible to make the in situ repair a permanent one. One of the important initial tasks when undertaking an in situ repair is to bring the spread-apart severed ends of the belt back into alignment and abutment or adjacency. In order to accomplish this task a succession of decreasingly make-shift clamp devices have been devised. In the classical prior art, which continues to be practiced in many mines even today, adjacent each broken end B1, B2 of the belt B, the respective belt end is sandwiched between an upper timber TU and a lower timber TL oriented one over the other crosswise to the run of the belt. The timbers are longer than the belt is broad, so the ends of each timber extend beyond the belt edges. Laterally outwardly of each side of the belt, at each broken end B1, B2, securement means S, such as studs or cap screws are vertically installed through superimposed holes through the respective timbers. These are fastened and made tight with the aid of respective nuts and flat washers, to provide full width clamps C1, C2, for the respective belt ends B1, B2. To prevent slippage of the timbers of the clamps, cap wedges CW are driven between the timber and the belt, as needed. (Cap wedges are generally on hand anyway for use at the top of mine roof support timbers.) Clamp C1 is then lashed to Clamp C2 by tensile means T1, T2 such as chains, cables, block and tackle, etc. and one is pulled toward the other using pulling means W, e.g. a portable winch or hoist, to or mobile equipment which can pull on the tensile means T1, T2. Sometimes both tensile means T1, T2 are attached to the same pulling device, and other times one pulling device is pulling on T1 in one direction and another is pulling on T2 in the other. The beauty of the above arrangement is that usually, when a belt breaks, all the parts needed to make and install the clamps C1 and C2, and the pulling means can be cobbled together from whatever is close at hand. However, especially in a low seam in an underground mine, where space is at a premium it is awkward trying to assemble, install and use such full width clamps made of timber and hardware. Other, made for the purpose, full width clamps are fine for making above ground repairs, but are at least as awkward to use in low seam coal. Not only are they cumbersome to use because of their bulk, but they have to be carried to the site of the break, and their bulk and weight are against them for this reason also. In response to the need for something more convenient to carry and use, edge clamp sets were developed, with four individual clamps to a set. A prior art clamp of this type is shown by itself in FIG. 2, and the set is shown installed and in use in FIG. 3. Each clamp CL1, CR1, CL2, CR2 has a set of jaws JU, JL which grip a respective marginal edge portion of the belts near the respective belt broken ends. Each of these clamps has an anchor point A to which the respective chain T end attaches for the pulling operation. Although these prior art edge clamps have been well received, some users have complained that all too often, when a sufficient tension is pulled on the chains to get the broken belt ends moving back toward one another, one or more of marginal edge portions of the belt will rip next to its edge clamp. The relative location where a rip generally developes is indicated next to the clamp C1L by the line R. The present inventor has studied the prior art clamp of FIGS. 2 and 3, and believes he has discovered what causes the belt rips to occur. His reasoning is presented graphically in FIG. 4. In brief, in this prior art clamp, the site where the jaw set JU/JL grips the respective marginal edge of the belt is laterally offset from the anchor point A of the clamp. So that when the chain is attached for pulling the resulting torque tends to concentrate a ripping force at R. Clearly, the shorter the jaw-contact "footprint" is in the lateral direction D, the less will be the ripping torque for any given pulling force on the anchor point A of the respective clamp. For this reason, the ideal prior art clamp of this type has zero length jaws. In the actual clamps of this type, the provision of jaws of a finite length is a compromise from zero length, which walks a fine line between being so long as to cause belt twisting and tearing and being so short as to have insufficient clamping area to apply the clamping force without generating excessive compressive stress in the belt under load. A clamp that is a particular variation of the one shown in FIGS. 2 and 3 is shown in the prior U.S. Pat. No. of Travis, 3,955,810, issued May 11, 1976. SUMMARY OF THE INVENTION The present invention provides a tension-setting edge clamp with an improved linkage and an improved anchor point location so that when in use in sets of pairs, to pull broken belt ends toward one another for reconnection, wherein the anchor point for the center of pull on each clamp is aligned with the center of the clamping jaws of the same clamp, to minimize belt twisting, yet not interfere with the site of the adjoining broken edges. This eliminates a cause of belt rupture and tearing, yet provides space for the reconnection to be made. The principles of the invention will be further discussed with reference to the drawings wherein a preferred embodiment is shown. The specifics illustrated in the drawings are intended to exemplify, rather than limit, aspects of the invention as defined in the claims. BRIEF DESCRIPTION OF THE DRAWINGS In the Drawings FIG. 1 is a perspective view of a broken conveyor belt being repaired in situ in a low seam underground coal mine by a classical PRIOR ART technique; FIG. 2 is a perspective view showing a single self-setting, edge-type clamp of the more recent PRIOR ART useful for the same purpose; FIG. 3 is a diagrammatic plan view of a broken coal conveyor belt being repaired using a set of two pairs of the PRIOR ART clamps of FIG. 2 to practice a PRIOR ART process to pull the broken ends back into adjacency so that a reconnection can be made using any technique, such as stapling, riveting, sewing, patching, battening, splicing or the like. FIG. 4 is a perspective view, for comparison with FIG. 2 of a single self-setting edge-type clamp of the present invention; FIG. 5 is a second perspective view thereof; FIG. 6 is a third perspective view thereof; FIG. 7 is a fourth perspective view thereof, showing the jaws in an open condition. FIG. 8 is a diagrammatic top plan view, for comparison with FIG. 3 of a broken conveyor belt being repaired using a set of two pairs of the clamps of the present invention. FIG. 9 is a schematic illustration of how loading on the clamp of the invention (dashed lines) would be adversely affected if its jaw gripping surfaces were parallel in the unloaded condition (full lines); FIG. 10 is a similar schematic illustration of how the problem portrayed in FIG. 9 is overcome by making the clamp jaw gripping surfaces slightly non-parallel in the unloaded condition (full lines), so that when the clamp is loaded (dashed lines) the gripping surfaces become parallel to uniformly grip the belt between them. FIG. 11 is a bottom plan view of the upper jaw showing preferred dimpling to provide gripping surface means; and FIGS. 12 and 13 are fragmentary cross-sectional views on lines 12--12 and 13--13 of FIG. 11. DETAILED DESCRIPTION (For convenience in the description, the longitudinal direction along a conveyor belt from both extremes of the run of the belt in which the break has occurred, towards the break will be termed longitudinally inwards.) The clamp 10 includes a generally vertically oriented outer edge bracket 12, to which the laterally outer base end 14 of a first, preferably lower, upwardly facing jaw 16 is fixed, e.g. by welding as at 18. The jaw 16 is generally inverted U-shaped in transverse cross-sectional figure, so that it has a relatively broad, flat generally horizontal web 20, with two flanking brace webs 22, which taper in vertical extensiveness, from the base end 14 out to the laterally inner free end 24. The outer edge bracket 12 is shown being generally bar-shaped, with the jaw securement at 18 being located generally at the top of the lower half of the outer edge bracket 12, on the laterally inner face 26 thereof. The clamp 10 further includes a crank link plate 28 pivotally secured to the outer edge bracket bar 12 near the upper end of the latter, so as to have a horizontally, laterally-oriented pivot axis 30, e.g. provided by a nut, bolt and washer assembly 32 installed through corresponding openings in the crank link plate 28 and the outer edge bracket bar 12. Accordingly, the crank link plate 28 is located laterally to the inside of the outer edge bracket bar and mounted for arcuate movement about the pivot axis 30. The laterally outer base end 33 of a second, preferably upper, downwardly facing jaw 34 is secured on the laterally inner face 36 of the crank link plate 28, e.g. by welding as at 38. The jaw 34 has generally the same shape as the jaw 16, but is shorter-based laterally by the same amount that the face 36 is located laterally inwardly from the face 26, so that the laterally inner free end 24 of the jaw 16 is laterally aligned with the laterally inner end 40 of the jaw 34. Accordingly, the jaw 34 has a portion 42, which is generally horizontal when the clamp is closed, and two flanking brace portions 44. The pivot axis 30 is assymetrical relative to the length of the flat central portion of the jaw 34 being located longitudinally somewhat outwardly of the plane of symmetry of the jaw 34. Accordingly, as the jaw 34 swings to open, it moves upwardly and longitudinally inwardly, and then it pivots to close, the jaw 34 swings downwardly and longitudinally outwardly. When the clamp is fully closed, the jaw 34 is vertically superimposed upon the jaw 16, e.g. with only the vertical spacing needed to accommodate knurling or other gripping surface means 46 which preferably are disposed on the surface 48 of the central web 42 of the jaw 34 for confrontation with the surface 50 of the central web 20 of the jaw 16. The gripping surface means 46 may be constituted by the heads of respective bolts threaded into respective openings in the jaw 34. The presently preferred gripping surface means is shown in detail in FIGS. 11-13. The crank link plate includes a lobe 56 which extends generally longitudinally inwardly. The clamp 10 further includes a generally trapezoidal link plate 58 having two pivot axes 60, 62 which are parallel to one another and lie in the plane of this link. Of these, the axis 60 is adjacent and parallel to the narrower base 63 of the trapezoid and the axis 62 is adjacent and parallel to the broader base 65 of the trapezoid. The laterally outer edge 68 of the link plate 58 is perpendicular to the bases 63, 65 and the laterally inner edge 70 extends at an angle, except for having flat bosses 72, 74 coincident with the axes 60, 62. Each of the bases 63, 65 of the link plate 58 is slotted, with the laterally outer one 64 being longer and located laterally in from the outer edge 68 by an amount equal to the corresponding lateral dimension of the outer edge bracket bar 12. The crank line plate lobe 56 is received in the slot 64. A bolt, nut and washer assembly 76 is installed along the pivot axis 60 through corresponding openings in the trapezoidal link plate 58 and the crank link lobe 56. The axis 60 passes through the lobe 56 longitudinally inwardly of the jaw 34 and above the back of the jaw 34, but only about half-way along the length of the crank link plate. Thus, a substantial portion of the lobe 56 lies in the slot 64, since the axis 60 lies near the mouth of the slot 64. The slot 64 is laterally only slightly broader than the corresponding lobe dimension, so the fit is free but snug and not binding. A bolt, nut and washer assembly 78 is installed along the pivot axis 62 through corresponding openings in the trapezoidal link plate 58 near the broader base 65. A portion of the shank of the bolt of assembly 78 intersects the shorter slot 66 near the base 66, thus providing an anchor point 82 that is located laterally intermediate the bases and free ends of the clamp jaws. The structure depicted also includes a link 84, having a lower end positioned against the laterally outer face of the outer edge bracket 12 below the jaw 16, and pivoted thereto along a fourth laterally horizontal pivot axis 86, using a nut, bolt and washer assembly 88. The upper end of the link 84 is positioned against the laterally outer side of the trapezoidal link plate 58 and pivoted thereto by having a corresponding opening through which the nut, bolt and washer assembly 78 is installed. Desirably the clamp 10 is strengthened by a short link 90, with openings therethrough near opposite ends thereof. This link is placed against the laterally outer face of the outer edge bracket 12 and pivotally connected thereto by having the nut, bolt and washer assembly 32 installed through its corresponding opening. Similarly, the other end of the link 90 lies against the laterally outer edge, i.e. the broader base of the trapezoidal link plate 58 and is pivotally connected thereto by having the nut, bolt and washer assembly 76 installed through its corresponding opening. In use, the clamp 10 is installed on the outer edge region of a broken conveyor belt near the break, with the jaws open. A pull on the anchor point 82 in the direction of the arrow 92 and pounding on the clamp will pull the jaw 34 down tight against the belt, so that the belt is clamped between the jaws 16 and 34. The knurling on the jaw 34 guards against slippage. The clamp 10 can be loosened and freed from gripping the respective edge region of the belt, by relaxing the pull on the anchor point 82, and, if necessary, pounding on the trapezoidal link plate 58 anvil region at 94. The clamp of the present invention is preferably constructed of steel plate and steel nut, bolt and washer assemblies. A steel chain 96 may be secured at the anchor point 82 by having an end link journalled on the corresponding bolt shank. In the preferred embodiment described, the clamp 10 is believed to have several unique features, including the guided association of the crank like lobe with the sides of the trapezoidal link plate slot in which it is received, providing structural stability against clamp bending; reinforcement provided by the additional link 90, also providing structural stability against clamp bending; the provision on the link 58 of an anvil region 94 to facilitate freeing the clamp from the belt; the placement of the anchor point 82 laterally inwardly so that it is centered so as to be located laterally half-way across the gripping "footprint" of the clamp; and desirably the clamp jaws are longer longitudinally of the belt, to allow a better grip without causing belt damage than is possible in the prior art where a clamp anchor point is substantially laterally off-center compared to the clamp footprint center line. Although one clamp 19 is shown, it should be apparent that such clamps are generally intended to be used in sets of two pairs, in which in each pair, one clamp is a mirror image of the other. A typical installation is shown in FIG. 8. In this figure, one pair of clamps 10 is installed on the respective left edge portions of the belt on opposite sides of the break, and the other pair of clamps 10 is installed on the respective right edge portions of the belt on opposite sides of the break. When the respective belt edges are fully received between the respective clamp jaws, the respective belt edges abut the respective clamp outer edge bracket laterally inner faces. Accordingly, in each pair of clamps 10, the anchor points 82 are substantially in longitudinal alignment. The chains attached to each pair of anchor points can be simultaneously pulled longitudinally in the direction of the arrows, using one, two or four pulling device(s) such as a portable winch, mobile equipment such as tractors, or pressurized fluid-activated expansible/contractile piston/cylinder arrangements, or the like generically illustrated at 100. Once the broken ends have thus been brought into adjacency, the actual reconnection may be done by any convenient mechanism and method as in the prior art. Of course, the clamps 10 may be used in sets of two, one at the right and the other at the left if only one belt broken end is being pulled. The clamps are designed to be pulled with a steady pull of about 2000 pounds each, without permanent bending or slipping and without tearing, cutting or rupturing the belt. Further, the clamps may be used singly where pulling loads are relatively low, for instance at the time of initial installation of a belt. The aligned loading provided by having the anchor points 82 on line with the clamp footprint centers virtually eliminates twisting of the belt and thus eliminates a cause of rupture and tearing inherent in use of prior art edge clamps (as described above with regard to FIGS. 2 and 3). The nut, bolt and washer assemblies described above are representative of any equivalent pivot connection, journal and spacer means. It is not essential that the plate 58 be mathematically trapezoidal in shape. It is referred to hereinabove by its approximate shape as a matter of convenience. It may more generically be termed an anchor point link plate. Referring now to FIGS. 9 and 10, if the clamp 10 of the invention were constructed so that in a closed, unloaded condition (as shown in full lines in FIG. 9), its gripping surfaces 48, 50 were parallel, then, when a belt (not illustrated) is gripped between the jaws with the amount of force needed for pulling on the belt to make a repair, the clamp jaws and bolt 32 will deflect so that the tips of the clamp jaws are no longer compressing the belt between them. The deflection shifts the effective center of gripping force from the center toward the bases of the clamp jaws, e.g. from full lines arrow N to the dashed line arrow N' illustrated in FIG. 9. To overcome this tendency, by preference, the clamp 10 is constructed as illustrated in FIG. 10, so that the jaw surfaces 48, 50, when the clamp is closed but unloaded, are slightly non-parallel, i.e. are slightly closer toward the jaw tips (as shown in full lines). Accordingly, when the clamp 10 is loaded by gripping a belt (not illustrated) between its jaws and being pulled, the clamp parts deflect to their dashed-line positions causing even gripping with a properly centered gripping effect. Although bolt heads may be used to provide knurling 46 on the upper jaw gripping surface, the presently preferred knurling is provided by dimpling the upper jaw as shown in FIGS. 11-13. It should now be apparent that the clamp for repair of separation in conveyor belt as described hereinabove, possesses each of the attributes set forth in the specification under the heading "Summary of the Invention" hereinbefore. Because it can be modified to some extent without departing from the principles thereof as they have been outlined and explained in this specification, the present invention should be understood as encompassing all such modifications as are within the spirit and scope of the following claims.
The present invention provides a tension-setting edge clamp with an improved linkage and an improved anchor point location so that when in use in sets of pairs, to pull broken belt ends toward one another for reconnection, wherein the anchor point for the center of pull on each clamp is aligned with the center of the clamping jaws of the same clamp, to minimize belt twisting, yet not interfere with the site of the adjoining broken edges. This eliminates a cause of belt rupture and tearing, yet provides space for the reconnection to be made.
1
This disclosure is based upon French Application No. 99/12991, filed on Oct. 14, 1999 and International Application No. PCT/FR00/02880, filed Oct. 13, 2000, the contents of which are incorporated herein by reference. BACKGROUND OF THE INVENTION The present invention relates to a countermeasure method in an electronic component which uses an RSA-type public key encryption algorithm. In the conventional model of secret key cryptography, two people wishing to communicate by means of a non-secure channel must first agree upon a secret encryption key K. The encryption function and the decryption function use the same key K. The drawback of the secret key encryption system is that said system requires the prior communication of the key K between the two people by means of a secure channel, before any encrypted message is sent across the non-secure channel. In practice, it is generally difficult to find a perfectly secure communication channel, especially if the distance separating the two people is large. Secure channel means a channel for which it is impossible to ascertain or modify the information passing across said channel. Such a secure channel can be implemented by a cable linking two terminals, owned by the said two people. The public key cryptography concept was invented by Whitfield Diffie and Martin Hellman in 1976. Public key cryptography makes it possible to solve the problem of key distribution across a non-secure channel. The principle of public key cryptography consists of using a pair of keys, a public encryption key and a private decryption key. It must be unfeasible by means of calculation to find the private decryption key from the public encryption key. A person A wishing to communicate an item of information to a person B uses the public encryption key of the person B. Only the person B possesses the private key associated with his public key. Only the person B is therefore capable of decrypting the message sent to him. Another advantage of public key cryptography over secret key cryptography is that public key cryptography allows authentication through the use of electronic signatures. The first public key encryption scheme implementation was brought out in 1977 by Rivest, Shamir and Adleman, who invented the RSA encryption system. The security of RSA is based on the difficulty of factorising a large number which is the product of two prime numbers. Since then, many public key encryption systems have been proposed, the security of which is based on different calculative problems (this list is not exhaustive): “Knapsack” by Merckle-Hellman: This encryption system is based on the difficulty of the subset sum problem; McEliece: This encryption system is based on the algebraic coding theory. It is based on the linear code decoding problem; ElGamal: This encryption system is based on the difficulty of the discrete logarithm in a finite body; Elliptical curves: The elliptical curve encryption system constitutes a modification of existing cryptographic systems in order to apply them to the field of elliptical curves. The advantage of elliptical curve encryption systems is that they require a smaller-sized key than the other encryption systems. The RSA encryption system is the most used public key encryption system. It can be used as an encryption method or as a signature method. The RSA encryption system is used in smart cards, for certain applications thereof. Possible RSA applications in a smart card are accessing data banks, banking applications, or remote payment applications such as for example pay television, petrol dispensing or payment of motorway tolls. The principle of the RSA encryption system is as follows. It can be divided into three distinct parts, these being: 1) Generation of the pair of RSA keys; 2) Encryption of a clear message into an encrypted message; and 3) Decryption of an encrypted message into a clear message. The first part is the generation of the RSA key. Each user creates an RSA public key and a corresponding private key, according to the following method comprising 5 steps: 1) Generation of two distinct prime numbers p and q of the same size; 2) Calculation of n=pq and =(p−1) (q−1); 3) Random selection of an integer e, 1<e< such that pgcd(e, =1; 4) Calculation of the unique integer d, 1<d< such that e*d=1 mod ; 5) The public key is (n,e); the private key is d or (d,p,q). The integers e and d are called respectively the encryption exponent and the decryption exponent. The integer n is called the modulus. The second part of RSA key generation consisting of encryption of a clear message denoted m by means of an algorithm with 1<m<n into an encrypted message denoted c is as follows: Calculate c=m^e mod n. The third part of RSA key generation consists of decryption using the private decryption exponent d by means of an algorithm. The algorithm for decryption of an encrypted message denoted c with 1<c<n into a clear message denoted m is as follows: Calculate m=c^d mod n. The RSA decryption algorithm described previously can be performed by two different methods. These two methods are: decryption with CRT and decryption without CRT. CRT is an acronym for Chinese Remainder Theorem. The advantage of the decryption algorithm with CRT is that it is theoretically four times faster than the decryption algorithm without CRT. The decryption algorithm without CRT consists of calculating m=c^d mod n as described previously. The decryption algorithm with CRT consists of the following four steps: 1) Calculate cp=c modulo p and cq=c modulo q 2) Calculate dp=d modulo p−1 and dq=d modulo q−1 3) Calculate mp=cp^dp modulo p and mq=cq^dq modulo q 4) Calculate m=mp*q*(q^(−1) mod p)+mq*p*(p^(−1) mod q) For carrying out the modular exponentiations necessary in the calculation methods described previously, a number of algorithms exist: the algorithm called “square and multiply”; the algorithm with addition chains; the algorithm with a window; the algorithm with signed representation. This list is not exhaustive. The simplest and most used algorithm is the square and multiply algorithm. The square and multiply algorithm takes as inputs a number c, an exponent d and a modulus n. The exponent d is denoted d=(d(t), d(t−1), d(0)), where (d(t), d(t−1), d(0)) is the binary representation of d, with d(t) the most significant bit and d(0) the least significant bit. For example, the representation of the number five in binary is 101, resulting from the fact that 5=1*2^2+0*2^1+1*2^0. The first 1 is the most significant bit and the last 1 the least significant bit. The algorithm returns as an output the number m=c^d mod n. The square and multiply algorithm has the following three steps: 1) Initialise an integer variable A with the value c; 2) For i from t−1 to 0, do: 2a) Replace A by A*A mod n; 2b) If d(i)=1, replace A by A*c mod n; 3) Return to step 1 above. In the case of RSA decryption without CRT, the decryption is performed as described previously using the square and multiply algorithm. In this case, the square and multiply algorithm therefore takes as inputs the encrypted message c, the modulus n and the decryption exponent d. In the case of RSA decryption with CRT, the decryption is performed as described previously using the square and multiply algorithm twice for the execution of step 3) of the decryption algorithm with CRT. The first time, the algorithm takes as inputs the integer cp, the modulus p and the exponent dp. The second time, the algorithm takes as inputs the integer cq, the modulus q and the exponent dq. It is possible to perform these operations inside a smart card, said operations being performed by the microprocessor on the smart card. It turned out that the implementation on smart cards of an RSA-type public key encryption algorithm was vulnerable to attacks consisting of a differential current consumption analysis making it possible to find the private decryption key. These attacks are referred to as DPA attacks, DPA being an acronym for Differential Power Analysis. The principle of these DPA attacks is based on the fact that the current consumption of microprocessors executing instructions varies according to the data being manipulated. In particular, when an instruction is manipulating an item of data in which one particular bit is constant, with the value of the other bits capable of varying, analysis of the current consumption connected with the instruction shows that the mean consumption for the instruction is not the same depending on whether the particular bit takes the value 0 or 1. The DPA type attack therefore makes it possible to obtain additional information on the intermediate data manipulated by the microprocessor on the card during the execution of a cryptographic algorithm. This additional information can in certain cases make it possible to reveal the private parameters of the decryption algorithm, making the cryptographic system non-secure. In the remainder of this document, two types of DPA attack on the RSA decryption algorithm will be described. The first DPA attack described relates to the RSA decryption algorithm without CRT. The second attack described relates to the RSA decryption algorithm with CRT. These two attacks make it possible to reveal the private decryption exponent d. They therefore seriously compromise the security of the RSA implementation on a smart card. The first DPA attack relates to the RSA decryption algorithm without CRT. The attack makes it possible to directly reveal the secret exponent d, also called the private key. The first step of the attack is recording of the current consumption corresponding to execution of the square and multiply algorithm described previously for N distinct encrypted messages c(1), . . . c(N). To make the description of the attack clear, a method is first described which makes it possible to obtain the value of the bit d(t−1) of the private key d, or (d(t), d(t−1), d(0)), the binary representation of d, with d(t) the most-significant bit and d(0) the least significant bit. Then the description is given of an algorithm which makes it possible to find the value of d. The messages c(1) to c(N) are grouped according to the value of the least significant bit of c^4 mod n, where c designates one of the messages c(1) to c(N). The first group consists of the messages c such that the least significant bit of c^4 mod n is equal to 1. The second group consists of the messages c such that said bit is equal to 0. The mean of the current consumptions corresponding to each of the two groups is calculated, and the difference curve between these two means is calculated. If the bit d(t−1) of d is equal to 0, then the exponentiation algorithm described previously calculates and puts in memory the value of c^4 mod n. This means that, during execution of the algorithm in a smart card, the microprocessor on the card will actually calculate c^4 mod n. In this case, in one group of messages the last bit of the data item manipulated by the microprocessor is always equal to 1, and in the other group of messages the last bit of the data item manipulated is always equal to 0. The mean of the current consumptions corresponding to each group is therefore different. A current consumption differential peak therefore appears in the difference curve between the two means. If on the contrary the bit d(t−1) of d is equal to 1, the exponentiation algorithm described previously does not calculate the value of c^4 mod n. During execution of the algorithm by the smart card, the microprocessor therefore never manipulates the data item c^4 mod n. Therefore no consumption differential peak appears. This method therefore makes it possible to determine the value of the bit d(t−1) of d. The algorithm described in the following paragraph is a generalisation of the preceding algorithm. It makes it possible to determine the value of the private key d: The algorithm takes as inputs N messages c(1) to c(N) and the RSA modulus n, and returns as an output an integer h. The steps of the above algorithm are as follows: 1) Put 1 in the variable h, 2) For i from t−1 to 1, execute the following steps: 2)1) Classify the messages c(1) to c(N) into two groups according to the value of the last bit of c^(4*h) mod n; 2)2) Calculate the current consumption mean for each of the two groups; 2)3) Calculate the difference between the two means; 2)4) If the difference reveals a consumption differential peak, calculate h=h*2; Otherwise, execute h=h*2+1. The result of the algorithm is contained in the variable h. The preceding algorithm supplies an integer h such that d=2*h or d=2*h+1. To obtain the value of d, it is then sufficient to test the two possible hypotheses which are d=2*h and d=2*h+1. The DPA type attack described therefore makes it possible to find the private key d when the RSA decryption algorithm is performed without CRT. The second possible DPA attack on the RSA decryption algorithm relates to the application of the decryption algorithm with CRT as described previously. The attack described is made with chosen messages and focuses solely on the modular reduction operation (step 1) in the description of the decryption algorithm with CRT. The attack consists of sending correctly chosen messages to the card. The size of the binary representation of p is an integer k. This therefore gives 2^(k−1)<p<2^k. Two cases are then distinguished: In the first case, 2^(k−1)+2^(k−2)<p<2^k. In the second case, 2^(k−1)<p<2^(k−1)+2^(k−2). The method consists of having the card decrypt a first group A of messages c such that c<2^(k−1). The modular reduction of c modulo p therefore gives exactly the integer c as the result. The card is also given for decryption a second group B of messages c such that 2^k<c<2^k+2^(k−2) in the first case, and 2^(k−1)+2^(k−2)<c<2^k in the second case. In both cases, the modular reduction of c modulo p gives c-p. The card will therefore subsequently manipulate the data item c-p. By analysing the difference in consumption between the messages in the group A for which the result is c and the messages in the group B for which the result is c-p, it is possible by comparison to ascertain all the necessary information making it possible to obtain p. This paragraph gives the method making it possible to obtain the least significant bit of p. The method is similar for obtaining the other bits of p. The messages in the group A are classified into two categories: a message group A0 for which the last bit of the messages is equal to 0 and a message group A1 for which the last bit is equal to 1. The same operation is carried out for the group B, obtaining the group B0 and the group B1. If the least significant bit of p is equal to 1, the difference in consumption between the groups A0 and B0 will reveal a consumption differential peak since in the group A0 the last bit of the result is equal to 0 and in the group B0 the last bit of the result is equal to 1. If the least significant bit of p is equal to 0, the mean consumption difference between the groups does not reveal any peaks. By means of this method, the least significant bit of p can be determined. By means of a similar method, the bits of p can be successively determined. DESCRIPTION OF THE INVENTION The method of the invention consists of developing two countermeasures making it possible to guard against the two types of DPA attack described previously (an attack with CRT and an attack without CRT). The first countermeasure method consists of performing the calculations modulo p*r and q*t, r and t being random numbers. The first countermeasure method constitutes an improvement of an already existing method, presented in patent application WO 99/35782 filed by the company Cryptography Research. In this patent application, a method making it possible to guard against DPA type attacks during the RSA decryption operation is described. The drawback of this method is that it requires the use of integer divisions, operations difficult to carry out inside a portable object of the smart card type. The first countermeasure method comprises only addition and multiplication operations. The second countermeasure consists of making the recombination random using the Chinese Remainder Theorem (CRT). The first countermeasure method consists of using a random calculation modulus at each new execution of the decryption algorithm with CRT. It consists of performing the calculations modulo p*r and q*t, where r and t are random numbers. This method takes as inputs a message c, a decryption exponent d and a security parameter s and comprises the following eight steps: 1) Take three random numbers r, t and u between 0 and 2^s; 2) Calculate p′=p*r and q′=q*t; 3) Replace c by c+u*n; 4) Calculate cp=c modulo p′ and cq=c modulo q′; 5) Calculate dp=d′ modulo p−1 and dq=d′ modulo q−1; 6) Calculate mp′=cp^dp modulo p′ and mq′=cq^dq modulo q′; 7) Calculate m=((mq−mp)*(p^(−1) mod q) mod q′)*p+mp; 8) Replace m by m mod n. The first countermeasure method comprises two variants relating to updating of the integers r and t. The first variant consists in that a new pair of integers r and t is calculated at each new execution of the decryption algorithm, according to the method described previously. The second variant consists in that a counter is incremented at each new execution of the decryption algorithm. When this counter reaches a fixed value T, a new pair of integers r and t is calculated according to the method described previously, and the counter is reset to 0. In practice, T=16 can be taken. The first countermeasure method comprises a third variant which is useful when the size of the operations, on the integers is limited. This third variant comprises the following steps: 1) Take four random numbers r, t, u and v between 0 and 2^s; 2) Calculate p′=p*r and q′=q*t; 3) Calculate cp=c modulo p′ and cq=c modulo q′; 4) Replace cp by cp+u*p and replace cq by cq+v*q; 5) Calculate dp d′ modulo p−1 and dq=d′ modulo q−1; 6) Calculate mp′=cp^dp modulo p′ and mq′=cq^dq modulo q′; 7) Calculate m=(((mq−mp)*(p^(−1) mod q) mod q′)*p mod n)+mp mod n; 8) Replace m by m mod n. The first countermeasure method comprises a fourth variant making it possible to increase the security of the operations. In this fourth variant, part of the decryption is carried out modulo p and modulo q using the Chinese Remainder Theorem and part of the decryption is calculated modulo n. The advantage of this fourth variant is arranging that the attacker does not know the output of the recombination using the Chinese Remainder Theorem. This fourth variant comprises the following steps: 1) Take three random numbers r, t and u between 0 and 2^s; 2) Calculate p′=p*r and q′=q*t; 3) Replace c by c+u*n; 4) Calculate cp=c modulo p′ and cq=c modulo q′; 5) Calculate dp=d′ modulo p−1 and dq=d′ modulo q−1; 6) Calculate dp′=(dp−1)/2 and dq′=(dq−1)/2. 7) Calculate mp′ cp^dp′ modulo p′ and mq′=cq^dq′ modulo q′; 8) Calculate m=((mq−mp)*(p^(−1) mod q) mod q′)*p+mp; 9) Replace m by m^2*c mod n. Thus, as the attacker does not know the output of the recombination using the Chinese Remainder Theorem corresponding to step 7, the attacker cannot carry out a DPA attack on the recombination using the Chinese Remainder Theorem. The second countermeasure consists of making the recombination random using the Chinese Remainder Theorem. The random nature is due to the use of random calculation moduli. This countermeasure consists of replacing steps 7 and 8 of the first countermeasure method by the following steps. The length (in bits) of the integer p′ is denoted k. a) Choose two random integers (a0, b0) such that b0=a0−1, the integers a0 and b0 being k bits in size; b) Calculate the integer C=(mq−mp)*(p^(−1) mod q) mod q′; c) Calculate (c mod a0)=(C*p+cp) mod a0 and (c mod b0)=(C*p+cp) mod b0; d) Calculate two random integers (a1, b1) such that b1=a1−1, the integers a1 and b1 being k bits in size; e) Calculate C=((c mod b0)−(c mod a0)) mod b0; f) Calculate (c mod a1)=(C*a0+(c mod a0)) mod a1 and (c mod b1)=(C*a0+(c mod a0)) mod b1; g) Repeat steps e and f for a new pair (a2, b2) with b2=a2−1, the integers a2 and b2 being k bits in size. The integers (a0, b0) and (a1, b1) are replaced respectively by the integers (a1, b1) and (a2, b2); h) Step g is repeated k times, k being an integer parameter; i) Step g is repeated for the pair of integers (a, b)=(2^k, 2^k−1); j) Calculate the integer c1 defined by c1=c mod 2^k and calculate the integer ch defined by ch=((c mod 2^k−1)−(c mod 2^k)) mod 2^k−1; k) Calculate the signature c=ch*2^k+c1. Application of the two preceding countermeasure methods makes it possible to protect the decryption algorithm on smart cards against DPA type attacks. The two countermeasures presented are furthermore compatible with one another: it is possible to apply to the RSA decryption algorithm one or two of the countermeasures described, as well as the four variants of the first countermeasure.
A countermeasure method in an electronic component which uses an RSA-type public key cryptographic algorithm. A first countermeasure method uses a random calculation for each new execution of the decryption algorithm with CRT. The calculations are made modulo p*r and q*t, r and t being random numbers. A second countermeasure makes the recombination random using the CRT theorem.
7
This invention relates to pluggable electronic cartridges used in typewriters and computers. More specifically, the invention relates to an extraction apparatus for pulling the cartridge connector from the electronic board of the host device BACKGROUND OF THE INVENTION As electronic typewriters become more sophisticated and provide ever increasing function, the products are following the lead of personal computers in that the functions or features may be added to the basic typewriter by the attachment of an auxiliary device which contains the necessary code to control the typewriter in the desired manner. The approaches that have been followed in adding function to typewriters includes the use of dedicated circuit boards which are contained within an enclosure which is then attached to the typewriter both electronically and physically. This approach is cumbersome and limits the operator to a few optional functions. Computers and more recently typewriters have begun using cartridges for the addition of function and memory capacity. The cartridges are connected to the electronics of the typewriter or computer by engaging a connector and a land pattern of a circuit board. To insure adequate contact between the connector and the lands, the connector exerts a significant force on the land when the connection is made. This force also serves to impede the removal of the connector. The natural tendency of the operator is to insert and remove the cartridge by rocking the cartridge relative to the circuit board of the machine. This is undesirable, particularly with cartridges which require that the electronic circuitry be electrically grounded prior to making the functional connections, since the ground protection is typically designed for a straight push insertion, and extraction. Additionally, it is desirable from a design standpoint, to have the cartridge contained within the machine housing as much as possible. This not only makes the appearance of the machine more pleasing, but also minimizes the possibility of causing a machine malfunction through undesired impact of the cartridge. The desired low profile or minimal exposure of the cartridge requires that only a minimum of the cartridge be exposed to the grip of the operator and thus hinders the extraction of the cartridge due to the small grip area and the relatively high engaging force exerted by the connector on the circuit board lands. U.S. Pat. No. 1,900,782 to C. M. May discloses a light plug which has a bellcrank lever movable by a person's thumb to pull the plug from the electrical wall socket. This device, while well suited for the environment in which it is used, exerts a force well off the center of the plug blades and actually tend to induce rocking or tilting of the plug, which in the present environment is very undesirable, as described above. SUMMARY OF THE DISCLOSURE The present invention is a cartridge with either a circuit board land pattern or a connector on the circuit board exposed through an opening in the cartridge housing. Attached to the cartridge housing near the extremity that will remain exterior to the machine housing is a device for assisting the operator in the extraction of the cartridge from the machine housing. The extractor comprises a handle which in turn is connected to at least a camming surface oriented in such a way as to engage the machine housing, when pivoted. The cam surface is defined so as to engage the machine housing at a fixed point to effect extraction of the cartridge from the connection with the electronic circuit of the machine. The handle is grasped by the operator and rotated to drive the camming member around its pivot axis and in so doing, the cartridge is force upward and outward from the machine housing. The line of force exerted on the cartridge by the cam members is such that the connector is disconnected from the circuit board without exerting a rocking or twisting motion. DRAWING FIG. 1 illustrates the cartridge positioned within the machine housing. FIG. 2 illustrates a portion of the cartridge partially withdrawn from the machine housing, and showing the keying arrangement necessary to control undesired interchangeability of cartridges. FIG. 3 is a section view of the cartridge and machine housing. FIG. 4 illustrates the cam profile and the relation of the cam with machine housing at the point of engagement. FIG. 5 illustrates the cartridge of the invention with the edge connector exposed through an opening in the cartridge for mating with the edge connector of the machine. DETAILED DESCRIPTION OF THE INVENTION The cartridge 10 is the type of pluggable cartridge in which the program or software for a particular function or feature of a typewriter or computer may be packaged or which may contain additional memory capacity. The cartridge 10 is insertable into the machine housing 12 which has a cavity or sleeve 14 formed to guide the cartridge 10 during insertion and extraction. The cartridge 10 may be provided with a connector 16 which is exposed to the exterior of the cartridge 10 or alternatively the circuit board 18 contained within the cartridge 10 may have a pattern of lands that will mate with a connector 16 as shown in FIG. 5. There is no significance to the choice of the location of the connector 16. The sleeve 14 of the machine housing 12 comprises a plurality of wals or slide surfaces 22 which act to constrain the cartridge 10 except in a direction which would permit insertion or extraction. The sleeve 14 may be keyed by means of a channel or some other irregularity 36 which will permit the insertion of a cartridge 10 with a complimentary irregularity 34. When the cartridge 10 is fully inserted as is the case in FIG. 1, the top of the cartridge 10 protrudes only slightly above the machine housing 12, providing only a small portion of the cartridge 10 to be grasped. In order to extract the cartridge 10 from the machine housing 12, and at the same time insure that the cartridge is not deflected or pushed to one side or the other with possible attendant electrical or physical damage to the circuit or the circuit board 18 or 19 and connector 16, it is desirable to pull the connection between the connector 16 and the mating circuit board 19 or 18 so that the direction of movement is parallel to the plane of the circuit board 18 or 19 and perpendicular to the connection edge of the circuit board 18 or 19. Connectors 16 of the edge connector type illustrated require a relatively large force to ensure both physical and electrical engagement. Overcoming such force with a small gripping area can be further compounded by the fact that many operators may have long fingernails which will interfere with the securing of a good grip on the cartridge 10. In order to easily extract the cartridge 10, and to insure that the extraction force was exerted in the desired plane, a camming member 23 is pivotally mounted on the cartridge, on the cartridge sides 24. The pivot 26 supports the camming member 23 so as to allow the rotation of the camming member 23 and the exertion of a force against the machine housing 12. The increasing radius cam profile 30 of the camming member 23 is configured to have a constant point of engagement on the machine housing. The constant point of engagement 39 prevents the shifting of the forces and a resulting rocking or twisting of the cartridge 10, relative to the circuit board 18 within the machine housing 12. As the camming member 23 is rotated to create an extraction force on the cartridge 10, the radius or rise of the cam profile 30 increases at such a rate as to maintain the point of engagement 39 in a constant position as described above. The camming member 23 is rotatable by exerting an upward force on handle 28 which extends from the camming member 23 and across the width of the cartridge 10, thus interconnecting the essentially identical camming members 23 on each side of the cartridge 10. The use of dual camming members 23 insures that the force exerted on the cartridge 10 will be balanced on pivots 26 on both sides of the cartridge 10. The cartridge 10 may be one where it should only be inserted into a designated sleeve and in those instances, may be keyed with a ridge 34 or other similar surface irregularity. The ridge 34 or alternative surface irregularity may be referred to as key 34. The key 34 is configured to mate with a complimentary shape such as a slot 36 in the sleeve 14. Unless the key 34 and the slot 36 match and the key 34 enters the slot 36, the cartridge 10 cannot be inserted into the machine housing 12. The cartridge 10 is inserted into the machine housing 12 by introducing the cartridge 10 into the sleeve 14 and pushing. Movement of cartridge 10 into sleeve 14 brings connector 16 into engagement with the circuit board 19 or 18. The sleeve 14 acts to prevent the cartridge 10 from being rocked to ease the connection to the circuit board 19 or 18 within the machine housing 12. Should the operator desire to remove the cartridge 10 from the machine housing 14, the handle 28 is grasped and lifted to rotate the camming members 23 forcing the cam profiles 30 of the camming members 23 against the machine housing 12. The engagement point between the camming devices 23 and the machine housing 12 remains at a constant point on the machine housing 12, thereby insuring a constant directional force exerted to cause the extraction of the cartridge 10 and disconnection of the cartridge 10 from the circuit board 19 contained within the machine housing 12. The constant engagement point on the machine housing 12 prevents a deflection of the cartridge 10 and the attendant risk of damaging either the circuitry on board 18 of the cartridge 10 or the circuitry on board 19 contained in the machine housing 12. The handle 28 and the camming members 23 on the cartridge 10 eliminate the need for a substantial portion of the cartridge 10 to be exposed above the machine housing 12 for gripping purposes.
The cartridge disclosed is provided with an extractor means which is instrumental in the removal of the cartridge from the machine, by providing a smooth camming action to move the cartridge away from the machine circuit board. The extractor allows the cartridge to protrude only a small amount outside the machine housing and still be removed such that the cartridge is not rocked or moved to and fro relative to the machine circuit board.
7
TECHNICAL FIELD [0001] The present invention relates generally to fluid retaining mop structures, and more particularly to a mop head incorporating fluid retaining strand elements of contoured, tubular construction incorporating an arrangement of elongate surface channel depressions extending at least partially along the length of such strand elements interposed between raised profile protrusions. A process for forming the mop head is also provided. BACKGROUND OF THE INVENTION [0002] Mop heads incorporating tubular strand elements of so-called “edgeless” construction are known. One such construction, which is marketed by Contec Inc. of Spartanburg, S.C., is formed from a skein of circular knit material of tubular construction which is formed on a winding apparatus using a pair of support bars which rotate relative to one another. The skein structure is formed from a single continuous tube of the knit material. Upon removal from the winding apparatus, the skein thus has an interior and two ends formed by the reverse folds in the knit tube where it has been passed around the winder bars. The skein structure is thereafter inserted into a relatively narrow width containment sleeve which is seamed to the interior of the skein structure at a substantially central location to contain the tubular elements in the wound structure. Seams are also applied at slightly inboard positions relative to the folded over ends of the skein structure so as to avoid undue spreading of the individual folded over elements. The mop head so formed is thereafter attached to a handle at the central containment sleeve. Importantly, the prior mop heads formed in this manner have utilized a circular SUMMARY OF THE INVENTION [0003] The present invention provides advantages and alternatives over the prior art by utilizing a relatively narrow diameter, knit tubular material to form the strands of a mop head substantially in the same manner as described above but wherein the tubular material incorporates an arrangement of elongate depressed channels and raised profile segments or ridges extending along its surface in the length direction rather than using the flat surface structure of the prior constructions. This construction has surprisingly been found to increase the overall fluid retaining or sorbency capacity of the mop relative to the prior flat surface construction even while lowering the overall mass of the mop head. That is, more fluid may be retained even though less fluid retaining material is utilized thus providing a substantial improvement over the prior known construction. BRIEF DESCRIPTION OF THE DRAWINGS [0004] The accompanying drawings which are incorporated in and which constitute a part of this specification illustrate potentially preferred embodiments and practices in accordance with the present invention and, together the general description of the invention given above and the detailed description set form below, serve to explain the principles of the invention wherein: [0005] FIG. 1 is a simplified illustration of a circular knitting machine as will be well known to those of skill in the art for use in forming the absorptive string elements of a mop head according to the present invention; [0006] FIG. 2 illustrates a mop head according to the present invention in attached relation to a handle structure; [0007] FIG. 3 is an elevation plan view of the mop head in FIG. 2 ; [0008] FIG. 4 is a cross-sectional side view of the mop head in FIG. 3 . [0009] FIG. 5 illustrates an exemplary cross-section of an individual strand taken through line 5 - 5 in FIG. 1 . [0010] While the invention has been illustrated and generally described above and will hereinafter be described in connection with certain potentially preferred embodiments and procedures, it is to be understood that in no event is the invention to be limited to such illustrated and described embodiments and procedures. On the contrary, it is intended that the present invention shall extend to all alternatives and modifications as may embrace the broad principles of this invention within the true spirit and scope thereof. DESCRIPTION OF THE PREFERRED EMBODIMENT [0011] Reference will now be made to the various drawings wherein to the extent possible, like reference numerals are utilized to designate like components throughout the various views. In FIG. 1 , there is illustrated a circular knitting machine 10 such as will be well known to those of skill in the art. By way of example only, and not limitation, one knitting machine 10 which has been identified as suitable for practice of the present invention is a model ST3AH/ZA high speed, single feed, circular knit machine having a cylinder size of 1.5 inches in diameter and 48 needle slots available manufactured by Lamb Knitting Machine Corporation having a place of business in Chicopee, Mass. USA. [0012] According to one contemplated practice, in operation a pair of yarns 12 , 12 A is delivered from spools 13 , 13 A to the knitting machine 10 for formation of a tubular knit structure 14 . The yarn 12 is preferably a 150 denier singles textured polyester having either an “S” or “Z” twist construction. The yarn 12 A is preferably a 150 denier two ply textured polyester wherein one ply has an “S” twist and the other ply has a “Z” twist. Thus, the two yarn system incorporates yarn orientations with a combination of opposing twists. This balance in twist permits the knit structure to avoid undue curling when subjected to laundering operations. Of course, the particular yarn system selected may be varied as desired by the user. [0013] The tubular knit structure 14 which is formed according to the potentially preferred practice of the invention includes an arrangement of elongate channel depressions 20 running along the length of the tubular knit structure 14 ( FIG. 5 ). The depressions 20 are disposed between raised profile surface protrusions 24 across the surface of the tubular knit structure 14 such that an undulating or corrugated surface profile is provided wherein the elongate channels and surface protrusions extend in alternating substantially parallel relation. [0014] According to a potentially preferred practice, the illustrated arrangement of channel depressions 20 and raised profile protrusions 24 is achieved by using a modified needle arrangement in the knitting equipment to create a space between courses formed during the knitting process. According to one exemplary practice, the circular knit machine as described above is modified to incorporate a needle arrangement with four needles in and two needles out in an arrangement which is repeated eight times around the circumference of the cylinder. This produces a profiled surface with eight cooperating channel depressions 20 and eight raised profile protrusions 24 . Of course this number may be greater or lower as desired but will preferably be at least four and will more preferably be about 6 or greater. According to one potentially preferred practice the machinery is set up to produce a tubular knit structure with fourteen courses per inch (relaxed state) and a weight of about 6.1 grams per linear yard (relaxed state). The resulting construction is a modified jersey knit utilizing thirty-two active needles for knitting. [0015] It is contemplated that the tubular knit structure as described will form the fluid retaining strands of a mop head 30 attached to a handle 40 to form a mop 50 as illustrated in FIG. 2 . As best illustrated through simultaneous reference to FIGS. 24 , the mop head 30 is formed from a skein of the tubular knit material 14 . As previously indicated, such a structure may be formed by winding an extended length of the tubular knit material multiple times around a pair of spaced-apart bars and then removing the formed structure from those spaced-apart bars. As illustrated, the resultant skein structure has an arrangement of folds 32 at either end of the skein structure. As will be appreciated, the folds 32 are formed at the location where the tubular knit material is wrapped around the opposing bars during the winding operation. Of course, it is also contemplated that a similar structure may be formed by hand coiling or other techniques as may be desired. Moreover, while it may be desirable to use a single long piece of tubular knit material 14 folded upon itself multiple times to form the mop head, it is also contemplated that two or more shorter lengths may be used if desired. Thus, it is to be understood that by the term “skein” is meant any structure in which one or more lengths of elongate material are folded upon themselves such that the folds define an edge boundary with discrete strand elements extending away from the edge boundary. [0016] According to the illustrated and potentially preferred practice, the skein structure forming the mop head 30 is fitted into a containment sleeve element 34 of fabric or the like which is then seamed in place so as to hold the strands of tubular knit material 14 in adjacent relation to one another at a central location. Moreover, the ends of the tubular knit material where the winding begins and concludes are also held in hidden relation beneath the containment sleeve element 34 . Finally, strips of material 36 are seamed in transverse relation to the strands of tubular knit material 14 at positions inboard of the folds 32 so as to maintain a desired adjacent relation of the strand elements at each end of the mop head 30 . The mop head 30 may thereafter be washed and dried prior to attachment to the handle 40 . [0017] As previously indicated, the adjustment of the circular knitting machine 10 to produce the tubular knit material 14 with interspersed elongate channel depressions 20 and raised profile protrusions 24 yields substantially improved moisture retention capacity even when lower weights of material are utilized. This moisture retention capacity is referred to as “sorbent capacity” and may be made up of moisture retention resulting from absorption and/or adsorption at the strands of tubular knit material. In this regard, it is contemplated that the benefits of the present invention will be applicable to both hydrophilic as well as hydrophobic materials of construction although polyester which is hydrophobic may be particularly preferred. [0018] In order to evaluate the relative performance of a mop head formed according to the present invention, exemplary mop heads formed with fluid retaining strands having elongate channel depressions and raised profile protrusions were weighed in a dry state and were thereafter immersed in water until fully saturated and then weighed in a wet state once dripping had substantially ceased. The contoured surface mop heads were formed according to the potentially preferred practice as described above on a 1.5 inch diameter circular knitting head with an arrangement of four needles in and two needles out repeated eight times around the circumference. Mop heads of similar construction but incorporating flat surface tubular strands of knit material formed on the same knitting head but with all needles in were tested according to the same procedure. Each of the structures was also tested to measure sorbency in a wet state wherein the wet mop was immersed after wringing excess moisture from the mop head following initial saturation. The results are set forth in Table I below: TABLE 1 Dry mop sorbent Wet mop sorbent Dry mop weight capacity capacity Wet mop weight In In Intrinsic Extrinsic Intrinsic Extrinsic % In grams ounces (mL/g) mL/mop (mL/g) (mL/mop) wringability In grams ounces FIat 1 433 15.3 2.83 1225 0.92 400 32.7% 1258 44.4 Flat 2 431 15.2 2.67 1150 0.93 400 34.8% 1181 41.7 Averages 432 15.2 2.75 1188 0.93 400 33.7% 1220 43.0 Contoured 1 399 14.1 4.39 1750 2.01 800 45.7% 1349 47.6 Contoured 2 399 14.1 4.26 1700 2.13 850 50.0% 1249 44.1 Contoured 3 402 14.2 4.35 1750 1.99 800 45.7% 1352 47.7 Contoured 4 399 14.1 4.26 1700 1.88 750 44.1% 1349 47.6 Contoured 5 400 14.1 4.25 1700 2.13 850 50.0% 1250 44.1 Contoured 6 401 14.1 4.49 1800 2.12 850 47.2% 1351 47.7 Contoured 7 399 14.1 4.39 1750 2.13 850 48.6% 1299 45.8 Averages 400 14.1 4.34 1736 2.05 821 47.3% 1314 46.4 FIat 1 and 2 are the prior structures and contoured 1-6 are specimens of the present invention. [0019] As can be seen, the mop structure of the present invention exhibited substantially greater intrinsic sorbent capacity in both the wet and dry states relative the prior structure using flat tube fluid containment strands. [0020] While the present invention has been illustrated and described in relation to certain exemplary and potentially preferred embodiments and practices, it is to be understood that such embodiments and practices are illustrative only and that the present invention in no event to be limited thereto. Rather, it is contemplated the modifications and variations will no doubt occur to those of skill in the art upon reading the above description and/or through practice of the invention. It is therefore contemplated and intended that the present invention shall extend to all such modifications and variations which may incorporate the broad concepts of the present invention within the full spirit and scope thereof.
An edgeless mop utilizing a relatively narrow diameter, knit tubular material to form the strands of a mop head wherein the tubular material incorporates an arrangement of elongate depressed channels and raised profile segments extending along its surface in the length direction. This construction increases the overall fluid retaining or sorbency capacity of the mop even while lowering the overall mass of the mop head.
3
[0001] This application claims priority from U.S. provisional applications Ser. Nos. 60/725,630 filed 13 Oct. 2005, which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION [0002] The invention relates generally to methods and compositions for genetically modifying microorganisms, and more particularly, to methods and compositions for selectively modifying genomic regions containing predefined sets of genes and/or genetic elements. BACKGROUND [0003] Metagenomics and the development of techniques for the facile production and manipulation of large fragments of DNA have spurred interest in engineering microorganisms for a host of important industrial and medical applications, e.g. Lorenz et al, Nature Reviews Microbiology, 3: 510-516 (2005); Branda et al, Developmental Cell, 6: 7-28 (2004); Kodumal et al, Proc. Natl. Acad. Sci., 101: 15573-15578 (2004); Tian et al, Nature, 432: 1050-1054 (2004). Metagenomics is the application of genomics techniques to the study of communities of microbial organisms directly in their natural environments, bypassing the need for isolation and laboratory cultivation of individual species, e.g. Reisenfeld et al, Annu. Rev. Genet., 38: 525-552 (2004). Such studies have revealed a wealth of genes encoding novel biochemical pathways and biocatalysts that potentially could play important roles in industrial processes, such as the extraction of fuels from refractory petroleum deposits, the conversion of agricultural raw materials into bulk and specialty chemicals, the generation of fuels from renewable resources, the discovery and development of therapeutically useful products, and the like, e.g. Handelsman, Microbiol. Mol. Biol. Rev., 68: 669-685 (2004); Van Hamme et al, Microbiol. Mol. Biol. Rev., 67: 503-549 (2003); Aitken et al, Nature, 431: 291-294 (2004). In particular, it is expected that metagenomics will provide an important source of raw materials for metabolic engineering, that is, the improvement of cellular activities by manipulation of enzymatic, transport, and regulatory functions of cells with the use of recombinant DNA technology, Bailey, Science, 252: 1668-1674 (1991). [0004] In parallel with the above developments, there has been great interest in designing host organisms that are genetically well defined and, in some sense, minimal, not only for engineering applications, but also for understanding the basic life processes of free living microbes, e.g. Koonin, Annu. Rev. Genomics Hum. Genet., 1: 99-116 (2000); Kolisnychenko et al, Genome Research, 12: 640-647 (2002); Kobayashi et al, Proc. Natl. Acad. Sci., 100: 4678-4683 (2003); Glass et al, Proc. Natl. Acad. Sci., 103: 425-430 (2006); Posfai et al, Science, 312: 1044-1046 (2006); and the like. The primary approach in such studies has been to compare genomes of related species or strains to identify common genes and then to systematically delete genes or elements that are not shared, or to randomly disrupt genes and measure the effect on organism viability, e.g. Hutchinson et al, Science, 286: 2165 (1999). While reduced bacterial genomes appear to provide some advantages for protein production, the basic genome structure of such organisms remains unchanged from the essentially unordered assembly of genes, operons, and gene clusters provided by evolution, in which the genetic elements involved in every life function are scattered throughout the genome, Wolf et al, Genome Research, 11: 356-372 (2001); Bentley et al, Annu. Rev. Genet., 38: 771-792 (2004); Ochman et al, Curr. Opin. Microbiol., 6: 109-113 (2003); Ward et al, Curr. Opin. Microbiol., 8: 564-571 (2005). Such lack of order increases the difficulties of manipulating multiple genes and/or regulatory elements that may be involved in the same metabolic pathway. [0005] In view of the above, it would be useful to have available a host organism for metabolic engineering that had a modular genome structure that permitted placement of functionally related genes and genetic elements in common regions and that allowed facile replacement of such regions, thereby taking advantage of recent advances in large-fragment polynucleotide synthesis and manipulation. SUMMARY OF THE INVENTION [0006] The invention provides methods and compositions for assembling large nucleic acid constructs, such as modular replacement genomes in host microorganisms. After such assembly, the host organism's genome is inactivated or otherwise removed to permit full control of host cellular functions by the replacement genome. A modular replacement genome comprises an assembly of nucleic acid fragments, or segments, derived from one or more natural organisms or from synthetic polynucleotides or from a combination of both. Such an assembly, or set, of segments making up a replacement genome comprises a substantially complete set of genes and regulatory elements for carrying out minimal life functions under predefined culture conditions. “Substantially complete” in reference to the set of such genes and/or regulatory elements means that a minority of one or more genes and/or regulatory elements may be provided by episomal elements, such as plasmids, or the like, separate from the replacement genome. In one aspect, genes and regulatory elements of a replacement genome are selected to be substantially compatible with host genome counterparts. Such compatibility is usually accomplished by selecting a host genome-replacement genome pair whose sequences are sufficiently orthologous that (i) a substantial majority of replacement genes encode gene products or give rise to metabolites that do not interfere with host organism growth or replication, or are not otherwise poisonous to the host organism, and (ii) any subset of replacement genes giving rise to interfering or poisonous gene products or metabolites can be placed under inducible control. [0007] In one aspect, component fragments, or segments, of a replacement genome are prepared separately in large-insert vectors wherein each different fragment is associated with one or more unique recombination elements. A plurality of such segment-containing vectors that collectively provide a complete sequence of a replacement genome is assembled stepwise in a predetermined order by repeated cycles of transformation of a host organism. In each successive cycle, a precursor replacement genome is formed that contains an additional segment, until a complete replacement genome is formed. Alternatively, a plurality of such segments may be assembled in parallel or in series by one or more cycles of co-transformation of a suitable host that permits self-assembly of multiple segments either by providing multiple segments with non-cross-reacting site-specific recombination elements or by the presence of a robust DNA repair system for joining double stranded breaks, e.g. as in D. radiodurans . After a complete replacement genome is formed, the host genome is then removed or rendered inoperable by inactivation, ablation or loss during cell partitioning, and any genes deleterious to the host are “turned on” by providing conditions for their induction, thereby forming a free-living synthetic cell with the replacement genome. [0008] In another aspect, a replacement genome is modular in that after assembly and removal of the host genome, segments of the replacement genome may be selectively replaced with modified segments or added to by insertion of new segments using the recombinant elements left over from its initial assembly. [0009] In another aspect, the invention provides a method of assembling a replacement genome in a host organism comprising the following steps: (a) providing a plurality of segments that cover a replacement genome, each segment being associated with one or more recombination elements; (b) transforming or co-transforming the host organism with one or more segments to form a precursor genome, the precursor genome being a recombinant of the one or more segments or a recombinant of a prior precursor genome and the one or more segments, such recombinant being formed by recombination of the recombination elements associated with the one or more segments; (c) repeating step (b) with segments of a predetermined ordering until the replacement genome is formed; and (d) removing the host genome. In one embodiment, the step of transforming or co-transforming may comprise co-transforming a host organism with the plurality of segments so that the replacement genome is formed in one step. In another embodiment, each end of each of the segments of a plurality has a unique overlapping sequence region with an end of another segment of the plurality so that the predetermined ordering is established upon formation of the replacement genome. [0010] In another aspect, the invention provides a method of assembling a replacement genome in a host organism comprising the steps: (a) providing a plurality of segments that cover a replacement genome, each segment being associated with one or more recombination elements; (b) transforming the host organism with a segment to form a precursor genome, the precursor genome being the segment or a recombinant of the segment and a prior precursor genome, such recombinant being formed by at least one recombinase acting on the recombination elements associated with the segment; (c) repeating step (b) with each of a predetermined ordering of segments until the replacement genome is formed; and (d) removing the host genome. In one embodiment, each of the segments is associated with at least one recombination element selected from a plurality of different kinds of recombination elements and each successive segment in the predetermined ordering is associated with a different kind of recombination element selected from the plurality. In particular, the successive recombination elements may be mutant loxP sites that do not cross react. In one approach of such assembling process the step of transforming may produce a precursor genome containing a pair of recombination elements of the same kind, in which case, in one embodiment, the step of transforming may further include modifying one of said pair of recombination elements of the same kind so that it is reactive with a different kind of recombination element, such as the recombination element of the next segment. [0011] In another aspect, the invention provides nucleic acid constructs made by serial site-specific recombination, as well as host organisms in which they are assembled and replicated. [0012] In still another aspect, the invention provides kits for assembling nucleic acid constructs from component polynucleotides, or segments, in a host organism, such kits comprising an ordered plurality of large-insert vectors, each large-insert vector being associated with one or more recombination elements and capable of incorporating an insert and each large-insert vector containing at least a first recombination element in common with its immediately preceding large-insert vector in the ordered plurality and at least a second recombinant element in common with its immediately succeeding large-insert vector in the ordered plurality, wherein such first and second recombination elements are different. In another embodiment, kits of the invention include an ordered plurality of large-insert vectors, each large-insert vector being associated with one or more recombination elements and capable of incorporating an insert and each successive large-insert vector in the ordered plurality having at least one recombination element selected from a plurality of different kinds of recombination elements and wherein each successive large-insert vector in the ordered plurality is associated with a different kind of recombination element selected from the plurality. Such kits may further include reagents for carrying out recombination reactions of the assembly process, including at least one recombinase, buffers, co-factors, and the like. [0013] The present invention advantageously addresses short comings of present technology by providing modular genomes having modules in the size range of several thousand basepairs, e.g. 5-10 kb, to many tens of thousands of basepairs, e.g. 50-100 kb, which are amenable to facile replacement, deletion, and/or additions. Such modules may be synthetic polynucleotides and may be designed for 1) controlling gene content, e.g. all of the genes in a multi-step metabolic pathway or numerous interacting or branching pathways may be contained on a single module, 2) excluding of genes that encode inhibitors or otherwise undesirable competing enzymes that divert a host cell from desired metabolic/synthetic processes, 3) modifying codon usage to maximize or minimize protein production, 4) modifying regulatory elements, including promoters, enhancers, repressors, activators, terminators, or the like, to modulate gene expression, 5) incorporating codons from non-natural amino acids, thereby making possible entirely new protein functions, 6) balancing enzymatic and transport activities to optimize fluxes of substrates, intermediates, and products in metabolic pathways, and like objectives. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIGS. 1A-1G illustrates schematically several methods of assembling in a host organism donor genome segments into a replacement genome. [0015] FIG. 2 illustrates alternating, or iterative, positive selection for successively using two positive selection markers in a segment assembly process. [0016] FIG. 3 is a genetic map of a vector incorporating loxP recombination elements for incorporating donor genome segments into a growing precursor replacement genome. [0017] FIG. 4 illustrates a recombination reaction between two single mutation loxP sites that results in a mutation-free site and a double mutation site in the recombinant product. DETAILED DESCRIPTION OF THE INVENTION [0018] The practice of the present invention may employ, unless otherwise indicated, conventional techniques and descriptions of organic chemistry, molecular biology (including recombinant techniques), cell biology, biochemistry, and immunology, which are within the skill of the art. Such conventional techniques include, but are not limited to, vector construction, microbial host transformation, selection and application of genetic markers, manipulation of large polynucleotide fragments, preparation of synthetic polynucleotides, application of recombination systems, nucleic acid sequencing and analysis, and the like. Specific illustrations of suitable techniques can be had by reference to the example herein below. However, other equivalent conventional procedures can, of course, also be used. Such conventional techniques and descriptions can be found in standard laboratory manuals such as Genome Analysis: A Laboratory Manual Series (Vols. I-IV), Using Antibodies: A Laboratory Manual, Cells: A Laboratory Manual, PCR Primer. A Laboratory Manual , and Molecular Cloning: A Laboratory Manual (all from Cold Spring Harbor Laboratory Press), Stryer, L. (1995) Biochemistry (4th Ed.) Freeman, New York, Gait, “ Oligonucleotide Synthesis: A Practical Approach” 1984, IRL Press, London, Nelson and Cox (2000), Lehninger, Principles of Biochemistry 3 rd Ed., W. H. Freeman Pub., New York, N.Y. and Berg et al. (2002) Biochemistry, 5 th Ed., W. H. Freeman Pub., New York, N.Y., Casali et al, editors, E. Coli Plasmid Vectors: Methods and Applications (Humana Press, Totowa, N.J., 2003), all of which are herein incorporated in their entirety by reference for all purposes. [0019] In one aspect, the invention provides a method of constructing in a host cell a microbial genome by assembling in a predetermined order polynucleotide segments. The segments may be synthetic or may be derived from one or more donor organisms. In one aspect, such assembling is carried out by use of a recombination system that permits pairs of polynucleotides to be combined, or linked to one another, to form a single larger polynucleotide of a predetermined structure. Usually, members of such pairs are each double stranded replicatable polynucleotides, such as plasmids, phages, cosmids, BACs, or the like, or comprise portions of such replicatable polynucleotides. A recombination system comprises one or more recombinases and one or more recombination elements, or nucleic acid sequences that are specifically recognized by a recombinase and that serve as the joining sites between a pair of polynucleotides. Usually, reactions using a recombination system take place within a host cell. In some cases, a reaction using a recombination system may generate multiple products from which a desired product is selected, e.g. by selectable markers, size separation, or the like. In accordance with the invention, a sequence of recombination reactions is carried out such that in each successive reaction one member of a pair of polynucleotides to be combined is a product of the previous reaction. In certain embodiments, the resulting product is referred to as a “precursor replacement genome.” Thus, by such a sequence of reactions, polynucleotide segments making up a replacement genome are assembled segment by segment until a replacement genome is completed. A recombination system is selected so that each different segment is associated with one or more unique recombination elements thereby allowing each segment to be assembled in a predetermined order without interfering with previously assembled segments. Preferably, the same recombination system may be used after assembly to selectively replace, delete from, add to, or otherwise alter, segments of a completed replacement genome. [0020] In one aspect of the invention, a plurality of segments are sequentially assembled to form a replicating nucleic acid construct inside of a host cell, wherein the size of the construct is larger than the expected size of conventionally handled genomic DNA, for example, that handled by conventional laboratory operations, such as, pipeting, mixing, stirring, transforming, and the like. In another aspect, the size of such construct is at least 500 kilobases (kb), or at least 600 kb, or at least 700 kb, or at least 800 kb. Typically, such constructs are not replacement genomes themselves, but may be precursor replacement genomes. In still another aspect, a plurality of segments collectively comprises a complete copy of a replacement genome; that is, the plurality of segments covers the replacement genome. Such coverage may or may not be redundant in that sequences of some segments of the plurality may overlap. In other aspects, such coverage is non-redundant in that there is no overlap among the sequences of segments in the plurality. A replacement genome may be derived directly from a genome of a natural strain or species of microorganism, which is referred to herein as a “donor genome.” A donor genome may be natural or unmodified, or it may have been modified to add, delete, substitute, or otherwise alter, genes, regulatory elements, operons, or other elements. Usually, segments in a plurality that comprise a donor genome are selected so that they collectively contain a substantially complete sequence of the donor genome and so that overlap is minimized; that is, each segment does not include any sequences that overlap with sequences of any other segment of the plurality, or if such overlap occurs, then it is minimal, for example, less than ten percent of either segment, or less than five percent of either segment, or less than two percent of either segment, or less than one percent of either segment. In other words, such segments, in some sense, represent a minimal tiling path of the donor genome. “Substantially complete” in reference to a set of segments derived from a donor genome means that the set contains sequences of the donor genome necessary for growth and replication under defined culture conditions. Thus, “substantially complete” includes situations where less than the entire genome sequence is included. In one aspect, “substantially complete” means at least 85 percent of a donor genome, or at least 90 percent of a donor genome, or at least 95 percent of a donor genome, or at least 98 percent of a donor genome. When a plurality of segments making up a donor genome is assembled in accordance with the invention it is referred to herein as a replacement genome. A replacement genome derived from a donor genome may be tailored later by selectively replacing segments containing the natural sequence components with synthetic polynucleotides in order to rearrange the ordering and/or composition of genes, regulatory elements, operons, gene clusters, and the like, for the purpose of enhancing performance of, or adding new functionality to, the resulting synthetic organism. [0021] In some cases, during initial cycles of an assembly process, replication of a precursor replacement genome in a host organism may occur by operation of an origin of replication from a large-insert vector used in its construction, whereas replication in later cycles is controlled by an origin of replication derived from a donor genome. In other cases, immediately after or within the first few cycles of assembly, e.g. 1-2, or 2-4, or 3-6 assembly cycles, replication of a precursor replacement genome occurs by operation of an origin of replication derived from a donor genome. In such embodiments, early assembled segments, e.g. segments 1 to 4, or so, contain sequences comprising the donor origin of replication. In either case, a host is preferably selected so that the nucleic acids and proteins responsible for replication are substantially cross-functional with those encoded by the donor genome. That is, host organism proteins responsible for replication are operable with the donor origin of replication. In some embodiments, donor transcription factors may be added, e.g. via a host plasmid, to ensure that necessary proteins for precursor replacement genome replication are available. In some cases, other donor transcription factors may be provided to ensure availability of other necessary proteins, e.g. a particular donor replication protein for which there is no cross-functional host protein, or the like. Accordingly, in one aspect, preferably, a segment early in the assembly process (e.g. cycle 1-2, or 1-4, or 1-6) contains the replacement genome origin of replication (which may be a donor genome origin of replication) and all genes encoding necessary replication factors or proteins. [0022] Likewise, whenever a donor genome contains genes that encode products that are incompatible with host organism growth and replication, then such genes, if indispensable, may be moved to the final segment in the assembly process; otherwise, if dispensable, such genes may be deleted. Optionally, such genes may be placed under inducible control, so that they may be activated after assembly is complete and the host genome and associated support functions are no longer required. In one aspect, donor genes (or other sequences) incompatible with a host organism can be identified by whole genome shotgun sequencing using conventional techniques, e.g. Weber et al, Genome Research, 7: 401-409 (1997); Adams et al, Science, 287: 2185-2195 (2000); Waterston et al, Proc. Natl. Acad. Sci., 99: 3712-3716 (2002); Reed et al, J. Virol. Meth., 129: 91-96 (2005); and the like, which references are incorporated by reference. Briefly, in whole genome shotgun sequencing, genomic DNA of a donor organism is randomly sheared, cloned in small-, medium-, and large-insert expression vectors, transformed into the host organism, and randomly selected clones are sequenced. A sufficient amount of sequencing is carried out so that if gaps remain in the assembled donor genome, it must be attributed to the presence of a cloned sequence that is incompatible with the host organism, and not with under sampling of donor genome fragments. The incompatible donor sequences are identified by the locations of the gaps in the assembled donor genome. Alternatively, or as a confirmation, individually selected donor sequences may be tested by introducing into a host in a suitable expression vector. [0023] In one aspect, a host organism and donor organism are selected so that proteins responsible for replication are substantially cross-functional, thereby allowing replication of precursor replacement genomes by host replication proteins. One approach to accomplish this is selection of host organisms and donor organisms that are close evolutionarily, e.g. as measured by genome sequence homology, particularly of core function genes, e.g. those involved with replication, transcription, protein synthesis, substrate transport, energetic metabolism, cell division, and the like. Guidance for selecting core function genes for determining a measure of cross-functionality of encoded proteins may be found in an extensive literature on minimal microbial genomes, e.g. as represented by the following references that are incorporated by reference: Koonin, Annu. Rev. Genomics Hum. Genet., 1: 99-116 (2000); Kobayashi et al, Proc. Natl. Acad. Sci., 100: 4678-4683 (2003); Glass et al, Proc. Natl. Acad. Sci., 103: 425-430 (2006); Gil et al, Microbiol. Molecular Biol. Rev., 68: 518-537 (2004); U.S. Pat. No. 6,673,567; U.S. Pat. No. 6,207,384; and the like. In one aspect, core function genes of host and donor genomes are at least 50 percent homologous; in another aspect, core function genes of host and donor genomes are at least 60 percent homologous; or at least 70 percent homologous, or at least 80 percent homologous, or at least 90 percent homologous, or at least 95 percent homologous, or at least 98 percent homologous. In one aspect, core function genes for determining cross-functionality are genes encoding proteins necessary for genome replication. Whenever Escherichia coli ( E. coli ) is employed as a host organism, core function genes for genome replication are well known to those of ordinary skill in the art, as evidence by the treatise: Komberg and Baker, DNA Replication, Second Edition (Freeman, San Francisco, 1992), which is incorporated by reference. In one aspect, such genes include those encoding polymerases, primases, ligases, helicases, and gyrases. In another aspect, such genes are selected from the following set: dnaA, dnaB, dnaC, dnaE, dnaG, dnaJ, dnaK, dnaN, dnaQ, dnaT, dnaX, dnaY, dnaZ, dut, grpE, gyrA, gyrB, lig, nrdA, nrdB, ori, polA, polB, priA, priB, priC, rep, mhA, rpoA, rpoB, rpoC, rpoD, ssb, ter, topA, trxA, and tus, where these gene designations are defined in Kornberg and Baker (cited above), and are defined by sequence in publicly available databases, such as NCBl, Ensembl, GenBank, or the like. In particular, the sequence of E. coli strain K-12 is disclosed in Blattner et al, Science, 277: 1453-1474 (1977), which is incorporated by reference. Whenever Bacillus subtilis is employed as a host organism core function genes for genome replication may be selected from the following set: dnaA, dnaB, dnaC, dnaD, dnaE, dnaF, dnaG, dnaH, dnaI, dnax, gyrA, gyrB, nrdA, and the like. [0024] Alternatively, activities of selected host proteins in carrying out donor functions may be assessed empirically where assays are available, e.g. a donor origin of replication may be cloned into a host using a vector whose own origin of replication is under conditional control, e.g. temperature sensitive control, so that upon disablement of the vector origin, cross-functionality may be tested by assessing whether and to what extent the vector replicates (by use of host replication proteins). [0025] Replacement genomes may be assembled in accordance with the invention in a wide variety of host organisms. Preferably, the host organism is a prokaryotic organism. In one aspect, the host organism is a bacterium, and more usually, an enteric bacterium, such an E. coli . In another aspect, the host organism is a Bacillus subtilis . Preferably, the donor organism is a prokaryotic organism. In one aspect, the donor organism is a bacterium. Exemplary donor organisms for use with an E. coli host include Hemophilus , and more particularly, Hemophilus influenzae, Pseudomonas , and more particularly, Pseudomonas putida. [0026] In one aspect, segments used in assembling a replacement genome are cloned or constructed using conventional techniques in conventional cloning vectors, including plasmids, phages, cosmids, and/or bacterial artificial chromosomes (BACs) and P1-derived artificial chromosomes (PACs), P1 vectors, and the like. In order to minimize assembly steps, preferably, most, if not all, segments are provided as inserts of large-insert cloning vectors, such as BACs or PACs. After assembly of a replacement genome is completed, the type of vector used and the sizes of replacement fragments for further alterations will depend on particular applications. A large-insert vector is a vector capable containing an insert having a length in the range of from 50 kb to 300 kb, or greater, and transforming a prokaryotic host organism, such as a bacteria. In particular, a large number of BACs are available for use in RecA − E. coli host organisms. In one aspect, a set of segments for assembling a replacement genome may comprise inserts in the same type of cloning vector or in different types of cloning vectors, e.g. a majority may comprise large fragments, i.e. greater than 100 kb, in BACs and a minority may comprise smaller fragments in other cloning vectors, such as phages, comids and/or plasmids. In another aspect, BACs are employed as the primary cloning vector for segments of a replacement genome; that is, a majority of the sequence of a replacement genome is provided in BACs. Lengths of segments in a plurality may vary widely depending on several factors including the size of a donor genome, the desirability of minimizing steps in the assembly process, the desired arrangement of genes, operons, gene clusters and the like, anticipated segment substitutions (for example, it may be more efficient to use several smaller synthetic segments separately rather than a single large synthetic segment), and so on. In one aspect, segments have lengths in the range of from a few thousands of basepairs, e.g. 2-10 kb, to several hundreds of thousands of basepairs, e.g. 100-300 kb. In another aspect, segments have lengths in the range of from tens of thousands of basepairs, e.g. 10-50 kb, to hundreds of thousand basepairs, e.g. 100-300 kb. Preferably, segments are cloned in BAC vectors, which are described in the following references that are incorporated by reference: Zhao et al, editors, Bacterial Artificial Chromosomes (Humana Press, Totowa, N.J., 2004); Kim et al, Genomics, 34: 213-218 (1996); Shizuya et al, Proc. Natl. Acad. Sci., 89: 8794-8797 (1992); U.S. Pat. Nos. 5,874,259 and 6,472,177; and the like. Techniques for assembling inserts into BACs from several smaller pieces are well known in the art, as evidenced by the following reference: O'Connor et al, Science, 1307-1312 (1989), which is incorporated by reference. Exemplary vectors that may be used with the invention, with no or minor modifications, include pBeloBAC11, pBACe3.6, pCC1BAC, pSMART VC, pIndigoBAC-5, SuperCos 1, and the like, which are commercially available or described in GenBank. [0027] Assembly of a replacement genome may be carried out using a variety of techniques, including the use of restriction endonucleases and ligases for inserting fragments, the use of hosts having robust DNA repair mechanisms, and the use of recombination based methods for site-specific insertion. Site-specific recombination systems for use with the invention include at least one recombinase that usually operates on a pair of reactive recombination elements (or sites) to catalyze strand scission and rejoining. Reactive recombination elements are usually, but not necessarily, recombination sites having identical sequences. Recombination systems may also include additional ancillary proteins that may be operationally associated with a recombinase. In one aspect, in order to sequentially assemble different segments into a growing precursor replacement genome, a recombinase is selected that is capable of catalyzing separate recombination events with recombination elements having different sequences without the occurrence of significant cross reaction among different recombination elements. Thus, in one approach, a sufficient number of different non-cross reacting recombination elements must be available for complete assembly of a replacement genome. In another approach, non-cross reacting recombination elements may be re-used in alternating steps of assembly; thus, only two non-cross reacting recombination elements are required. Many recombination systems are useful in the present invention and may be used alone or in combination with one another. Suitable recombination systems include, but are not limited to: 1) linear homologous recombination using two crossover sites near the ends of the sequence of interest, exemplified by a Red/ET system; 2) circle homologous integration followed by a second resolving recombination, exemplified by Cre-10× or flp-frt sites in a recombination mediated cassette exchange (RMCE) approach; 3) linear, sequence-specific recombination (e.g., via a phage integrase such as λ or phiC31); and 4) sequence-specific circle integration. Exemplary site-specific and homologous recombination systems include, but are not limited to, Cre-loxP, Flp-FRT, att-Int (Gateway), Red/ET, RecA, and the like. These and other recombination systems are well-known to those of ordinary skill in the art and are described in the following references, which are incorporated by reference: Branda et al, Developmental Cell, 6: 7-28 (2004); Baer et al, Curr. Opin. Biotech., 12: 473-480 (2001); Sauer, Nucleic Acids Research, 24: 4608-4613 (1996); Yu et al, Proc. Natl. Acad. Sci., 97: 5978-5983 (2000); Lee et al, Genomics, 73: 56-65 (2001); Muyrers et al, EMBO Rep., 1: 239-243 (2000); Cheo et al, Genome Research, 14: 2111-2120 (2004); Missirlis et al, BMC Genomics, 7: 73 (2006); U.S. Pat. Nos. 6,509,156; 6,465,254; 6,720,140; 5,776,449; 5,888,732; and the like. Recombinases may be provided by expression of genes that may be carried by the host genome, or by an episome, such as a plasmid, or by one or more segments of a precursor replacement genome. Preferably, expressions of recombinases are under inducible control in order to minimize the occurrence of spurious or undesired recombination during the assembly process. Also, preferably, a host organism is selected that is free of recombination elements used in the replacement genome (or DNA circle) assembly process, or a selected organism is treated to remove or disable such elements to prevent spurious or unintended recombination reactions. [0028] In one aspect, the assembly process of the invention includes successive steps of recombining in a host organism a new segment of a replacement genome with segments that have previously been assembled, and which constitute a precursor replacement genome. Such steps are carried out using conventional vectors and transformation techniques in conjunction with a recombination system, such as one of those indicated above. Typically, each such step includes substeps of transforming the host with a vector containing a new segment operationally associated with one or more unique recombination elements, culturing transformed host organisms, and selecting host organisms containing recombinants, i.e., precursor replacement genomes that have successfully recombined with a new segment to generate a successive precursor replacement genome (or a completed replacement genome), as the case may be. In some embodiments, multiple segments may be recombined with a precursor replacement genome in a single cycle, e.g. using the approach of Church et al, International patent publication WO 2006/055836, which is incorporated herein by reference. [0029] In one aspect of the invention, segment assembly is carried out with site-specific recombination, as illustrated in FIGS. 1A-1G . Site-specific recombination elements are selected and arranged in vectors to drive recombination reaction to the desired products. Sets of site-specific recombination elements are provided that (i) have substantially no cross reactivity with one another, and (ii) are oriented so that stable integration occurs in each step of the assembly process. As reviewed by Branda et al (cited above), for example, the λ integrase family of site-specific recombination elements, which include loxP and FRT, share a common mechanism of DNA recombination that involves strand cleavage, strand exchange, and ligation. Although distinct at the nucleotide level, loxP and FRT sites share an overall structure which includes two 13 basepair palindromic sequences, or inverted repeats, separated by an 8 basepair asymmetric core, or spacer, sequence. In the presence of two sites, recombinase monomers bound to the inverted repeats promote the formation of a synaptic complex and recombination between the two sites. Strand cleavage, exchange, and ligation occur within the spacers. Because of spacer asymmetry, strand exchange is possible only when target sites are connected by synapses in one orientation. Consequently, the relative orientation of target sites with respect to one another determines the outcome of recombination: Cre and Flp recombinases will excise a circular molecule from between two directly repeated target sites, integrate a circular molecule into a linear molecule each possessing a target site, invert the DNA between two inverted sites, and exchange sequences distal to target sites present on two linear molecules. Because insertion ordinarily leaves two identical sites in cis configuration, which are themselves substrates for recombination, stable insertions are difficult or impossible using two wild type sites. However, many recombinases, such as Cre and Flp, tolerate certain variations in their target sequences and effectively catalyze recombination only between certain subsets of the alternative sites. This property is exploited to permit successive recombination events for replacement genome assembly. Variant target sites for λ intergrase recombinases, such as Cre and Flp, fall into two classes: spacer variant and invert-repeat variants. The first class contains nucleotide substitutions within the spacer sequence and exploits the finding that it is spacer length, not sequence that is the critical factor for efficient recombination, so long as the sequence between participating sites is identical. Recombination is therefore efficiently mediated between pairs of homotypic (e.g. FRT/FRT or F 3 /F 3 ) but not heterotypic (e.g. FRT/F 3 ) sites. The second class of alternative sites (inverted repeat variants) may also be exploited to provide stable insertions. A target site containing a nucleotide substitution in the “left side” inverted repeat (an “LE” mutant site) can recombine with a site containing an analogous substitution in the “right end” inverted repeat (an “RE” mutant site), although at a slower reaction rate than wild type sequences. Such mutants are designed so that the recombination product harbors one wild type site and one LE/RE double mutant site, the latter being effectively inert. Thus, insertion with such single mutant LE and RE sites results in the formation of only one potentially active recombination element, which itself may be inactivated or modified and used for subsequent insertions. These concepts are illustrated in FIGS. 1A-1G for several embodiments of the invention. [0030] FIG. 1A illustrates a plurality of segments (100) carried in vectors, lox1 through loxK, that each have a unique combination of site-specific recombination elements labeled “A 01 ,” “A 10 ,” “B 01 ,” “B 10 ,” “C 01 ,” . . . “K 10 ,” where each different letter, “A,” “B,” etc., indicates a different non-cross-reacting site-specific recombination element, and where subscripts “01” and “10” indicate a recombination element has an RE mutant site (“01”) or an LE mutant site (“10”). Correspondingly, a letter with subscripts “11” indicates a double mutant site and a letter with subscripts “00” indicates a mutant-free site. It is noted that the diagrams of vectors are only symbolic representations and are not to scale or proportion. For example, even though the site-specific recombination elements are shown at opposite sides of the vectors, this is not a required configuration. The recombination elements may be juxtaposed or they may be interspersed in the vector or segment. Vector lox1 ( 101 ) containing initial segment ( 102 ) requires only a single recombination element “A 01 ” ( 104 ) in this embodiment. Likewise, vector loxK ( 106 ) containing the final segment ( 108 ) requires only a single recombination element “K 10 ” ( 110 ). Vectors lox2 through loxK-1 each have two different recombination elements, as exemplified by vector lox4 ( 112 ), which comprises segment ( 114 ), recombination element “C 10 ” ( 116 ), recombination element “D 01 ” ( 118 ), and portion ( 120 ), which may be part of segment ( 114 ) or simply a connection between the two recombination elements (e.g. a bond connecting two adjacent sequences or an intervening polynucleotide). In this embodiment, each of the segments-containing vectors of plurality ( 100 ), except for the first (lox1) and the last (loxK), contains at least a first recombination element (e.g. “A 10 ” of lox2) in common with its immediately preceding vector (i.e. “A 01 ” of lox1) in the predetermined order shown and at least a second recombinant element (e.g. “B 10 ” of lox2) in common with its immediately succeeding vector (i.e. “B 10 ” of lox3), wherein such first and second recombination elements are different (i.e. in this embodiment, the first is type “A” and the second is type “B”). Again, an important property of the different types (or kinds) of recombination elements is that members or variants of one type (or kind) do not cross react (or substantially do not cross react) with members or variants of another type (or kind). As illustrated in FIG. 1B , segments of plurality ( 100 ) are assembled stepwise by adding them on segment at a time to form a succession of precursor replacement genomes. In one aspect, each step in the assembly process comprises a cycle of steps (or substeps) including transforming a host and selecting a resulting transformant using a selectable marker. The relative ordering of recombination elements is shown in first recombinant ( 122 ), which is the first precursor replacement genome. Since site-specific recombination is conservative, in that DNA synthesis is not required and sequences are neither lost nor gained in the reaction, first recombinant ( 122 ) contains pieces of all the recombination elements of the two vectors that were combined, i.e. two copies of an “A” type recombination element in double mutant form ( 104 ) and in mutant-free form ( 105 ), and one copy of recombination element “B 01 ” (124), which serves as the unique recombination site for the next vector, lox3. After transformation, recombination and selection, the resulting host harboring first recombinant ( 122 ) is transformed with vector lox3 to form the next recombinant, or precursor replacement genome ( 126 ). Again, sequences are conserved in the recombinant of ( 122 ) and lox3 so that precursor replacement genome ( 126 ) contains five recombination elements: “A 00 ” (active), “A 11 ” (inert), “B 00 ” (active), “B 11 ” (inert), and “C 01 ” (128), which again is the unique recombination site for the next vector, lox4. The process continues until a replacement genome is complete. The ordering of the active recombination elements (“A 00 ,” “B 00 ,” “C 00 ,” etc.) relative to the inert recombination elements (“A 11 ,” “B 11 ,” “C 11 ,” etc.) may be varied by changing the ordering of the LE and RE mutant sites in vectors ( 100 ). For example, if lox2 contained “B 10 ” and lox3 contained “B 01 ,” then the positions of “B 11 ” and “B 00 ” would be swapped and the resulting vector corresponding to ( 126 ) would have inert site “A 11 ” sandwiched between “A 00 ” and “B 00 .”. As indicated, in this embodiment, recombination takes place in a host cell, such as illustrated diagrammatically in FIG. 1C . Host organism ( 130 ) is transformed by initial vector ( 101 ) to form a host containing a host genome ( 132 ) and vector ( 101 ). In subsequent cycles of the assembly process, successively larger recombinants ( 134 ), i.e. precursor replacement genomes, are formed until a completed replacement genome ( 136 ) is present. Host genome ( 132 ) is then removed or ablated to give synthetic cell ( 138 ) containing only replacement genome ( 136 ). [0031] As discussed more fully below, the above process may be carried out with pairs of LE and RE mutant recombination elements for each type, “A” through “K,” as taught by Missirlis et al, BMC Genomics, 7: 73 (4 Apr. 2006), which is incorporated by reference. Briefly, LE and RE mutant pairs are prepared for each type of recombination element. When a recombination event occurs (e.g., part of element “B10” on lox3 is combined with element “B01” on lox3), both mutants are present in only one of the product sites, and the other product site is free of mutations. This results directly in a modular replacement genome. That is, the operable recombination sites may be used with the recombination system employed to exchange segments for modifying the properties of the synthetic organism, e.g. using a RMCE procedure. [0032] In another aspect, segments may be assembled into a replacement genome by using fewer recombinations elements, as illustrated in FIGS. 1D and 1E . A plurality of segments is provided in vectors V 1 through V K (150). In this embodiment, the vectors do not each have one or more unique recombination elements; instead, the recombination elements are re-used in alternating cycles of segment incorporation. Such re-cycling of recombinIation elements may be accomplished with a plurality of different types of recombination elements, each of which is provided as a pair of single mutants that may recombine with each other to produce an active mutant-free form and an inert double mutant form. Such a plurality of different recombination elements may contain two, three, four, five, six, seven, eight recombination elements. In one aspect, recombination elements may be conveniently introduced into BACs carrying the segments by Red/ET recombination, e.g. as disclosed in U.S. Pat. No. 6,509,156; and Yu et al, Proc. Natl. Acad. Sci., 97: 5978-5983 (2000); and/or using reagents commercially available from GeneBridges GmbH (Dresden, Germany). In particular, using appropriate host bacteria, sequences to be inserted into a BAC may be prepared by PCR, where the resulting amplicon contains unique flanking sequences of 30-50 basepairs. Such amplicons are recombined with regions of the BAC bounded by the same unique sequences. [0033] In FIG. 1D , vector V 1 containing the first segment and vector V K containing the last segment, V K , each have a single recombination element, and the rest of the vectors, V 2 through V K , 1 , each have two. Recombination element A 01 ( 152 ) on V 1 is a single mutant site that is operable with recombination element A 10 (154) on V 2 , which is a different single mutant site. Likewise, recombination element B 01 ( 156 ) on V 2 is a single mutant site that is operable with recombination element B 10 ( 158 ) on V 3 , which is a different single mutant site. The same four sites may be used with all of the vectors V 1 through V K , when used as follows. V 1 and V 2 are transformed into a Red/ET competent host that also expresses an appropriate recombinase to form recombinant (160), in which recombination elements A 01 (V 1 ) and A 10 (V 2 ) are changed to functional A 00 site ( 162 ) and non-functional A 11 site ( 164 ). An amplicon is prepared containing 30-50 basepair flanking sequences that are identical to sequences flanking A 00 ( 162 ) on recombinant ( 160 ). The host bacteria containing recombinant ( 160 ) is transformed with the amplicon so that it can recombine ( 166 ) with the portion of recombinant ( 160 ) containing A 00 ( 162 ) to produce recombinant ( 169 ), which is shown to have a disabled recombination site “X” ( 168 ). An advantage of the Red/ET system is that recombinants can be detected by PCR; growth on a selective medium is not required. Modified recombinant ( 169 ) may then be used in the next assembly step by transforming its host with vector V 3 containing a third segment and recombination elements B 10 and A 01 to form ( 171 ) recombinant ( 179 ), which contains a functional B 00 site and a non-functional B 11 site. As above, after selection of a recombinant ( 179 ), the functional B 00 site is disrupted ( 176 ) to form modified recombinant (or precursor replacement genome) ( 180 ). Assembly of a replacement genome continues in a similar manner for the remaining segments. [0034] A recombination system, such as Red/ET may also be used as illustrated in FIGS. 1F-1G to modify an undesired functional recombination element within a segment-addition cycle. A plurality of vectors ( 180 ) is provided that each contains only one single mutant form of one type of recombination element. As above, only two types recombination elements are shown in the embodiment of FIG. 1F (A's and B's); however, further types of recombination elements may be employed in alternative embodiments. Vectors V 1 and V 2 are recombined to form recombinant ( 182 ) that contains active recombination element Aoo ( 184 ) and inert recombination element A 11 ( 186 ). In this embodiment, instead of inactivating element A 00 , a homologous recombination system, such as Red/ET, is employed to exchange the active recombination element A 00 with a recombination element complementary to the element of the next vector to be inserted. (As above, this allows the type A recombination elements to be re-used in subsequent steps). After such exchange ( 188 ), precursor replacement genome ( 190 ) is formed that has one inactive recombination element A, ( 192 ) and one active recombination element B 01 ( 194 ). Precursor replacement genome ( 190 ) is then combined with vector V 3 so that element B 01 recombines ( 195 ) with element B 10 of vector V 3 to form precursor replacement genome (196) containing active B 00 ( 198 ) and inert B 11 ( 199 ). In the next step, B 00 is exchanged ( 1901 ) with A 01 to produce precursor replacement genome ( 1902 ). Similar cycles ( 1904 ) of transforming to add a segment and transforming to exchange a recombination element are carried out until a replacement genome is assembled. [0035] As mentioned above, assembly of nucleic acid constructs, DNA circles, or replacement genomes may also be carried out in part or wholly in parallel by partial or complete self-assembly after co-transformation. In one aspect of this embodiment, multiple segments are co-transformed into a host organism wherein each segment is associated with a site-specific recombination element that does not cross-react with its co-transforming segments, so that recombination results in correctly ordered segments in the nucleic acid construct produced, whether it is a precursor replacement genome or a completed replacement genome. Segments may contain multiple independent selective markers so that successful co-transformants can be identified. Suitable non-cross reacting recombination elements may be selected from the group of mutant loxP recombination elements disclosed below. In another aspect of this embodiment, a plurality of segments having unique overlapping ends of identical or homologous sequences (i.e. each overlapping region comprises unique sequences, or at least distinct from other overlapping regions) may be assembled in parallel by co-transforming into a suitable host having a robust DNA repair system, such as Deinococcus radiodurans , which has been studied for potential applications in bioremediation of radioactively contaminated environments, e.g. Zahradka et al, Nature, 443: 569-573 (2006); Makarova et al, Microbiol. Mol. Biol. Rev., 65: 44-79 (2001); Brim et al, Nature Biotechnology, 18: 85-90 (2000); Langer et al, Nature Biotechnology, 16: 929-933 (1998); Narumi et al, U.S. Pat. No. 6,770,476; which references are incorporated herein by reference. Suitable overlapping sequences may have lengths of from a few hundred basepairs, e.g. 100-1000, to several thousand basepairs, e.g. 1000-20,000. In still another embodiments, a plurality of segments having unique overlapping ends of identical or homologous sequences as above may be assembled in parallel by co-transforming into a suitable host having a homologous recombination system that recombines the overlapping ends, such as a Red/ET system, or the like. [0036] Generally, and in the particular examples above, transforming host microorganisms with vectors carrying segments is carried out with conventional techniques. As used herein, the terms “transformation” and “transfection” are intended to refer to a variety of art-recognized techniques for introducing an exogenous nucleic acid sequence (e.g., DNA) into a host cell, including calcium phosphate or calcium chloride co-precipitation, DEAB-dextran-mediated transfection, lipofection, electroporation, optoporation, mechanical injection, biolistic injection, and the like. Suitable methods for transforming or transfecting host cells are found in Sambrook, et al. (Molecular Cloning: A Laboratory Manual. 2nd, ed., Cold Spring Harbor Laboratory, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., 1989), and like laboratory manuals. [0037] Transformed microorganisms, that is, those containing recombinant molecules, may be selected with a variety of positive and/or negative selection methods or markers. In certain aspects, the positive selection marker is a gene that allows growth in the absence of an essential nutrient, such as an amino acid. For example, in the absence of thymine and thymidine, cells expressing the thyA gene survive, while cells not expressing this gene do not. A variety of suitable positive/negative selection pairs are available in the art. For example, various amino acid analogs known in the art could be used as a negative selection, while growth on minimal media (relative to the amino acid analog) could be used as a positive selection. Visually detectable markers are also suitable for use in the present invention, and may be positively and negatively selected and/or screened using technologies such as fluorescence activated cell sorting (FACS) or microfluidics. Examples of detectable markers include various enzymes, prosthetic groups, fluorescent markers, luminescent markers, bioluminescent markers, and the like. Examples of suitable fluorescent proteins include, but are not limited to, yellow fluorescent protein (YFP), green fluorescence protein (GFP), cyan fluorescence protein (CFP), umbelliferone, fluorescein, fluorescein isothiocyanate, rhodamine, dichlorotriazinylamine fluorescein, dansyl chloride, phycoerythrin and the like. Examples of suitable bioluminescent markers include, but are not limited to, luciferase (e.g., bacterial, firefly, click beetle and the like), luciferin, aequorin and the like. Examples of suitable enzyme systems having visually detectable signals include, but are not limited to, galactosidases, glucorinidases, phosphatases, peroxidases, cholinesterases and the like. In other aspects, the positive selection marker is a gene that confers resistance to a compound which would be lethal to the cell in the absence of the gene. For example, a cell expressing an antibiotic resistance gene would survive in the presence of an antibiotic, while a cell lacking the gene would not. For instance, the presence of a tetracycline resistance gene could be positively selected for in the presence of tetracycline, and negatively selected against in the presence of fusaric acid. Suitable antibiotic resistance genes include, but are not limited to, genes such as ampicillin-resistance gene, neomycin-resistance gene, blasticidin-resistance gene, hygromycin-resistance gene, puromycin-resistance gene, chloramphenicol-resistance gene and the like. In certain aspects, the negative selection marker is a gene that is lethal to the target cell in the presence of a particular substrate. For example, the thyA gene is lethal in the presence of trimethoprim. Accordingly, cells that grow in the presence trimethoprim do not express the thyA gene. Negative selection markers include, but are not limited to, genes such as thyA, sacB, gnd, gapC, zwJ, talA, taiB, ppc, gdhA, pgi, Jbp, pykA, cit, acs, edd, icdA, groEL, secA and the like. [0038] Selection methods and/or markers may be used efficiently in a multi-step assembly process, such as called for by the invention, by employing a pair of selection methods or markers that are switched, or used reciprocally, between successive recombination steps, e.g. as taught by O'Connor et al, Science, 244: 1307-1312 (1989); Kodumal et al, Proc. Natl. Acad. Sci., 101: 15573-15578 (2004); or the like. For example, as illustrated diagrammatically in FIG. 2 a first segment-containing vector ( 200 ) is transformed ( 211 ) into a host containing a recombination element ( 201 ) embedded in a gene for a positive selective marker (“Marker 1”) ( 202 ), e.g. SacBll. The SacBll gene codes for an enzyme that converts sucrose to levansucrase, which is toxic to bacterial cells (see Pierce et al., Proc. Natl. Acad. Sci 89; 2056-2060. 1992). Element ( 201 ) divides marker ( 202 ) into two parts ( 203 ) and ( 204 ). A successive segment-containing vector (206) is transformed ( 211 ) into the host containing a recombination element ( 201 ) complimentary to that in the prior recombinant, and a second non-complementary recombination element ( 205 ) embedded in a second selectable marker gene (“Marker 2”) ( 208 ) (for example, the tetracycline resistance gene, which confers sensitivity to fusaric acid, e.g. Bochner et al., J. Bacteriology 143; 926-933. 1980). As above, recombination element ( 205 ) divides Marker 2 gene ( 208 ) into two parts ( 209 ) and ( 210 ). Recombination between clone 1 ( 200 ) and vector ( 206 ) containing segment ( 212 ) forms clone 2 ( 219 ) that has a disrupted marker 1 gene (see the separation of parts ( 203 ) and ( 204 )), but a fully functional tetracycline resistance gene ( 208 ) containing recombination element ( 205 ); thus, when plated on solid media containing sucrose, only recombinant clones will grow. Clone 2 ( 219 ) may then be recombined ( 222 ) with vector ( 227 ) containing (i) complementary recombination element ( 205 ), (ii) marker 1 gene ( 214 ) containing embedded recombination element ( 215 ) (which divides marker 1 into parts ( 216 ) and ( 217 )), and segment ( 218 ). As above, recombination element ( 205 ) of vector ( 227 ) reacts with element ( 205 ) of clone 2 ( 219 ) to form clone 3 ( 231 ), in which marker 2 ( 208 ) of clone 2 is disrupted by the separation of parts ( 209 ) and ( 210 ), but which also contain a functional marker ( 214 ) that permits selection of recombinants by exposure to tetracycline. Functional marker ( 214 ) also contains embedded recombination element ( 215 ). Segments ( 212 ) and ( 218 ) are contained clone 3. Assembly continues by providing vector ( 233 ) that contains the next segment ( 224 ) and a marker 2 gene ( 225 ) containing another embedded recombination element ( 229 ) as well as a complementary recombination element ( 215 ) for insertion into clone 3. Vector ( 233 ) and clone 3 ( 231 ) form recombinant clone 4 ( 240 ) and three segments, the final one of which ( 224 ) disrupts marker 1 gene ( 214 ) (by splitting its coding region, see ( 216 ) and ( 217 )) and provides new operational marker 2 gene ( 225 ). Alternating disruptable positive selection markers in this manner allows stepwise accrual of donor genome segments in the host organism. A disruptable positive selection marker may also comprise a recombination element that is positioned between a marker gene and its promoter site. [0039] After a replacement genome is assembled and becomes operable in a host organism, the host genome is removed or ablated. In one aspect, it is removed by creating conditions that select against host organisms that retain the host genome. In another aspect, ablating the host genome includes creating conditions that both select for the replacement genome, e.g. via antibiotic resistance markers, and select against the host genome, e.g. inserting an inducible SacB, or like gene, in the host genome. In still another aspect, in certain selections of host and donor genomes, restriction endonucleases are available that cleave host genome DNA but not donor genome DNA. In such circumstances, providing an inducible gene that expresses such a restriction endonuclease may be provided to remove a host genome. For example, the restriction enzyme Fsel cleaves at four sites in E. coli , but none in H. influenzae. Mutant LoxP Sites for Serial Site-Specific Recombination [0040] In one aspect, pairs of loxP sites may be used for assembling replacement genomes or large DNA circles in accordance with the invention. As illustrated in FIG. 4 , loxP sites comprise a left end ( 400 ), i.e. “LE” Cre recognition site, or “arm,” a right end ( 404 ), i.e. “RE,” Cre recognition site, or “arm,” and sandwich between the LE and RE arms, a spacer region ( 402 ). In most wild type and mutant loxP sites, the LE and RE arms ( 400 and 404 ) are each 13 basepair in length, and the spacer region ( 402 ) is 8 basepairs in length. Also, in the wild type and in most mutant loxP sites, the LE and RE arms are inverted repeats. The components of the loxP site may be modified to produce sets of mutant loxP pairs, as illustrated in FIG. 4 , which have the following properties: (i) members of a pair react with each other (i.e. to form recombinants), but essentially do not react with other member pairs of the set, and (ii) the product of a reaction between members of a pair are one inoperable loxP site (i.e., Cre is substantially unable to catalyze a recombination involving the site) one active loxP site (i.e., Cre is able to catalyze a recombination involving the site). In one aspect, the latter active loxP site is the wild type loxP site. Such pairs of loxP sites operate as illustrated in FIG. 4 . There single mutant loxP site ( 408 ) recombines with single mutant loxP site ( 410 ) to produce recombinant ( 420 ) that has double mutant loxP site ( 422 ) and mutant-free loxP site ( 424 ). Single mutant loxP site ( 408 ) comprises mutant LE ( 400 ), wild type RE ( 402 ), and spacer region ( 402 ). Single mutant loxP site ( 410 ) comprises wild type LE ( 414 ), mutant RE ( 416 ), and spacer region ( 418 ). Spacer regions ( 402 ) and ( 418 ) usually (but not necessarily) have the same sequence within a pair of interacting (or compatible) sites. In one aspect, non-interacting loxP sites have spacer regions with different sequences. A Cre catalyzed recombination of mutant loxP sites ( 408 ) and ( 410 ) produces ( 425 ) a product ( 420 ) containing two separate loxP sites in which both mutant arms are brought together and both wild type arms are brought together. Mutant loxP sites are selected so that whenever a double mutant loxP is produced it is substantially inoperable with respect to further Cre catalyzed recombinations. This prevents undesired recombinations involving the sites when Cre is used in later steps of serial site-specific recombination. In another aspect, the second loxP site of recombinant ( 420 ) (which is usually the wild type loxP site) is fully active with other compatible loxP sites (e.g. that have the same spacer region). Thus, such sites may be used to add further segments to a replacement genome or pairs of such sites may be used to exchange fragments of a replacement genome, e.g. in a recombinase mediated cassette exchange (RMCE) type of reaction, Seibler and Bode, Biochemistry, 36: 1740-1747 (1997); and Bode et al, U.S. Pat. No. 6,992,235; which references are incorporated by reference. [0041] Many mutant loxP sites are available for use with the invention. For example, six mutant spacer sites that may be used with the invention have been described in the literature. e. g. Nucleic Acids Res. 14, 2287-2300 (1986)); Gene 216, 55-65 (1998); Nucleic Acids Res. 30, 3067-3077 (2002), and U.S. Pat. No. 6,465,254, which are incorporated by reference. Additional loxP mutants may be obtained by various screening methods, e.g. as disclosed in Missirlis et al. (cited above); Langer et al, Nucleic Acids Research, 30: 3067-3077 (2002), and the like, which are incorporated by reference. Table 1 lists published loxP sites. The following formula provides a general description of pairs of loxP sites that may be used in the invention, e.g. as illustrated in FIGS. 1A-1E , wherein a first member of a pair is defined as: LE 1 -S 1 -RE, and a second member of the pair is defined as: LE 2 -S 2 -RE 2 where: [0042] LE 1 is a mutant or wild type left end loxP site Cre recognition sequence and RE, is a mutant or wild type right end loxP site Cre recognition sequence such that whenever LE 1 is a wild type sequence, RE, is a mutant sequence, and whenever LE 1 is a mutant sequence, RE 1 is a wild type sequence; [0043] LE 2 is a mutant or wild type left end loxP site Cre recognition sequence and RE 2 is a mutant or wild type right end loxP site Cre recognition sequence such that whenever LE 2 is a wild type sequence, RE 2 is a mutant sequence, and whenever LE 2 is a mutant sequence, RE 2 is a wild type sequence; with the proviso that whenever LE1 is a mutant sequence, then LE2 is a wild type sequence; and [0044] S 1 and S 2 are compatible non-promiscuous loxP spacer regions. As used herein, “non-promiscuous” in reference to a loxP spacer sequence means that loxP sites containing such sequence (or pair of non-self recombining sequences) are substantially unreactive, or non-cross-reactive, with loxP sites containing other spacer sequences. In one aspect, non-promiscuous means that such sequence or pairs of sequences cross-react with less than 100 other loxP sites having a spacer selected from the set defined by formula NNNTANNN; in another aspect, such cross-reactivity is with less than 50 of such sites; in another aspect, such cross-reactivity is with less than of 20 such sites; and in another aspect, such cross-reactivity is with less than of 10 such sites. [0045] In one aspect, LE 1 is the lox71 left end loxP site Cre recognition sequence whenever it is a mutant sequence and RE 1 is the lox66 right end loxP site Cre recognition sequence whenever it is a mutant sequence. Likewise, LE 2 is the lox71 left end loxP site Cre recognition sequence whenever it is a mutant sequence and RE 2 is the lox66 right end loxP site Cre recognition sequence whenever it is a mutant sequence. [0046] In another aspect, S 1 and S 2 are both the same sequence selected from the group consisting of: GTATAGTA GCGTATGT GGTTACGG GGCTATAG TTGTATGG TTTTAGGT TCGTAGGC GGATAGTA GAGTACGC GTGTATTT AGGTATGC [0047] In still another aspect, S 1 and S 2 are both the same sequence selected from the group consisting of: GTATAGTA GCGTATGT GGTTACGG GGCTATAG TTGTATGG TTTTAGGT TCGTAGGC GGATAGTA GAGTACGC GTGTATTT AGGTATGC [0048] In another aspect, S 1 is GTGTACGC whenever S 2 is GTGTACGG; and S 2 is GTGTACGC whenever S 1 is GTGTACGG. TABLE I (deviations from wild type shown in lower case) SEQ ID Site Name LE spacer RE NO wild type ATAACTTCGTATA ATGTATGC TATACGAAGTTAT 1 lox511 ATAACTTCGTATA ATGTATaC TATACGAAGTTAT 2 lox5171 ATAACTTCGTATA ATGTgTaC TATACGAAGTTAT 3 lox2272 ATAACTTCGTATA AaGTATcC TATACGAAGTTAT 4 m2 ATAACTTCGTATA AgaaAcca TATACGAAGTTAT 5 m3 ATAACTTCGTATA taaTAcca TATACGAAGTTAT 6 m7 ATAACTTCGTATA AgaTAgaa TATACGAAGTTAT 7 m11 ATAACTTCGTATA cgaTAcca TATACGAAGTTAT 8 lox71 taccgTTCGTATA ATGTATGC TATACGAAGTTAT 9 lox66 ATAACTTCGTATA ATGTATGC TATACGAAcggta 10 [0049] FIG. 3 is a genetic map of a representative pLOX vector that may be used for maintaining a plurality of segments for assembly into a replacement genome. Each vector has mutant loxP site for integration with a precursor replacement genome, and a recipient lox P site for receiving the next incoming clone in a subsequent assembly step. The replicon region of the vector is removed by FseI digestion prior to transformation. Kits of the Invention [0050] In one aspect, kits of the invention comprise a plurality of vectors for accepting segments as inserts, each vector comprising at least one recombination element. Vectors for use with methods of the invention may each further include one or more selectable markers for determining the presence of a recombinant molecule. Kits of the invention may further include one or more recombinases to catalyze recombination reactions involving recombination elements in the vectors of the kits, as well as ancillary proteins, co-factors, and necessary buffers and salts for conducting recombination reactions. In one embodiment, kits of the invention include at least one Cre recombinase. Kits of the invention may further include reagents for selecting host organisms carrying desired recombinant molecules, including reagents for positive and/or negative selection. Kits of the invention also include any delivery system for delivering materials or reagents for carrying out a method of the invention. In the context of recombination reactions for assembling a nucleic acid construct, such delivery systems include systems that allow for the storage, transport, or delivery of reaction reagents (e.g., vectors, enzymes, etc. in the appropriate containers) and/or supporting materials (e.g., buffers, written instructions for performing the reactions etc.) from one location to another. For example, kits include one or more enclosures (e.g., boxes) containing the relevant reaction reagents and/or supporting materials. Such contents may be delivered to the intended recipient together or separately. For example, a first container may contain an enzyme for use in a reaction, while a second container contains vectors. EXAMPLE I Use of H. influenzae as Genome Donor to an E. coli Host [0051] In this example, H. influenzae was selected as a donor organism because of its free living status and its relatively compact genome (1.83 Mbp). The strain of H. influenzae employed is Rd KW20, which is kanamycin resistant and RecA negative (to eliminate the possibility of confounding homologous recombination). E. coli was selected as the host organism, specifically the HMS174 strain (Novagen), as it has K12 background, supports IPTG inducible recombinant protein expression, and is RecA negative. H. influenzae and E. coli are closely related, commensal gammaproteobacteria and the complete genome sequence is available for both organisms [( Science 269, 496-512 (1995); Science 277, 1453-1452 (1997)]. [0052] A BAC library was constructed from an MboI partial digest of H. influenzae gDNA. BAC clones from this library were end sequenced at high redundancy (>200× clone coverage) and mapped to the reference H. influenzea genome sequence. A minimal tiling path of 19 BAC clones that represents 95% of the H. influenzae genome and 98.6% of H. influenzae genes in intact predicted operons were selected. The tiling set was selected to maximize genome coverage, to minimize clone overlap, and to disrupt the fewest number of genes and predicted operons. This set of donor clones (i.e. segments) are used for re-assembly in the host organism. A 10 kb plasmid library was also constructed and end sequenced leading to the selection of 15 plasmids that can close most gaps in the BAC tiling path, if necessary. [0053] Assays were carried out to assess the following: (i) H. influenzea genes that cannot be cloned in E. coli . There are at least 24 annotated genes present in the physical gaps that remain between clones in the minimal tiling set. (Generally, different minimal tiling sets may have different numbers of such genes). While there is no obvious pattern in this gene set of the presently selected minimal tiling set, there are several genes involved in galactose metabolism and also several uncharacterized genes, which may be dispensable. There are, however, five genes that encode what seem to be essential proteins, including three ribosomal proteins, a GTP-binding protein, and a DNA polymerase III subunit. These genes appear in the predicted set of 206 essential genes from a recent meta-analysis of all experimental and bioinformatic approaches undertaken to date that have attempted to define the core set of essential genes in a free living organism (Gil et al, cited above). While the non-essential toxic genes can likely be ignored, those that are toxic but essential are included in the replacement genome. Such genes may be of utility in resolving the donor and host genomes in the final hybrid organism. (ii) Which cloned H. influenzae genes are expressed in E. coli . A primary cDNA library was constructed from one of the BAC clones (M01) in the minimal tiling set which contained 135 predicted genes. A total of 9,216 ESTs were sequenced and a total of 123 unambiguous hits to Haemophilus genes were present in BAC M01. These ESTs collapsed into 17 clusters (i.e. 17 genes were represented). Thus, despite the limitations of this sampling procedure where most hits were against the host cell ( E. coli ) transcripts, it is clear that genes encoded in Haemophilus BACs are transcribed by the host cell machinery. A functional expression test was performed next. Surprisingly, the Haemophilus restriction systems appeared to be clonable in E. coli . This may occur due to the fact that restriction endonuclease genes are co-transcribed with a methylase gene that protects the cell from self-digestion. The HindIII restriction enzyme system is encoded by clone C09 in the minimal tiling set, and it was verified that genomic DNA extracted from this E. coli clone is in fact protected by expression of the HindIII methylase such that it is resistant to digestion by the HindIII restriction endonuclease. EXAMPLE II In Vivo Assembly of Episomal Elements in E. coli [0054] In this example episomal elements that contain mutant LoxP sites are constructed using standard molecular biology procedures. These constructs are transformed sequentially into an E. coli host and fusion is mediated by induction of Cre expression within the host cell. Separately, Bacterial Artificial Chromosomes (BACs) containing large segments of the H. influenzae genome are retrofit with mutant lox sites and selectable markers using the RED/ET system. BACs retrofitted in this manner are suitable for serial recombination in Cre expressing RED/ET E. coli host cells. [0055] A short DNA segment with an EcoRI compatible overhang on one end plus a HindIII compatible overhang on the opposite end, and containing a LoxP site that has both an LE arm mutant (ATAAC to TACCG) and a spacer mutant (C to G at spacer position 2 and A to C at spacer position 7) was ligated into EcoRI/HindIII cut and gel purified pET19b expression vector. This ampicillin resistant pET19b construct contains the coding sequence for the Cre enzyme inserted into the NdeI site of the multiple cloning region, under control of an IPTG inducible promoter. This construct was transformed into HMS — 174 E. coli cells (Novagen), and a batch of electro-competent cells containing the pET19b construct was prepared. Separately, a complementary mutant LoxP site was designed that contained the same mutant spacer region as the above site, and a right element arm mutation (GTTAT to CGGTA). This site was inserted into the tetA (tetracycline resistance) gene in plasmid pBR322 by fusion PCR, using end primers tailed with SacI and NotI restriction sites. The PCR product, comprised of the tetA gene with the embedded RE mutant loxP site was digested with SacI and Not and gel purified, then ligated into SacI/NotI digested and gel purified BAC vector pECBACl. This construct was propagated in E. coli DH10B cells and DNA was isolated by alkaline lysis and transformed into the electro-competent HMS — 174 E. coli host cells already harboring the pET19b LE mutant LoxP construct. Cells were grown first on solid media containing IPTG and ampicillin, then harvested and transferred to plates containing tetracycline and fusaric acid. Fusaric acid is toxic to cells expressing a functional tetA gene. Since the pECBACl construct contains a RE mutant LoxP site embedded in the tetA gene, upon Cre mediated recombination that joins the pECBACl and pET19b constructs, the pECBACl tetA insert is disrupted, allowing recombinants to grow on fusaric acid containing solid media. A total of 96 clones were screened for recombination by colony PCR using a left primer complementary to the Cre gene in the pET19b construct and a right primer complementary to a region of the tetA gene in the pECBACl construct. The expected junction fragment was observed in two of the 96 clones screened. Subsequent sequencing of these positive clones indicated a fusion of the tetA and Cre genes and conversion of the single arm mutant loxP sites to a wild type site, thus verifying successful in vivo recombination. [0056] The RED/ET system was used to retrofit a BAC (BAC 1) containing a large (104 kbp) segment of the H. infuenzae genome with a mutant LoxP site. A double stranded oligonucleotide was prepared that comprised a LoxP site with the LE arm mutation (ATAAC to TACCG), a wild type spacer region, and EcoRI compatible overhang on one end plus a HindIII compatible overhang on the opposite end. This oligonucleotide was ligated into EcoRI/HindIII cut and gel purified pET19b vector. Subsequently, a segment of this pET19b construct containing the beta-lactamase (bla) gene for ampicillin resistance next to the inserted LE mutant LoxP site was amplified by PCR. The PCR primers were tailed with 44 bp sequences homologous to a non-essential segment of the backbone of the pECBACl vector. The H. influenzae BACl was transformed into electro-competent EL350 cells. These cells carry the Cre gene under control of an arabinose inducible promoter, and a segment of the bacteriophage lambda genome encoding the exo, bet and gam genes under control of a temperature sensitive repressor (Yu et al. PNAS, 2000). Heat induced, electro-competent EL350 cells carrying the 104 kbp H. influenzae segment in chloramphenicol-resistant pECBACl were prepared and transformed with the PCR product containing the bla gene, mutant lox site and pECBACl homology arms. Transformed cells were plated on solid media containing chloramphenicol and ampicillin. Numerous colonies were picked and targeted insertion of the mutant LoxP cassette was sequence verified. [0057] For H. influenzae precursor genome assembly, the neighboring clone in the H. influenzae BAC minimal tiling path (BAC II) is retrofit with a cassette containing a complementary LoxP site. A double stranded oligonucleotide is prepared that comprises a LoxP site with the RE arm mutant (GTTAT to CGGTA), a wild type spacer region, and SpeI compatible overhangs. This oligonucleotide is ligated into Spe1 cut and gel purified pGPS1.1 vector. Subsequently, a segment of this pGPS1.1 construct containing the kanamycin resistance gene next to the inserted RE mutant LoxP site is amplified by PCR. The PCR primers are tailed with the 44 bp sequences, as above, that are homologous to a non-essential segment of the backbone of the pECBACl vector. BACII is transformed into electro-competent EL350 cells and heat induced, electro-competent EL350 cells carrying the H. influenzae genome segment in chloramphenicol-resistant pECBACl are prepared, followed by transformation of the PCR product containing the kanamycing resistance gene, RE mutant lox site and pECBAC homology arms and integration of this cassette into BACII. [0058] Cells containing RE loxP retrofit BACII are grown and BAC DNA is isolated by standard alkaline lysis procedures and purified by pulsed field gel electrophoresis (PFGE). Electro-competent EL350 cells containing LE loxP retrofitted BACI are prepared, and transformed with purified retrofitted-BACII DNA and grown in liquid media in the presence of L(+)-arabinose for induction of Cre gene expression plus double antibiotics (ampicillin and kanamycin) which are necessary to maintain both retrofit-BACI and retrofit-BACII in the host cells to allow their recombination. The F replicon in the BAC vector maintains stringent copy number control such that only one or two copies are present per cell. Cells are plated and colonies picked and screened for the presence of the BACI/BACII fusion, which represents the first recombinant precursor genome in the modular genome construction process. The orientation of the two genome segments in the consolidated BAC is predetermined by defining the orientation of the spacer regions of the LoxP sites introduced into the original BACs, BACI and BACII. Post recombination, the consolidated circular DNA molecule (BACI/II) will have one reactive wild type LoxP site, an inert double arm mutant LoxP site, an amplicillin resistance gene, a kanamycin resistance gene and two juxtaposed copies of the pECBACl vector backbone. Using RED/ET recombination, the wild type LoxP site and the adjacent antibiotic resistance marker are replaced with a new cassette that contains a new LE arm mutant loxP site and a previously unused antibiotic resistance marker, such as the zeocin resistance gene or the gentamycin resistance gene. The next adjacent clone in the tiling path (BACIII) is retrofit as above with a complementary RE arm mutant site and an antibiotic resistance gene, which may be the antibiotic resistance gene removed from BACI/II or a different antibiotic resistance gene. DNA is prepared from BACIII and transformed into host cells harboring BACI/II. Cells are grown in liquid media in the presence of L(+)-arabinose for induction of Cre gene expression and the appropriate double antibiotics to maintain both BACI/II and BACIII in the host cells, so as to allow their recombination. In this manner, each BAC in the tiling path is added to the growing precursor genome until the genome is tiling path is completely reassembled, or until a desired state of re-assembly is achieved. Definitions [0059] Terms and symbols of nucleic acid chemistry, biochemistry, genetics, and molecular biology used herein follow those of standard treatises and texts in the field, e.g. Kornberg and Baker, DNA Replication, Second Edition (W.H. Freeman, New York, 1992); Lehninger, Biochemistry, Second Edition (Worth Publishers, New York, 1975); Strachan and Read, Human Molecular Genetics, Second Edition (Wiley-Liss, New York, 1999); Eckstein, editor, Oligonucleotides and Analogs: A Practical Approach (Oxford University Press, New York, 1991); Gait, editor, Oligonucleotide Synthesis: A Practical Approach (IRL Press, Oxford, 1984); and the like. [0060] “Amplicon” means the product of a polynucleotide amplification reaction. That is, it is a population of polynucleotides, usually double stranded, that are replicated from one or more starting sequences. The one or more starting sequences may be one or more copies of the same sequence, or it may be a mixture of different sequences. Amplicons may be produced by a variety of amplification reactions whose products are multiple replicates of one or more target nucleic acids. Generally, amplification reactions producing amplicons are “template-driven” in that base pairing of reactants, either nucleotides or oligonucleotides, have complements in a template polynucleotide that are required for the creation of reaction products. In one aspect, template-driven reactions are primer extensions with a nucleic acid polymerase or oligonucleotide ligations with a nucleic acid ligase. Such reactions include, but are not limited to, polymerase chain reactions (PCRs), linear polymerase reactions, nucleic acid sequence-based amplification (NASBAs), rolling circle amplifications, and the like, disclosed in the following references that are incorporated herein by reference: Mullis et al, U.S. Pat. Nos. 4,683,195; 4,965,188; 4,683,202; 4,800,159 (PCR); Gelfand et al, U.S. Pat. No. 5,210,015 (real-time PCR with “taqman” probes); Wittwer et al, U.S. Pat. No. 6,174,670; Kacian et al, U.S. Pat. No. 5,399,491 (“NASBA”); Lizardi, U.S. Pat. No. 5,854,033; Aono et al, Japanese patent pubi. JP 4-262799 (rolling circle amplification); and the like. In one aspect, amplicons of the invention are produced by PCRs. An amplification reaction may be a “real-time” amplification if a detection chemistry is available that permits a reaction product to be measured as the amplification reaction progresses, e.g. “real-time PCR” described below, or “real-time NASBA” as described in Leone et al, Nucleic Acids Research, 26: 2150-2155 (1998), and like references. As used herein, the term “amplifying” means performing an amplification reaction. A “reaction mixture” means a solution containing all the necessary reactants for performing a reaction, which may include, but not be limited to, buffering agents to maintain pH at a selected level during a reaction, salts, co-factors, scavengers, and the like. [0061] “Duplex” means at least two oligonucleotides and/or polynucleotides that are fully or partially complementary undergo Watson-Crick type base pairing among all or most of their nucleotides so that a stable complex is formed. The terms “annealing” and “hybridization” are used interchangeably to mean the formation of a stable duplex. In one aspect, stable duplex means that a duplex structure is not destroyed by a stringent wash, e.g. conditions including temperature of about 5° C. less that the T m of a strand of the duplex and low monovalent salt concentration, e.g. less than 0.2 M, or less than 0.1 M. “Perfectly matched” in reference to a duplex means that the poly- or oligonucleotide strands making up the duplex form a double stranded structure with one another such that every nucleotide in each strand undergoes Watson-Crick basepairing with a nucleotide in the other strand. The term “duplex” comprehends the pairing of nucleoside analogs, such as deoxyinosine, nucleosides with 2-aminopurine bases, PNAs, and the like, that may be employed. A “mismatch” in a duplex between two oligonucleotides or polynucleotides means that a pair of nucleotides in the duplex fails to undergo Watson-Crick bonding. [0062] “Hybridization” refers to the process in which two single-stranded polynucleotides bind non-covalently to form a stable double-stranded polynucleotide. The term “hybridization” may also refer to triple-stranded hybridization. The resulting (usually) double-stranded polynucleotide is a “hybrid” or “duplex.” “Hybridization conditions” will typically include salt concentrations of less than about 1M, more usually less than about 500 mM and less than about 200 mM. Hybridization temperatures can be as low as 5° C., but are typically greater than 22° C., more typically greater than about 30° C., and preferably in excess of about 37° C. Hybridizations are usually performed under stringent conditions, i.e. conditions under which a probe will hybridize to its target subsequence. Stringent conditions are sequence-dependent and are different in different circumstances. Longer fragments may require higher hybridization temperatures for specific hybridization. As other factors may affect the stringency of hybridization, including base composition and length of the complementary strands, presence of organic solvents and extent of base mismatching, the combination of parameters is more important than the absolute measure of any one alone. Generally, stringent conditions are selected to be about 5° C. lower than the T m for the specific sequence at s defined ionic strength and pH. Exemplary stringent conditions include salt concentration of at least 0.01 M to no more than 1 M Na ion concentration (or other salts) at a pH 7.0 to 8.3 and a temperature of at least 25° C. For example, conditions of 5×SSPE (750 mM NaCl, 50 mM NaPhosphate, 5 mM EDTA, pH 7.4) and a temperature of 25-30° C. are suitable for allele-specific probe hybridizations. For stringent conditions, see for example, Sambrook, Fritsche and Maniatis. “Molecular Cloning A laboratory Manual” 2 nd Ed. Cold Spring Harbor Press (1989) and Anderson “Nucleic Acid Hybridization” 1 st Ed., BIOS Scientific Publishers Limited (1999), which are hereby incorporated by reference in its entirety for all purposes above. “Hybridizing specifically to” or “specifically hybridizing to” or like expressions refer to the binding, duplexing, or hybridizing of a molecule substantially to or only to a particular nucleotide sequence or sequences under stringent conditions when that sequence is present in a complex mixture (e.g., total cellular) DNA or RNA. [0063] “Inducible” or “inducible control” in reference to gene expression means that gene expression is controlled by a promoter and possibly of regulatory elements such that a promoter is transcriptionally active under a specific set of conditions, e.g., a change in physical conditions, such as a change in pH, temperature, salt concentration, or the like, or the presence of a particular chemical signal or combination of chemical signals that, for example, affect binding of the transcriptional activator to the promoter and/or affect function of the transcriptional activator itself. [0064] “Ligation” means to form a covalent bond or linkage between the termini of two or more nucleic acids, e.g. oligonucleotides and/or polynucleotides, in a template-driven reaction. The nature of the bond or linkage may vary widely and the ligation may be carried out enzymatically or chemically. As used herein, ligations are usually carried out enzymatically to form a phosphodiester linkage between a 5′ carbon of a terminal nucleotide of one oligonucleotide with 3′ carbon of another oligonucleotide. A variety of template-driven ligation reactions are described in the following references, which are incorporated by reference: Whitely et al, U.S. Pat. No. 4,883,750; Letsinger et al, U.S. Pat. No. 5,476,930; Fung et al, U.S. Pat. No. 5,593,826; Kool, U.S. Pat. No. 5,426,180; Landegren et al, U.S. Pat. No. 5,871,921; Xu and Kool, Nucleic Acids Research, 27: 875-881 (1999); Higgins et al, Methods in Enzymology, 68: 50-71 (1979); Engler et al, The Enzymes, 15: 3-29(1982); and Namsaraev, U.S. patent publication 2004/0110213. [0065] “Nucleic acid construct” is used synonymously with “recombinant DNA molecule.” [0066] “Nucleoside” as used herein includes the natural nucleosides, including 2′-deoxy and 2′-hydroxyl forms, e.g. as described in Kornberg and Baker, DNA Replication, 2nd Ed. (Freeman, San Francisco, 1992). “Analogs” in reference to nucleosides includes synthetic nucleosides having modified base moieties and/or modified sugar moieties, e.g. described by Scheit, Nucleotide Analogs (John Wiley, New York, 1980); Uhlman and Peyman, Chemical Reviews, 90: 543-584 (1990), or the like, with the proviso that they are capable of specific hybridization. Such analogs include synthetic nucleosides designed to enhance binding properties, reduce complexity, increase specificity, and the like. Polynucleotides comprising analogs with enhanced hybridization or nuclease resistance properties are described in Uhlman and Peyman (cited above); Crooke et al, Exp. Opin. Ther. Patents, 6: 855-870 (1996); Mesmaeker et al, Current Opinion in Structual Biology, 5: 343-355 (1995); and the like. Exemplary types of polynucleotides that are capable of enhancing duplex stability include oligonucleotide N3→P5′ phosphoramidates (referred to herein as “amidates”), peptide nucleic acids (referred to herein as “PNAs”), oligo-2′-O-alkylribonucleotides, polynucleotides containing C-5 propynylpyrimidines, locked nucleic acids (LNAs), and like compounds. Such oligonucleotides are either available commercially or may be synthesized using methods described in the literature. [0067] “Polymerase chain reaction,” or “PCR,” means a reaction for the in vitro amplification of specific DNA sequences by the simultaneous primer extension of complementary strands of DNA. In other words, PCR is a reaction for making multiple copies or replicates of a target nucleic acid flanked by primer binding sites, such reaction comprising one or more repetitions of the following steps: (i) denaturing the target nucleic acid, (ii) annealing primers to the primer binding sites, and (iii) extending the primers by a nucleic acid polymerase in the presence of nucleoside triphosphates. Usually, the reaction is cycled through different temperatures optimized for each step in a thermal cycler instrument. Particular temperatures, durations at each step, and rates of change between steps depend on many factors well-known to those of ordinary skill in the art, e.g. exemplified by the references: McPherson et al, editors, PCR: A Practical Approach and PCR2: A Practical Approach (IRL Press, Oxford, 1991 and 1995, respectively). For example, in a conventional PCR using Taq DNA polymerase, a double stranded target nucleic acid may be denatured at a temperature >90° C., primers annealed at a temperature in the range 50-75° C., and primers extended at a temperature in the range 72-78° C. Reaction volumes typically range from a few hundred nanoliters, e.g. 200 mL, to a few hundred μL, e.g. 200 μL. [0068] “Polynucleotide” or “oligonucleotide” are used interchangeably and each mean a linear polymer of nucleotide monomers. Monomers making up polynucleotides and oligonucleotides are capable of specifically binding to a natural polynucleotide by way of a regular pattern of monomer-to-monomer interactions, such as Watson-Crick type of base pairing, base stacking, Hoogsteen or reverse Hoogsteen types of base pairing, or the like. Such monomers and their internucleosidic linkages may be naturally occurring or may be analogs thereof, e.g. naturally occurring or non-naturally occurring analogs. Non-naturally occurring analogs may include PNAs, phosphorothioate internucleosidic linkages, bases containing linking groups permitting the attachment of labels, such as fluorophores, or haptens, and the like. Whenever the use of an oligonucleotide or polynucleotide requires enzymatic processing, such as extension by a polymerase, ligation by a ligase, or the like, one of ordinary skill would understand that oligonucleotides or polynucleotides in those instances would not contain certain analogs of internucleosidic linkages, sugar moities, or bases at any or some positions. Polynucleotides typically range in size from a few monomeric units, e.g. 5-40, when they are usually referred to as “oligonucleotides,” to several thousand monomeric units. Whenever a polynucleotide or oligonucleotide is represented by a sequence of letters (upper or lower case), such as “ATGCCTG,” it will be understood that the nucleotides are in 5→3′ order from left to right and that “A” denotes deoxyadenosine, “C” denotes deoxycytidine, “G” denotes deoxyguanosine, and “T” denotes thymidine, “I” denotes deoxyinosine, “U” denotes uridine, unless otherwise indicated or obvious from context. Unless otherwise noted the terminology and atom numbering conventions will follow those disclosed in Strachan and Read, Human Molecular Genetics 2 (Wiley-Liss, New York, 1999). Usually polynucleotides comprise the four natural nucleosides (e.g. deoxyadenosine, deoxycytidine, deoxyguanosine, deoxythymidine for DNA or their ribose counterparts for RNA) linked by phosphodiester linkages; however, they may also comprise non-natural nucleotide analogs, e.g. including modified bases, sugars, or internucleosidic linkages. It is clear to those skilled in the art that where an enzyme has specific oligonucleotide or polynucleotide substrate requirements for activity, e.g. single stranded DNA, RNA/DNA duplex, or the like, then selection of appropriate composition for the oligonucleotide or polynucleotide substrates is well within the knowledge of one of ordinary skill, especially with guidance from treatises, such as Sambrook et al, Molecular Cloning, Second Edition (Cold Spring Harbor, Laboratory, New York, 1989), and like references. [0069] “Primer” means an oligonucleotide, either natural or synthetic, that is capable, upon forming a duplex with a polynucleotide template, of acting as a point of initiation of nucleic acid synthesis and being extended from its 3′ end along the template so that an extended duplex is formed. The sequence of nucleotides added during the extension process are determined by the sequence of the template polynucleotide. Usually primers are extended by a DNA polymerase. Primers usually have a length in the range of from 14 to 36 nucleotides. [0070] “Recombination element” means a sequence that is a site of recombination of DNA sequences in a recombination reaction. A recombination element may be a segment of DNA that is homologous to another segment that participates in a recombination reaction (e.g. as in homologous recombination), or it may be a specific sequence where recombination takes place by action of an associated recombinase, and perhaps additional ancillary factors, that recognizes all or part of the specific sequence (e.g. as in site-specific recombination). In one aspect, a recombination element is a recombination site of a site-specific recombination system, such as Cre-LoxP, Flp-FRT, or the like. [0071] “Regulatory elements” in reference to gene expression means DNA sequences that are operably linked to the expression of one or more genes. Such elements are commonly located at positions adjacent to the expressed genes and can include promoters, terminators, antiterminators, activators, attenuators, and the like, e.g. Kornberg and Baker, DNA Replication, 2 nd Edition (Freeman, San Francisco, 1992), Makrides, Microbiological Reviews, 60: 512-538 (1996). Frequently, one or more co-regulated genes are associated with the same set of regulatory elements in an operon. [0072] “Synthetic” in reference to a polynucleotide segment of the invention means that all or a portion of the segment is constructed from one or more polynucleotides that were initially chemically synthesized. After synthesis, such synthetic polynucleotide segments may be replicated by in vivo or in vitro enzymatic methods, e.g. by conventional cloning or by amplification, such as by PCR, RCR, or the like. Various approaches may be used to constructing synthetic polynucleotide segments for use with the invention including, but not limited to, those described in the following references that are incorporated herein by reference: Tian et al, Nature, 432: 1050-1054 (2004); Soldatov et al, International patent publication WO 2004/092375; U.S. patent publication 2003/0138782A1; U.S. patent publication 2003/0165946A1; U.S. patent publication 2005/0106606A 1; International patent publication WO 2006/044956; Cleary et al, Nature Methods, 1: 241-248 (2004); Zhou et al, Nucleic Acids Research, 32: 5409-5417 (2004); Chen et al, J. Chem. Soc., 116: 8799-8800 (1994); Mandecki et al, Gene, 68: 101-107 (1988); Kodumal et al, Proc. Natl. Acad. Sci., 101: 15573-15578 (2004); Smith et al, Proc. Natl. Acad. Sci., 100: 15440-15445 (2003); or the like.
The invention provides methods and compositions for assembling a modular replacement genome in a host microorganism. After such assembly, the host organism's genome is inactivated or ablated to permit full control of host cellular functions by the replacement genome. A modular replacement genome comprises an assembly of nucleic acid fragments, or segments, derived from one or more natural organisms or from synthetic polynucleotides or from a combination of both. Such an assembly, or set, of segments making up a replacement genome comprises a substantially complete set of genes and regulatory elements for carrying out minimal life functions under predefined culture conditions. The invention provides modular genomes having modules that are amenable to facile replacement, deletion, and/or additions. Such modules may be synthetic polynucleotides and may be designed for controlling gene content, excluding of genes that encode inhibitors or otherwise undesirable competing enzymes that divert a host cell from desired metabolic/synthetic processes; modifying codon usage to maximize or minimize protein production; modifying regulatory elements, including promoters, enhancers, repressors, activator, or the like, to modulate gene expression; balancing enzymatic and transport activities to optimize fluxes of substrates, intermediates, and products in metabolic pathways, and like objectives.
2
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is concerned with the preparation of sulfonyl isocyanates having the general formula R--SO.sub.2 --NCO I wherein an isocyanate group is linked directly to the SO 2 group and R is a C 1 - to C 18 -alkyl, a phenyl, a C 1 - to C 18 -alkyl phenyl radical or an isocyanate group. 2. Discussion of the Prior Art Compounds having the formula I became of importance with respect to the stabilization of organic isocyanates against decomposition and discoloration (see U.S. Pat. No. 33,330,849, DE-Pat. No. 2 030 316), and the stability increase of polyurethane prepolymers (DE-Pat. No. 1 245 590). Furthermore sulfonyl diisocyanate forms an intermediate compound for producing diacyl sulfamides which are used for stabilization and acceleration of reactive acrylate adhesives (German patent application No. P 31 37 306.2-43). Although sulfonyl isocyanates are already known since the beginning of this century, systematic studies of this class of substances started only 50 years later. For one reason this results from the difficulty of obtaining these compounds synthetically and for another from their high reactivity. A summary of the methods of forming these compounds known in 1964 is given by H. Ulrich in Chem. Rev. 65 (3), 369-376 (1965). From the voluminous recent literature the following important general methods of obtaining sulfonyl isocyanates are available: 1. Methods of preparing aliphatic sulfonylisocyanates 1.1. Reaction of sulfonylchlorides and anhydrides with silver isocyanate: CH.sub.3 --SO.sub.2 --Cl+AgNCO→CH.sub.3 --SO.sub.2 --NCO+AgCl O. C. Billeter, Ber. 38, 2013-2015 (1905); L. Field, P. H. Settlage, J.Am.Chem.Soc. 76, 1222-1225 (1954). 1.2 Elimination of alcohols from sulfonylurethanes or their silylated analogues: ##STR1## 1.3 Heterogeneous reaction of sulfochlorides with alkali metal cyanates: ##STR2## 2. Methods of preparing aromatic sulfonylisocyanates. 2.1. Reaction of sulfonamides with phosgene in high boiling inert solvents: ##STR3## 2.2 Reaction of N-alkyl-N'-arylsulfonylureas, which are intermediates from the reaction of sulfonamides with alkyl isocyanates, with phosgene: ##STR4## 2.3 Reaction of aromatic sulfonylchlorides with alkali metal cyanates: ##STR5## 2.4 Reaction of aromatic hydrocarbons with chlorosulfonylisocyanate: ##STR6## 3. Methods of forming sulfonyldiisocyanate 3.1 Reaction of bromocyanogen with SO 3 : 2BrCN+2SO.sub.3 →OCN--SO.sub.2 --NCO+SO.sub.2 +Br.sub.2 R. Graf, DE-PS 940 351. 3.2 Thermal or catalytic decomposition of chlorosulfonylisocyanate: ##STR7## 3.3 Reaction of chlorosulfonylisocyanate with silver isocyanate: Cl--SO.sub.2 --NCO+AgNCO→OCN--SO.sub.2 --NCO+AgCl R. Appel, H. Gerber, Ber. 91, 1200 (1958). All of the above mentioned processes suffer from substantial disadvantages. The use of silverisocyanate for instance is impeded by the high price and the laborious, time-consuming and expensive regeneration of the substance while when using potassium cyanate only a small yield is obtained from the heterogeneous reaction. It is impossible to obtain a homogeneous reaction by use of a suitable solvent since the strong reactivity of the sulfonylisocyanate results, especially under the influence of high temperature, in a yield-reducing reaction of the same with the solvents in question. In reactions using phosgene it is disadvantageous that the substance is highly poisonous and thus a health hazard; furthermore the by-products have to be removed. In elimination reactions from sulfonylurethanes it is an unfavourable fact that these starting materials first have to be specially synthesized and subsequently it is not possible to regenerate the elimination products in the conversion reaction itself. In the methods of preparing sulfonyldiisocyanate known in the art it is on the one hand the high toxicity of the rather expensive bromocyanogen which is interfering and on the other hand the fact that during the thermal decomposition of chlorosulfonylisocyanate only one moiety of the starting material is utilized, while the other moiety forms chlorine and sulfurdioxide which again require special exhaust gas treatment. SUMMARY OF THE INVENTION It is the object of the present invention to find a reaction by which aliphatic and aromatic sulfonyl isocyanates as well as sulfonyldiisocyanates are obtained in a simple manner with high yield and purity while avoiding the mentioned disadvantages. Unexpectedly it was found that the above disadvantages are avoided when sulfonylhalides are reacted with trimethylsilylisocyanates in the presence of suitable catalysts as for instance Lewis acids, and that especially sulfonyldiisocyanate and aromatic sulfonyl isocyanates but also aliphatic sulfonyl isocyanates are obtained with higher yield and purity, according to the following equation wherein R has the same meaning as set forth above: ##STR8## The use of trimethyl silylisocyanate has indeed been proposed by W. Buss, H. J. Krannich and W. Sundermeyer in Ber. 109, 1486-1490 (1976) for introduction of an isocyanate group into trimethyl silyloxysulfonylchloride. But when reacting chlorosulfonylisocyanate, which is the most reactive sulfonylisocyanate of the above series, with trimethyl silylisocyanate under the given conditions, it is impossible to isolate the desired sulfonyldiisocyanate but only traces of this substance are detectable by gas chromatography. On the other hand an extraordinarily smooth reaction is obtained wherein sulfonyldiisocyanate for instance is formed with high purity and a yield of 80% by adding the catalysts of the invention. The present invention is thus directed to a new method of forming sulfonylisocyanates having the general formula R--SO.sub.2 --NCO, I wherein R is a linear or branched C 1 - to C 18 -alkyl radical, a phenyl radical, an alkyl phenyl radical having at least one linear or branched alkyl group containing from 1 to 18 C-atoms, or an isocyanate group, by reacting the corresponding sulfonylchloride having the formula R--SO.sub.2 --Cl, II wherein R has the meaning set forth above, with an isocyanate. The process is characterized in that trimethyl silylisocyanate is used as the isocyanate and that the reaction is carried out in the presence of catalytic amounts of Lewis acids. It is one advantage of the conversion reaction of the present invention that merely a suitable rectification apparatus with packed columns is needed. The expensive high temperature reactors necessary for thermic decomposition of chlorosulfonylisocyanate to obtain sulfonyldiisocyanate can thus be dispensed with. It is a further important economic advantage of the present method, that a favourable space-time-yield is obtained by the high reaction rate which results from the homogeneous reaction. On the other hand it is possible to re-use the chlorotrimethyl silane which is recovered from the reaction nearly quantitatively, for producing again trimethyl silylisocyanate so that the following over all reaction equation results, which is not obtainable through a direct path since the direct conversion would be a heterogeneous reaction: R--SO.sub.2 --Cl+NaOCN→R--SO.sub.2 --NCO+NaCl DETAILED DESCRIPTION OF THE INVENTION The organic sulfonylchlorides required as a starting material can easily be formed from the corresponding sulfonic acids. As described by L. Graf in DE-Pat. No. 928 896 chlorosulfonylisocyanate is easily available from chlorocyanogen and sulphur trioxide. Trimethyl silylisocyanate can advantageously be prepared according to DE-Pat. No. 1 965 741 with 89% yield by reacting chlorotrimethyl silane with sodium cyanate using dimethyl formamide as a solvent. By selection of a suitable catalyst and the reaction temperature the course of the conversion can be substantially influenced. A great many metal and non-metal halides, which generally can be considered Lewis acids are useful for catalyzing the reaction of the invention, especially the halides, i.e. the fluorides, bromides, iodides and especially the chlorides of boron, aluminum, titanium, tin, vanadium, antimony, iron and zinc, having the general formula AX n (n=valence of A). Each of the mentioned compounds can be used alone or as a mixture. Within the scope of the invention titanium and tin halides as for instance titanium tetrachloride or tin tetrachloride are especially suitable, whereby in the case of the reactive chloro sulfonylisocyanates better results are obtained with tin tetrachloride while for preparation of aromatic or aliphatic sulfonylisocyanates titanium tetra-chloride or combinations of tin and titanium tetra-chloride are preferred. The amount of catalyst is about 0.1 to 20% by weight preferably about 5 to 10% by weight, based on the amount of trimethyl silylisocyanate used. Although the exact principle of the catalytic action cannot yet be explained, some observations point to a complex first being formed between the catalyst and the trimethyl silylisocyanate, resulting in the formation of a small amount of chlorotrimethyl silane. Presumably this intermediate compound reacts with the sulfochloride, by which reaction the NCO-groups are transferred and the catalyst is regenerated. It is also possible to influence the reaction considerably by temperature control. Although the reaction can be started by heating the mixture of all components, it became evident, that especially in the case of the less reactive sulfonylchlorides it is more favourable to add the trimethyl silylisocyanate during the course of the reaction in such a manner that a bottom temperature of 120° to 130° C. can be maintained and the temperature does not rise above 160° C. subsequently. The sulfonylisocyanates obtained by the method of the invention were separated by subsequent rectification of the reaction mixture, using vacuum if necessary. The sulfonylisocyanates were definitively characterized by reaction with benzyl alcohol and the structure of the resulting addition compounds obtained in quantitative yield was proven by IR-, 13 C-NMR- and 1 H-NMR-spectra. The following examples are given for illustration of the invention. EXAMPLE 1 Preparation of sulfonyldiisocyanate 28,30 g of chlorosulfonylisocyanate (0,200 mol) and 23,04 g of trimethyl silylisocyanate (0,200 mol) where heated to reflux temperature by means of an oil bath with stirring within a round flask equipped with a packed column. 1.0 ml of tin tetrachloride were added to the boiling mixture, whereupon a quick temperature drop at the column head from 91° to 58° C. was observed. The head product (chlorotrimethyl silane) was removed in such a manner, that a still temperature of 58° to 60° C. could be maintained. After a reaction time of 2,5 h the bottom temperature had increased from 97° to 143° C. while in spite of infinite reflux the still temperature did not drop beneath 126° C. By rectification of the reaction mixture over a Vigreux-column under vacuum 23,74 g of pure sulfonyldiisocyanate (80% of theory), bp. (18 mbar) 46° to 47° C., a colorless liquid, were obtained. According to GC-analysis the distillation product obtained during the reaction (26,00 g of colorless liquid) consisted of 82% chlorotrimethyl silane and 18% trimethyl silylisocyanate; thus 21,32 g or 98% of the theoretical amount of chloro trimethyl silane were recovered. Characterisation of the sulfonyldiisocyanate 5,41 g of anhydrous benzyl alcohol (0,050 mol) were dissolved in 200 ml of absolute benzene and 3,70 g of sulfonyldiisocyanate were added dropwise. As a result the reaction temperature increased and a colorless precipitate formed. The precipitate was suction filtered and dried (4.05 g, 99% of theoretical value). After re-cristallization from diethylether/petrol ether 7,61 g of N,N'-bis(benzyloxycarbonyl)-sulfamide, colorless crystals, m.p. (decomposition) 141° C., were obtained. Structure: ______________________________________ ##STR9## ______________________________________IR-spectrum (KBr): 3280/3200 cm.sup.-1 ν(NH) 1750 cm.sup.-1 ν(CO) ν(SO.sub.2)as + ν(SO.sub.2)sy Assignment not definite .sup.13 CNMR-spectrum 151,36 ppm CO(acetone d.sub.6) ##STR10## 64,42 ppm CH.sub.2 .sup.1 HNMR-spectrum 10,71 ppm, s, 2 H for NH(acetone d.sub.6) 7,34 ppm, s, 10 H for ArH 5,16 ppm, s, 4 H for CH.sub.2.______________________________________ The IR-spectrum was completely identical to the spectrum of a substance synthesised from a sulfonyldiisocyanate (which was prepared according to K. Appel, H. Gerber, Ber. 91, 1200 (1958) from chlorosulfonylisocyanate and silverisocyanate) and benzyl alcohol. EXAMPLE 2 Preparation of 4-methyl benzenesulfonylisocyanate 95,44 g of 4-methyl benzene sulfonylchloride (0,500 mol) were molten in an round flask, 2.5 ml of titanium tetrachloride were added--resulting in a brown color of the reaction mixture--and heated to 120° C. with a packed column mounted on the flask. Subsequently 61,13 g of trimethyl silylisocyanate (0,600 mol) were added dropwise in such a manner that the bottom temperature was maintained at 120° C. When the addition was started a yellow precipitate formed and at the same time the still temperature dropped to 58° C. Corresponding to example 1 the head product distilled at a temperature of 58° to 59° C. while the bottom temperature was gradually increased to 150° C. In this way 46,66 g of a colorless liquid, bp. 58° to 59° C., were distilled off within 3 hours (GC: pure chlorotrimethyl silane). The reaction mixture was distilled through a Claisen-bridge under oil pump vacuum, whereby 83,60 g of a slightly yellow liquid, bp. (1 mbar) 92° to 96° C., were obtained. By rectification of the same through a Vigreux-column 72,94 g (74% of theoretical value) of colorless 4-methyl benzene sulfonylisocyanate, bp. (0,9 mbar) 94° to 94,5° C., were obtained which according to GC-analysis still contained 8% 4-methyl-benzene-sulfonyl-chloride. Characterisation of 4-methyl-benzenesulfonylisocyanate To 2,74 g of anhydrous benzyl alcohol (0,025 mol) in 50 ml of absolute benzene 5.00 g of 4-methyl benzenesulfonylisocyanate were added dropwise. The temperature of the reaction mixture increased and a clear solution was obtained. By evaporation of the benzene solution, addition of some petroleum ether and suction filtering 7,05 g of colorless crystals were obtained. After recristallisation from benzene/petrol ether 6,20 g of N-benzyl oxycarbonyl4-methyl benzosulfonamide, colorless crystals, m.p. 100° to 101° C., homogeneous in thin layer chromatography (silica gel, benzene/diethyl ether) were obtained. Structure: ______________________________________ ##STR11##______________________________________IR-spectrum (KBr) 3290 cm.sup.-1 ν(NH) 1740 cm.sup.-1 ν(CO) 1350 cm.sup.-1 ν(SO.sub.2)as 1160/1170 cm.sup.-1 ν(SO.sub.2)s .sup.13 CNMR-spectrum 150,77 ppm (O)(CDCl.sub.3) ##STR12## 68,48 ppm CH.sub.2 21,51 ppm CH.sub.3 .sup.1 HNMR-spectrum 8,54 ppm, s, 1 H, exchangeable for(CDCl.sub.3) D.sub.2 O for NH 7,91/7,81/7,23/7,13 ppm, AB-Type 4 H for C.sub.6 H.sub.4SO.sub.2 7,21 ppm, s, 5 H for C.sub.6 H.sub.5 CH.sub.2 5,02 ppm, s, 2 H for CH.sub.2 2,34 ppm, s, 3 H for CH.sub.3______________________________________ EXAMPLE 3 Preparation of methane sulfonylisocyanate A round flask with affixed packed column was charged with 44,56 g of methane sulfochloride (0,389 mol), 2 ml of TiCl 4 and 2 ml of SnCl 4 and heated to 120° C. in an oil bath. Subsequently 15 g of a total of 53,74 g of trimethyl silylisocyanate (0,466 mol) were added, whereby precipitation of a yellow-brown precipitate within the reaction mixture was observed. After the still temperature had dropped to 58° C. chlorotrimethyl silane was continually removed at the head at 58° to 60° C. until the bottom temperature had reached 135° C. The remaining portion of trimethyl silylisocyanate was then added portionwise in such a manner that a bottom temperature of 135° to 150° C. was maintained, while the chlorotrimethyl silane distilled at 50° to 60° C. The conversion was thus controlled for 9 hours, a bottom temperature of 160° C. in combination with a still temperature of 60° C. being registered. As in example 2 the reaction mixture was first distilled through a Claisen-bridge under vacuum, by which process 31,80 g of a nearly colorless liquid of bp. (22 mbar) 73° to 80° C. were obtained. After rectification through a Vigreux-column 19,32 g of colorless methane sulfonylisocyanate, bp. (22 mbar) 79° to 81° C., were recovered, which according to gaschromatographic analysis still contained 6% methane sulfochloride. Characterisation of methane sulfonylisocyanate To 3,57 g of anhydrous benzyl alcohol (0,033 mol) in 50 ml absolute benzene 4,00 g methane sulfonyliscyanate (0,033 mol) were added dropwise within 5 minutes. Again a spontaneous exothermic reaction resulted. The benzene was evaporated leaving 7,61 g of a colorless, crystalline residue. After recristallisation from benzene/petrol ether 6,41 g N-benzyl oxycarbonyl methane sulfonamide, colorless crystals, fp. 111° to 112° C., were obtained. Structure: ______________________________________ ##STR13##______________________________________IR-spectrum (KBr): 3250 cm.sup.-1 ν(NH) 1750 cm.sup.-1 ν(CO) 1345 cm.sup.-1 ν(SO.sub.2)as 1155 cm.sup.-1 ν(SO.sub.2)s .sup.13 CNMR-spectrum 152,42 ppm CO(acetone d.sub.6) ##STR14## 68,48 ppm CH.sub.2 41,25 ppm CH.sub.3 .sup.1 HNMR-spectrum 9,98 ppm, s, 1 H, exchangeable for(acetone d.sub.6) D.sub.2 O, for NH 7,37 ppm, s, 5 H for C.sub.6 H.sub.5 5,20 ppm, s, 2 H for CH.sub.2 3,25 ppm, s, 3 H for CH.sub.3.______________________________________
Sulfonyl isocyanates having the formula R--SO 2 --NCO (wherein R is a C 1 - to C 18 - alkyl radical, a phenyl radical, a C 1 - to C 18 - alkyl phenyl radical or an isocayanate group) are obtained in high yield and excellent purity by reaction of the corresponding sulfonyl chlorides R--SO 2 --Cl with trimethyl silyl isocynate in the presence of catalytic amounts of Lewis acids. The preferred Lewis acids are halides having the formula AX n (A=B, Al, Ti, Sn, V, Sb, Fe or Zn; n=valence of A).
2
This application is a continuation application of application Ser. No. 08/840,647, filed Apr. 25, 1997, Now U.S. Pat. No. 6,136,214. BACKGROUND OF THE INVENTION The present invention relates to a plasma processing method and a plasma processing apparatus and, more specifically, to plasma etching used for a dry etching process that ionizes a source gas in a gas phase and processes the surface of a semiconductor material by physical or chemical reaction of highly activated particles of the plasma. With the advance of miniaturization of semiconductor devices in recent years, there has been a growing tendency to form a wiring layer in multiple layers and to make the device structure three-dimensional. Under these circumstances, the fabrication of an isolation film used to keep wires and devices electrically isolated from one another has come to play an increasingly important role in the device manufacture. Etching of a silicon oxide film, the isolation film, has been done by using perfluorocarbon gas (PFC), such as CF 4 and C 2 F 8 , and hydrofluorocarbon gas (HFC), such as CH 2 and CHF 3 . This is because a carbon-containing gas is needed to cut off an Si—O bond of the silicon oxide film and generate a volatile compound. As global environmental concerns are attracting growing attention, PFC and HFC are expected to be subjected to limited use or become difficult to obtain in the future because these gases easily absorb infrared rays, stay in atmosphere for as long as 3000 years and thus contribute greatly to the greenhouse effects on the earth. The PFC and HFC gas plasmas contain fluorine, fluorocarbon radicals such as CF 1 , CF 2 and CF 3 , and ions. An etching mechanism of a silicon oxide film operates as follows. These reactive species (e.g., radicals) stick to the surface of the silicon oxide film to be etched. The energy of ions incident on the surface gives rise to a localized quasi-high temperature condition, under which volatile products are formed by chemical reaction. Hence, to obtain good etching characteristics requires controlling the reactive species incident on a sample intended for etching and also controlling the energy and density of ions impinging on the sample. The control of the reactive species and of the density of ions in the plasma has been conducted by a plasma producing system in the etching equipment. To generate reactive species in a reactor, Japanese Patent Laid-Open No. 74147/1995 for example discloses a method which involves forming the interior of the reactor using a carbon-based material and supplying carbon components into a plasma for etching. Japanese Patent Laid-Open No. 363021/1992 describes making the reactor using ceramics to prevent degradation in the etching action of reactive species on the sample being etched and also discloses arranging a heater around the periphery of the reactor to alleviate plasma's thermal shocks on the ceramics reactor. When PFC and HFC gas plasmas are used, fluorocarbon- or carbon-based polymers adhere to the inner wall of the reaction chamber as the etching process of the sample proceeds. A method of removing the adhering polymers is known, which, as described in Japanese Patent Laid-Open No. 62936/1993, involves the installation of split, multiple electrodes-isolated from an outer wall of the reaction chamber-on the inner wall of the reaction chamber and the application of a radio frequency (RF) voltage between plasma generating electrodes successively to perform plasma cleaning. Further, Japanese Patent Laid-Open No. 231320/1989, 231321/1989 and 231322/1989 describe plasma cleaning methods which involve applying a voltage to electrodes electrically isolated with respect to the outer wall of the reaction chamber. If such a conventional plasma cleaning is performed, there still will be particles adhering to the inner wall of the reaction chamber before the next cleaning operation. Because fluorine in the plasma reacts with the adhering layer on the inner wall of the reaction chamber, the fluorine density in the plasma decreases gradually, increasing the ratio of carbon in the plasma. That is, as a growing amount of particles adheres to the inner wall of the reaction chamber, the radical composition changes, causing a time-dependent change in etching characteristic, which poses a serious problem. Etching equipment can be classified, according to the plasma producing system, into a capacitive coupling type, an ECR (electron cyclotron resonance) type, an ICP (induced coupling) type, and a surface wave excitation type. In the capacitive coupling type etching equipment, a material to be etched is placed on a bottom electrode and two voltage application systems apply differing frequencies and voltage to the upper electrode and the bottom electrode to control the plasma generation and the energy incident on the sample. The structure of this equipment, however, does not allow independent control of plasma generation and incident energy. The control of excited species in this equipment is considered to be performed by carbon or silicon used in the electrodes. However, no parameters on this control are available. Hence, it is necessary to perform three controls, i.e., control of the ion density, control of the energy of ions incident on the material being etched and control of reactive species, by controlling two, upper and lower, power supplies. Therefore, the range of parameters in which satisfactory etching characteristics can be obtained (defined as a process window) is narrow, making it difficult to produce stable etching conditions. The parameters that determine the etching characteristics include, in the plasma generation system, for example, RF power and microwave power applied between the electrodes, gas flow rate, gas pressure and gas composition. In the incident ion energy control, the etching characteristic determining parameters include the waveform and the frequency of the applied voltage and power. In the plasma generation methods other than the capacitive coupling type, although the plasma generation control and the energy control of ions incident on the sample can be performed independently of each other, the mechanism for controlling the reactive species depends on the plasma generation control. Hence, these plasma generation methods have a drawback of having a narrow process window. In more detail, when a silicon oxide film of SAC (self-aligned contact) is processed in the high density plasma etching equipment, such as an ECR, there is a problem of a tradeoff between etch stopping at the bottom of holes and over-etching into a silicon nitride film. Further, the use of a high density plasma to perform a highly selective etching gives rise to another problem, a micro-loading phenomenon or RIE lag, in which the etching rate decreases as the hole diameters decrease, and an inverted micro-loading phenomenon or inverted RIE lag. Further, when metal films, such as TiN and Al laminated layers, are etched using this equipment, localized abnormal side-etched portions are formed (notching) at the boundary between different materials, such as TiN and Al. Furthermore, with the method described in Japanese Patent Laid-Open No. 74147/1995, it is not possible to control the appropriate amount of excited species, making it difficult to perform an intended etching. The method disclosed in Japanese Patent Laid-Open No. 363021/1992 has a drawback of not being able to generate reactive species in the reactor. SUMMARY OF THE INVENTION The above problems can be solved by generating an exact amount of reactive species required for the etching in a region where the plasma comes into contact with the material to be etched. This is detailed in the following. In the process of etching a silicon oxide film and a silicon nitride film on the sample to be processed, a gas containing fluorine, for example, is introduced into the reaction chamber, which is kept at a low gas pressure of 0.3 Pa to 200 Pa. An electric discharge is produced in the gas by applying an input power in the microwave and RF wave ranges to the gas to generate a plasma. Then, a solid material containing carbon, which is installed in the region where it contacts the plasma, has a DC or RF voltage applied thereto to release a required amount of carbon, thereby transforming fluorine radicals in the plasma into fluorocarbon radicals such as CF, CF 2 , CF 3 , CF 4 for etching the material. A gas containing fluorine, but not carbon, is introduced into the reaction chamber where the fluorine-containing gas reacts with the solid carbon allowing the silicon oxide film and silicon nitride film to be selectively etched without using PFC or HFC. That is, a plasma is produced from a fluorine gas not containing carbon and fluorine atom ions are made to react with solid carbon installed in the reaction chamber to produce compounds of carbon and fluorine, such as CF 4 , CF 2 , CF 3 and C 2 F 3 . These compounds, radical molecules, have conventionally been able to be generated directly from dissociation of the PFC gas. These radical molecules thus generated have been used for etching the silicon oxide film. The present invention is characterized in that reactive species required for etching the silicon oxide film and silicon nitride film are not supplied directly from PFC or HFC gas, but rather are generated from reaction with the solid carbon in the plasma chamber. This method makes it possible to generate reactive species necessary for etching so that the etching can be performed while maintaining selectivity as in the conventional process, even when the use of PFC and HFC gas is restricted or prohibited. As for the improvement of selectivity and process margin during the process of making self-aligned contacts, this can be achieved by transforming reactive species into a single species of CF2, the etchant for the silicon oxide film. We have found that using carbon as the material for radical control and arranging it on the boundary surface with plasma can reduce the amount of fluorine in the plasma to one-half and increase CF 1 , CF 2 and CF 3 fivefold, tenfold and twofold, respectively, when compared to the case where aluminum is used as the radical control material. This is shown in FIG. 2, which illustrates the result of measurement of fluorine and CF 2 in a CF 4 plasma when Al, SiO 2 and C are used for the radical control materials. The result indicates that when aluminum is used as the radical control material, there is no reaction with fluorine so that the fluorine atom density is large and that when carbon is used, the fluorine atom density is reduced to one-half. This means that a conversion reaction is considered to have occurred in which the carbon as the radical control material reacts with fluorine in the plasma to increase CF 2 . It is also found that during this process CF 1 and CF 2 have also increased. The fact that the use of SiO 2 as the radical control material has resulted in reductions in CF 1 , CF 2 and CF 3 indicates that chemical reactions have occurred between CF 1 , CF 2 and CF 3 and the radical control material, SiO 2 . In this way, by placing in the plasma region a radical control material that reacts with reactive species in the plasma to produce volatile products, it is possible to transform the radical composition in the plasma. The use of silicon and silicon carbide for the radical control material, too, is found to cause chemical reactions that generate volatile products such as SiF 2 , thereby reducing fluorine in the plasma. It was also found that the transforming of reactive species into a single selected species can be promoted by installing a voltage application system on the radical control material and applying a voltage to the radical control material during the sample etching. FIG. 3 shows densities of radicals, CF 1 , CF 2 and CF 3 , measured by applying a negative DC voltage to carbon, the radical control material, in a CF 4 gas plasma. It was found that as the applied voltage increases, CF 3 decreases and CF 2 increases. This phenomenon results from an ion-assisted reaction on the radical control material. Because of this phenomenon, fluorine in the plasma is transformed into CF 2 and the plasma containing a single reactive species enables selective etching, in which reaction products on the silicon oxide film evaporate allowing the etching of the silicon oxide film to continue, whereas residual materials on the silicon nitride film stop the etching. This eliminates a problem of shoulder etching of the nitride film that would occur due to reduced selectivity. While the conventional etching balances carbon and fluorine, this invention is characterized by the use of CF 2 , which has a lower sticking parameter for sidewalls of the features being etched than that of carbon. This has been found to suppress the micro-loading and inverted micro-loading phenomena. When etching samples having materials with largely differing etch rates, the following steps are taken. For the radical control material we use a compound which includes the same elements as those of the materials to be etched or at least one of the same elements as those of the etched materials. Depending on the material to be etched, the voltage applied to the radical control material is controlled according to the etching time or by monitoring the consumption or release of a certain kind of radical from the radical control material. This process is found to minimize localized abnormal deformations that would occur between different materials. The problem of local deformations between different materials during metal etching can be solved by minimizing variations of the etchant. That is, this problem was able to be eliminated by using a radical control material having the same components as the material being etched and controlling the density of radicals according to the etching time or the monitoring of the result of radicals. The time-dependent change of etching characteristic can be minimized by removing deposits from the surface that is in contact with the plasma. That is, by arranging the radical control material so as to enclose the plasma and then applying a voltage from outside during the etching of the sample, it was possible to automatically remove deposits adhering to the plasma contact surface. It is also noted that application of voltage during the sample etching process has improved the through-put. FIG. 5 shows the result of measurements by a step meter of a layer deposited when an arbitrary voltage was applied to an aluminum plate placed on a surface contacting a C 4 F 8 plasma having a pressure of 1.5 mTorr and a microwave power of 200 W. The deposited film thickness depends on the density of the plasma, and deposits can be prevented from adhering to the surface by applying an appropriate voltage to the boundary surface with plasma, thus minimizing time-dependent variations in the etching characteristics. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a cross section of a plasma etching apparatus, representing a first embodiment of this invention, mounting a radical control material; FIGS. 2 ( a ) and 2 ( b ) are graphs showing the densities of fluorine and CF 2 , respectively, in a CF 4 plasma when Al, SiO 2 and C are used as the radical control materials; FIG. 3 is a graph showing changes in the densities of radicals, CF 1 , CF 2 and CF 3 , when a negative DC voltage is applied to a radical control material of carbon in the CF 4 gas plasma; FIG. 4 ( a ) is a diagram showing a resist-TiN-Al-TiN laminated structure etched by a conventional ECR plasma etching equipment and FIG. 4 ( b ) is a graph which shows changes in the density of chlorine atoms present in the plasma; FIG. 5 is a diagram showing the thickness of a deposited layer when a voltage is applied to an aluminum plate placed on a surface contacting the C 4 F 8 plasma; FIG. 6 is a waveform diagram showing a plasma potential, an applied voltage, a plasma sheath voltage and a self-bias voltage when an area of the radical control material is almost equal to an area of a portion that determines the plasma potential; FIG. 7 is a diagram showing timings for applying voltages to each of three divided blocks of the radical control material; FIGS. 8 ( a ) and 8 ( b ) are schematic diagrams showing the operation of a voltage application circuit incorporating a relay circuit when the radical control material is divided into three blocks; FIG. 9 ( a ) is a schematic diagram showing the configuration of the voltage application circuit connected to a multiple phase power supply and FIG. 9 ( b ) is a waveform diagram showing a plasma potential, applied voltages, plasma sheath voltages and a self-bias voltage; FIG. 10 is a schematic diagram of an embodiment of a means to detect the deposition rate or sputter rate on the radical control material; FIG. 11 is a schematic diagram showing an ECR type UHF wave plasma etching equipment using a gas composition and a radical control material of this invention; FIG. 12 is a cross section of an etching apparatus according to this invention which applies a capacitive coupled plasma to the plasma generation system; FIG. 13 is a cross section of an etching apparatus according to this invention which applies an induced coupled plasma to the plasma generation system; FIG. 14 is a cross section of an etching apparatus according to this invention which applies a surface wave plasma to the plasma generation system; FIG. 15 is a cross section of an etching apparatus according to this invention which applies a magnetron RIE plasma to the plasma generation system; FIG. 16 ( a ) is a diagram showing a structure of a sample before the SAC (self-aligned contact) forming process by the oxide film etching is performed, FIG. 16 ( b ) is a diagram showing a shoulder-etched condition resulting from a conventional SAC process, FIG. 16 ( c ) is a diagram showing an etch stop condition during a conventional SAC process, and FIG. 16 ( d ) is a diagram showing an etched shape when an SAC process according to this invention is performed; FIG. 17 is a schematic diagram showing a mechanism for controlling the magnitude and frequency of an RF voltage to be applied according to the sample process time; FIG. 18 is a diagram showing a conductive plate inserted between the radical control material and an insulator and connected to the voltage application circuit; FIG. 19 is a cross section of an etching apparatus according to this invention which applies a magnetron RIE plasma to the plasma generation system; FIG. 20 is a cross section of an etching apparatus according to this invention which applies a parallel plate plasma to the plasma generation system; and FIG. 21 is a diagram showing an etched structure of a TiN—-Al—-TiN metal wiring layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 FIG. 1 is a schematic diagram of an etching apparatus according to this invention as seen from the side, and which employs an ECR plasma, one of the plasma generation systems that utilize interaction between magnetic fields and electromagnetic waves. A reaction chamber 104 includes a microwave introducing window 103 , an evacuating system 108 and a gas introducing pipe 109 , and there is also a sample holder 107 inside the chamber on which to place a sample 106 . The plasma generation system comprises a microwave generator 101 , a waveguide 102 and an electromagnet 105 . The sample holder 107 is connected with an RF power supply 110 that accelerates ions incident on the sample 106 . The RF power supply 110 produces radio waves at several hundred kHz to several tens of MHz, which accelerate ions that impinge on the sample 106 promoting the etching process. A gas is introduced from the gas introducing pipe 109 into the reaction chamber 104 where a plasma 113 is generated. When performing etching on an oxide film, in particular, a fluorocarbon gas plasma is used, which contains reactive species such as fluorine, CF 1 , CF 2 and CF 3 . If there is an excess amount of fluorine in the plasma, both a nitride film and an oxide film are etched during, for example, an SAC process, which means it is difficult to perform a selective etching. Thus, to perform selective etching during the SAC process, it is necessary to reduce the amount of fluorine in the plasma. This etching equipment newly incorporates a radical control material 112 that contains materials that will control reactive species. The radical control material 112 is temperature-controlled by a heater 116 , a cooling pipe 117 and a temperature control circuit 121 . The temperature is monitored by a temperature monitor 114 . The temperature control will be explained in Embodiment 5 . In this equipment the plasma state is monitored by an optical emission spectrometer having a feedback circuit. It has been found that applying a voltage to the radical control material 112 further promotes the above-mentioned transformation reaction. A means for applying a voltage to the radical control material 112 is constructed by inserting an insulator 111 between the radical control material 122 and the reaction chamber 104 and installing a voltage application circuit 115 consisting of a blocking capacitor 118 and an AC power supply 119 . The blocking capacitor blocks a DC current from the plasma and produces a DC voltage Vdc that enables ions to be accelerated effectively. The voltage application circuit 115 may use an AC power supply 119 , a pulse power supply or, if the radical control material is a conductive material, a DC source. The insulator 111 is preferably made of alumina and silicon nitride that can withstand a temperature as high as 400° C. It is of course not necessary to provide the insulator 111 if a voltage is not applied. When insulators such as quartz and silicon nitride are used for the radical control material 112 , a better voltage introducing efficiency is obtained if a conductive plate 401 is inserted between the radical control material 112 and the insulator 111 as shown in FIG. 18, and the conductive plate 401 is connected with the voltage application circuit 115 . FIG. 3 shows measurements of the densities of radicals CF 1 , CF 2 and CF 3 when a negative DC voltage is applied to the radical control material 112 of carbon in the CF 4 gas plasma. It is found that, as the applied voltage increases, CF 3 decreases and CF 2 increases. This results from an ion-assisted reaction in which chemical reactions are accelerated by localized quasi-high temperature conditions that are generated by ions impinging on a fluorocarbon-based layer deposited over the radical control material. Generally, chemical reaction products formed at high temperatures are known to be likely to produce molecules that are unstable at normal temperatures at which there are fewer atoms to combine. For example, chlorine atoms adsorbed onto a silicon substrate are known to produce SiCl 2 from a chemical reaction with the base silicon at the substrate temperature of 600° C., whereas it produces SiCl at 900° C. Hence, under the ion energy obtained in our experiments, it is assumed that CF 2 is likely to be produced stably. That is, by utilizing the ion-assisted reaction, which is obtained by using carbon for the radical control material 112 in the fluorocarbon gas plasma and applying a voltage to the radical control material, it is possible to transform F and CF 3 in the plasma into CF 2 and thereby control the reactive species in the plasma. The plasma density used determines the lower limit of the frequency of an RF voltage that can be applied to the radical control material. The plasma density used for etching is around 10 11 -10 12 particles/cm 3 and the corresponding saturated ion current density I e is around 10 −2 -10 −4 A/cm 2 . When an RF wave is applied to an electrode in the plasma, the frequency required is more than about I e /(CV). This relation is derived qualitatively from the fact that a voltage of the electrode that has dropped by the voltage application mechanism needs to change more rapidly than does the amount of ions flowing in that act to cancel the voltage change. Here, C is an electrostatic capacitance per unit area and is about 10 −11 farad, and V is an applied voltage and is around 10 2 volt. Thus, in the above plasma used for etching, the applicable frequency of the RF wave must be more than 100 kHz. The upper limit of the frequency, where ions can follow the voltage change and the effect of an ion-assisted reaction is produced, is found to be around 100 MHz. If a pulse power supply and a DC power supply are used for the voltage application circuit 115 , it is possible to localize the energy of ions incident on the radical control material and converge the transformation reaction path, allowing efficient, selective generation of reactive species by the ion-assisted reaction. When the radical control material is an isolator, the above effect can only be obtained by a pulse voltage. When it is a conductive material, however, a DC voltage should preferably be used also in terms of equipment cost. While the frequency of pulses used varies depending on the electrostatic capacitance of the voltage application system, a general system with a capacitance of about several tens of nF is required to have more than 100 kHz. The present invention can induce the ion-assisted reaction in a deposited layer on the radical control material 112 to transform reactive species into a desired species effective for etching or removing selected species, not only when a fluorocarbon gas plasma is used but also when a carbon-based gas is used or when an organic resist is used as a mask. Embodiment 2 An embodiment for etching a silicon oxide film without using PFC or HFC gas now will be described. In the embodiment that employs the ECR type microwave-discharged plasma, as shown in FIG. 1, no electrode is disposed opposite the wafer. Because carbon cannot be used for the electrode opposing the wafer, it is theoretically difficult to perform etching with a gas not containing carbon. In our experiment, however, SiC was selected for the radical control material 112 and a gas containing Ar and SF 6 but not carbon was introduced into the reaction chamber 104 . The total gas flow was set at 20-300 sccm and SF 6 was changed in the range of 1-10 sccm. The electric discharge pressure was set at 0.1-5 Pa. The introduced gas was ionized and reacted with SiC to generate the reactive species necessary for etching. The wafer is covered with a silicon oxide film to be etched and the mask for the etching is formed of a photoresist, which has a fine pattern made by lithography. Formed under the silicon oxide film as underlying layers are a silicon nitride film and a silicon film. For the condition in which the etching rate of a SiC plate is in the range of 50 nm/min to 600 nm/min, the etching rate of the oxide film ranges from 400 nm/min to 2000 nm/min and the etching rate of the resist film ranges from 500 nm/min to 80 nm/min. That is, the etching rate of the resist can be adjusted by the etching rate of the SiC wall electrode to increase the selectivity. The etching rate of the silicon film also ranges in the similar way to the resist. To etch the silicon nitride film most selectively requires increasing the etching rate of the SiC wall electrode. That is, for the SiC etching rate of 250 nm/min, the oxide film etching rate was 1000 nm/min and the silicon nitride film etching rate was 70 nm/min, and the selectivity with respect to the silicon nitride film was 14.2. Under these conditions, the temperatures of the wall electrode and the wafer electrode were varied from −60° C. to 250° C. to investigate the effect of their temperatures on the etching. Our examination found that setting the temperature of the wafer electrode as high as possible enables selective etching of the silicon oxide film with respect to the silicon nitride film. A particularly preferred temperature was more than 0° C. At the SiC temperature of 200° C., the selectivity with respect to the silicon nitride film was 5 . As for the wall electrode, reaction products easily deposit on its surface at low temperatures. As in the case of the upper electrode, the temperature was found to constitute one of the factors that determine the etching rate on the electrode surface. Hence, the temperature needs to be kept at a constant value as practically as possible. In addition, as the temperature increases, the etching rate becomes high. When the temperature is set low, the efficiency of transformation reaction of the reactive species deteriorates. Thus, in the above temperature ranges, a desired etching rate can be set. This embodiment has demonstrated that when a gas plasma not containing carbon is used, a silicon oxide film can be etched at a high etching rate by including carbon in the solid surface contacting the plasma, by causing this solid to perform an etching reaction, and by setting the temperature of the solid at specifically more than 0° C. This has verified the effectiveness of this invention. The gas used in this embodiment that does not contain carbon is a gas mixture of Ar and SF 6 . Other inert gases such as Ne, Kr and Xe may be used. A fluorine-containing gas, such as SF 6 , though it has a high greenhouse effect coefficient and a long lifetime and is thus not desirable, has the advantage of requiring only a very small consumption. Effective gases other than SF 6 include F 2 , HF, XeF 2 , PF 3 , BF 3 , NF 3 , SiF 4 , and halides such as fluorine chlorides ClF and ClF 3 , fluorine bromides BrF, BrF 3 and BrF 5 and fluorine iodide IF 5 . It is also found that materials that can play a similar role to that of SiC include a pyrolytic graphite plate, an organic resin film, SiCN, a diamond plate, Al 4 C 3 , and a carbon-containing material such as boron carbide. A structure having these carbides formed on the surface of other materials can similarly produce reactive species necessary for etching. Embodiment 3 An embodiment that uses for the radical control material the same material as the one to be etched will be explained. The use of such a material is particularly effective in improving abnormal deformations that would occur when etching a sample having laminated layers of different materials in the same plasma. For example, FIG. 4 ( a ) shows a cross section of a laminated structure consisting of a resist layer 301 , a TiN layer 304 , an Al layer 303 and a TiN layer 304 formed over an SiO 2 layer 305 , after being etched in a chlorine plasma by conventional ECR plasma etching equipment during a metal wiring process. As shown in the figure, the etched shape obtained with the conventional equipment has defects (notched portions) in the Al portion 302 at the boundary with the upper TiN layer 304 . FIG. 4 ( b ) shows variations in chlorine atom density in the plasma during etching. The graph indicates that the chlorine atom density 307 at the notched portion sharply decreases from a high chlorine atom density 306 , that corresponds to the TiN etching, to a low stable density 308 , which corresponds to the Al etching. This means that abnormal deformations are produced during the etching process corresponding to the notched portion 302 because of an excessively high chlorine atom density. The use of Al for the radical control material 112 during etching can lower the chlorine atom density during the etching of the TiN 304 to the chlorine radical density 309 (FIG. 4 ( b )) by consuming the chlorine atoms with aluminum atoms from the wall surface. This minimizes a sharp change in the chlorine radical density when the layer being etched switches to the aluminum layer. This is shown in FIG. 21 . That is, when the etching process moves from one layer to another with different consumptions of reactive species, excess reactive species may remain. This is considered the major cause for the abnormal deformations between different materials. Hence, when etching a layer with a smaller consumption of reactive species, the radical control material has a voltage applied thereto which is sufficient to consume the etchant and thereby make the amount of reactive species impinging on the sample constant. With this method, variations in the etchant density were minimized. Because the use of radical control material which is the same material as the mask can reduce variations in the densities of oxygen and carbon in the plasma produced from the etched mask material, it is possible to form a sidewall protection film that is stable over time and to produce a desirable etched configuration with no undercut 310 (FIG. 4 ( a )). This invention is also applicable to other laminated layer structures. They include, for example, a resist-polysilicon lamination structure, an SiO 2— Si 3 N 4 structure, an Al—W—Al structure, a TiN—AlCu—TiN—Ti structure, a TiN—Cu—TiN structure, an SiO 2 mask-Pt structure, and a polysilicon-SiO 2 structure. For these laminated structures, it is necessary to use polysilicon, Si 3 N 4 , W, Al, Cu, Pt and SiO 2 for the radical control material. While the effectiveness of this invention is assured if the radical control material includes the same material as the material being etched, a similar effectiveness can be obtained if other materials are used whose rate of reaction with the etchant is similar to the etchant reaction rate of the material being etched. In this case, the difference in the etchant density between different materials is roughly the ratio between the areas of the etched surface and the radical control material. The surface of the sample to be etched comprises a mask portion and a material portion to be etched. It is possible to minimize a change in the density of reactive species by making the area of the radical control material in contact with the plasma larger than the area of the mask portion or the material portion, whichever is smaller. Embodiment 4 Another embodiment will be described which shows a method and system for applying a voltage to the radical control material. When, during the application of an RF wave to the radical control material, the area of the radical control material is almost equal to the area of a portion that determines the plasma potential, the plasma potential 602 changes following the applied voltage 601 , as shown in FIG. 6 . When this applied voltage, follow phenomenon of the plasma potential 602 takes place, the sheath voltage 603 between the plasma and the radical species control material becomes as shown at 603 and its DC component, a self-bias voltage 604 , is no longer applied, making it impossible to control the energy of ions incident on the sample 106 and the radical control material 112 This must be avoided. For this purpose, it is effective either to make the area of the radical control material to be supplied with a voltage smaller than the area of the portion that determines the plasma potential, or to reduce the amount of ions flowing in one cycle by increasing the frequency of the applied voltage, or to increase the capacitance of the blocking capacitor 118 . It is preferred that the radical control material 112 be divided into a plurality of isolated blocks. This method reduces the total amount of ion current entering from the plasma when a voltage is applied, and is thus effective in avoiding the applied voltage-follow phenomenon of the plasma potential. Another effective method is shown in FIG. 8 ( a ) and FIG. 8 ( b ), which are schematic diagrams representing the operation of the voltage application circuit, which has the radical control material divided into three blocks 802 , 803 , 804 isolated from one another by an isolator 111 and which incorporates a relay circuit 801 . The relay circuit 801 can further reduce the area ratio between the block portion supplied with a voltage and a portion that determines the plasma potential (in this case the ground portion). A similar effect can be obtained if a plurality of radical control materials of small areas are arranged. The operation of the relay circuit 801 when the three divided radical control materials are supplied with RF voltages at timings shown in FIG. 7 will be explained by referring to FIG. 8 ( a ) at time 1 and FIG. 8 ( b ) at time 2 . First, at time 1 , a block 802 is connected to the RF power supply 119 , with other blocks grounded. Next, at time 2 . a block 803 is connected to the RF power supply 119 , with other blocks grounded. Likewise, at time 3 , a block 804 is connected to the RF power supply 119 with other blocks grounded. In this way, by successively applying a voltage to one block at a time and grounding the remaining blocks, it is possible to effectively prevent variations of the plasma potential. Although the radical control material is divided into three blocks in this case, it only needs to be divided into two or more to attain similar effects. While the method of FIG. 8 ( a ) and FIG. 8 ( b ) can satisfy the need of only removing deposits, the efficiency of controlling reactive species is considered to deteriorate as the area of the radical control material decreases. To cope with this problem, a multiple phase RF power supply 901 , instead of the RF power supply 119 , is connected to the three divided blocks, i.e. block 802 , block 803 and block 804 , as shown in FIG. 9 ( a ), to apply RF waves of different phases to these blocks simultaneously (the block 802 is supplied with a sine wave 902 with an initial phase of 0 degree, the block 803 is supplied with a sine wave 903 with an initial phase of 120 degrees, and the block 804 is supplied with a sine wave 904 with an initial phase of 240 degrees). This smoothes out the plasma potential 602 with respect to time, as shown in FIG. 9 ( b ). Because voltages can be applied to a plurality of blocks at the same time, the reactive species control efficiency is improved over the method of FIG. 8 ( a ), which in turn leads to an improved deposit removing efficiency. This method can also be implemented by using a plurality of RF poller supplies of different phases. For controlling the energy of ions incident on the radical control material, it is of course possible to produce a similar effect by applying different frequencies to the divided blocks. Embodiment 5 An embodiment that has a temperature control mechanism for the radical control material will be described in the following by referring to FIG. 1 . For the control of reactive species, this invention provides two methods, one that utilizes the fact that there are different stable products at different temperatures during the process of chemical reaction and one that performs macroscopic control on the temperature of the radical control material. Both methods are effective for the control of reactive species. The temperature of the radical control material 112 during the operation of the equipment is kept constant without using heat from the plasma to keep constant the amount of desorbed substances from the radical control material 112 , such as oxygen, water and hydrogen, and the efficiency of chemical reaction at all times. An example of a way to keep the temperature of the radical control material constant comprises use of a heater 116 as a heating means, a cooling pipe 117 as a cooling means,,a temperature monitor 114 as a temperature sensing means, and a temperature control circuit 121 that regulates the temperature of the heater 116 and the cooling pipe 117 in response to the measurement from the temperature monitor 114 . The heating means may use an infrared lamp and the cooling means may use liquid nitrogen, water or oil. Embodiment 6 An embodiment will be described which shows a system that controls the voltage and frequency to be applied to the radical control material according to the amount of reactive species in the plasma, the deposition rate on the radical control material 112 , the plasma condition and the sample processing condition. As seen in FIG. 1, an insulator 111 is disposed inside a reaction chamber 104 . An embodiment having a means to detect the deposition rate and sputter rate on the radical control material is shown in FIG. 10 . The sputter rate detection means has a quartz oscillator probe 1001 on which there is sputtered a substance 1003 constituting the radical control material, the quartz oscillator probe 1001 being connected to the RF power supply 119 through a blocking capacitor 118 , so that the substance 1003 can be supplied with the same voltage as is applied to the radical control material 112 . The rate at which the particles are adhering to or removed from the radical control material during the operation of the etching equipment is measured from changes in the oscillation of the quartz, and a voltage corresponding to the oscillation changes is fed back from the feedback circuit 1002 to the voltage application circuit 115 in order to control the voltage and frequency applied to the radical control material 112 and thereby control the etching rate to an appropriate level. This prolongs the life of the radical control material 112 and also makes it possible to deal with the constantly changing plasma conditions. A detector to detect a change in the amount of reactive species in the plasma includes an optical emission spectrometer 120 , as seen in FIG. 1, and an electric circuit which, based on an increase or decrease in the amount of reactive species, controls the voltage applied to the radical control material. This detector controls the amount of reactive species in the plasma in real time and keep it constant at all times. FIG. 17 shows a control system for controlling an RF applied voltage and frequency according to the sample process time. For the time control, a time control computer 1701 and a control program are used. Based on the programmed time sequence, the computer changes the voltage and frequency applied to the radical control material 112 over time. Digital signals corresponding to the voltage and frequency values from the time control computer 1701 are converted by a D/A converter 1702 into analog voltages, which are then fed to the voltage application circuit 115 that changes the voltage and frequency applied to the radical control material 112 . This method has fewer mechanisms to be added to the reaction chamber and allows arbitrary time control from outside the reaction chamber. That is, if the etching rate and the thickness of a film to be etched in the sample process are known, the voltage and frequency values corresponding to the process time can be freely programmed and set, and this method can be advantageously implemented at relatively low cost. For the above embodiment to be realized, the voltage application circuit 115 needs to have the ability to change the voltage and frequency to be applied to the radical control material 112 by, for example, an input voltage from outside. Embodiment 7 An embodiment that sets the DC component (self-bias voltage) applied to the radical control material to −20 V or less will be described. To accelerate positively charged ions requires the use of at least a negative bias, i.e., a voltage lower than 0 V. It is assumed that the area of chemical reaction based on the ion-assisted reaction is almost proportional to the range of incident ions. For example, the range R (Å) of Ar ion having the energy R (eV) of less than 1000 eV is known to have the following elation: R= 0.08× E In this case, it is necessary that there is at least one molecule in the reaction region that participates in the reaction. Because quartz with a short interatomic distance among the possible reaction species producing materials has an Si—O bond of 1.62 Å, the reaction species transformation requires an ion energy of at least 20 ev. Thus, by setting the voltage applied to the radical control material to less than −20 V, the reactive species control can be performed efficiently. Embodiment 8 An embodiment which sets the DC component (self-bias voltage) applied to the radical control material to −50 V or higher will be explained. FIG. 5 shows a measurement taken by a step meter of the thickness of a deposited film over an aluminum sample placed in a C 4 E 8 gas plasma generated by an ECR plasma system that operates at 800 kHz. The measurement shows that for the condition of 1.5 mTorr and microwave power of 200 W, setting the self-bias voltage, which is a DC component of the sheath voltage, to −45 V results in the surface with no deposits and with its ground aluminum layer remaining not etched. The result of measurement suggests that, considering the surface roughness errors of the aluminum sample used for the measurement, the condition under which the radical control material is not etched can be produced by setting the applied voltage to more than −50 V. Because these voltages change depending on the unique sputter threshold voltage for the adhering reactive species, the amount of species incident on the radical control material and the plasma density, they may be adjusted by the above sputter rate detection means. Therefore, there is an applied voltage between 0 V and −50 V that permits sputtering of only the carbon-based deposits. By applying this voltage during the sample processing, not only can the reactive species control be performed, but also deposits on the plasma boundary surface can be removed, which in turn shortens or eliminates the oxygen cleaning, improving the total throughput. In this case, the sample processing and the voltage application to the radical control material may be performed at different timings. The plasma boundary surface can also be cleaned in a similar manner by introducing a cleaning gas (oxygen, argon, etc.) in the above equipment. Embodiment 9 Effective use of a gas according to this invention will be explained by referring to FIG. 11 in an example of etching a silicon oxide film in UHF wave plasma etching equipment using a magnetic field. This embodiment uses ClF 3 as a gas not containing carbon. The inert gas used is a mixture of Ne, Ar, Kr and Xe. Fluorine-containing gases, such as SF 6 and NF 3 , though they have a high greenhouse effect coefficient and a long lifetime and are thus not desirable, have the advantage of requiring only a very small consumption. ClF 3 has a similar advantage. In this embodiment, a UHF wave radiation antenna 71 is disposed opposite the wafer and is formed of a pyrolytic graphite plate. It is found that the pyrolytic graphite plate needs only to be made of a carbon-containing material, such as SiC, an organic resin film, SiCN, a diamond plate, Al 4 C 3 , and a boron carbide. A similar effect is also obtained if these carbides are formed on a surface. A low-path filter and an RF power supply are installed outside the UHF wave radiation antenna 71 to form an opposing electrode structure in which generated particles impinge on the sample efficiently, enhancing the effectiveness of the reactive species control. The total gas flow was set at 50-500 sccm and SF 6 was changed at the rate of 1-10 sccm. The pressure for electric discharge was set at 0.5-5 Pa. A UHF wave is transmitted from a plasma discharge UHF wave source 74 through a coaxial cable 79 and is emitted from the radiation antenna 71 to produce a plasma. A bottom wafer electrode 107 is supplied with an RF power 110 that accelerates ions in the plasma. The distance between the upper and lower electrodes was set at 10-200 mm and a mechanism was provided for applying the RF power 119 to the pyrolytic graphite plate, the radical control material 112 . Denoted at 78 is a magnet. The wall uses surface-treated SiC as a carbon-containing material. Applying power to SiC causes the SiC to be etched by the plasma. The wafer is similarly formed with a silicon oxide film as a film to be etched. The etching mask was formed of a photoresist, which was finely patterned by lithography. The underlying layer for the oxide film used a silicon nitride film and a silicon film. When the oxide film is etched under the condition that the etching rate for the pyrolytic graphite plate of the upper electrode is 50 nm/min to 600 nm/min, the etching rate for the oxide film varied from 400 nm/min to 1400 nm/min and the etching rate of the resist film varied from 600 nm/min to 60 nm/min. This means that the etching rate of the resist can be adjusted by the etching rate of the Sic wall electrode to increase the selectivity. The etching rate for the silicon film also varied in the same way as the resist. To etch the silicon nitride film most selectively requires increasing the etching rate for the SiC wall electrode. Under this condition, the temperatures of the upper and lower electrodes and the wall electrode were changed from −60° C. to 250° C. to investigate the effect the temperature has on the etching. It was found that selective etching of the silicon oxide film with respect to the silicon nitride film can be assured by setting the wafer electrode temperature as high as possible. A particularly preferred temperature was more than 0° C. The temperature of the upper electrode was one of the factors that determine the etching rate of the electrode surface. Hence, the temperature must be kept as constant as practically possible. Further, as the temperature increases, the etching rate becomes high. Setting the temperature low reduces the efficiency of transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature ranges, a desired etching rate can be set. As for the wall electrode, reaction products easily deposit on its surface at low temperatures. As in the case of the upper electrode, the temperature was found to constitute one of the factors that determine the etching rate on the electrode surface. Hence, the temperature needs to be kept as constant as practically possible. It is also found that the higher the temperature, the faster the etching rate and that setting the temperature low reduces the efficiency of transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature ranges, a desired etching rate can be set. This embodiment has thus demonstrated that when ClF3 is used as a gas not containing carbon, this invention can etch a silicon oxide film at a high etching rate by including carbon in a solid surface contacting the plasma, by causing this solid to perform etching reaction, and by controlling the temperature of the solid in a range of −60° C. to 250° C. This has verified the effectiveness of this invention. Embodiment 10 FIG. 14 shows an embodiment of this invention that employs a surface wave plasma as a plasma generation system. Electromagnetic waves from a waveguide 1402 impart a plasma energy through a dielectric 1401 to produce a plasma. Other elements and effects are similar to those of the ECR type plasma generation system. Embodiment 11 An embodiment that uses carbon as the radical control material in performing the SAC process will be explained. FIG. 16 ( a ) shows a structure of a sample before being subjected to the SAC process. A gate electrode 1504 of polysilicon is formed over a silicon substrate 1505 . The SAC process is an oxide film processing that forms contact holes by etching the oxide film 1502 with the nitride film 1503 as a stopper layer, and is a favorable method when forming contact holes in DRAMs of 256 M or larger. Denoted at 1501 is a resist. When a conventional method that has no reactive species control concept or in which the reactive species control system cannot be controlled independently, for example, high-density plasma etching equipment, is used to perform etching under the condition of C 4 F 8 5 mTorr and a microwave power of 1100 W, a variety of problems are encountered. For example, the shoulder portion of the nitride film is eroded as shown at 1506 in FIG. 16 ( b ), failing to keep the polysilicon gate 1504 isolated, or etching is stopped halfway at the bottom of the contact hole as shown at 1507 in FIG. 16 ( c ). In this way the process window for desirable selective etching is narrow. With this invention, it is possible to make the composition of a deposited film, essential for the etching reaction of an oxide film, suitable for selective etching. That is, fluorine that etches both the oxide film and the nitride film in the plasma is reduced in density and converted into CF 2 that is suited for selective etching. On the nitride film, this allows the deposits to remain minimizing the shoulder erosion and, on the oxide film, promotes a satisfactory surface reaction that allows etching to proceed smoothly. Hence, performing the SAC process using the method of this invention ensures a satisfactory etching geometry as shown in FIG. 16 ( d ). Embodiment 12 An embodiment that etches a silicon oxide film in a parallel flat plate type etching apparatus by introducing a gas not containing carbon in the compounds will be explained by referring to FIG. 20 . In this embodiment an electrode 1202 opposing the wafer 106 is made from a pyrolytic graphite plate. The discharge gas not containing carbon was a mixture of Ar and SF 6 . The gas mixture was supplied from the top of the chamber through a gas introducing hole in the pyrolytic graphite plate. The total gas flow was set at 100-500 sccm and SF 6 was changed in the range of 1-10 sccm. The discharge pressure was set at 1-5 Pa. The upper electrode was supplied with an RF power 1201 to produce a plasma. The bottom electrode 107 was supplied by an RF power 110 to accelerate ions in the plasma. The distance between the upper and bottom electrodes was varied in the range of 5-50 mm. The wafer used has formed thereon a resist film, a silicon oxide film, a silicon film and a silicon nitride film. Here, the silicon oxide film was etched with a photoresist as a mask. When the etching rate of the pyrolytic graphite plate of the upper electrode was changed from 100 nm/min to 1000 nm/min, the etching rate of the oxide film changed from 500 nm/min to 2000 nm/min and the etching rate of the resist film changed from 800 nm/min to 90 nm/min. The etching rate of the resist was able to be adjusted by the etching rate of the pyrolytic graphite plate to keep the selectivity high. The etching rate of the silicon film changed in a similar manner to the etching rate of the resist. This suggests that to etch the silicon oxide film most selectively requires setting the etching rate of the pyrolytic graphite plate to 100 nm/min or higher. This embodiment has demonstrated that the silicon oxide film can be etched at a high etching rate with a gas not containing carbon, verifying the effectiveness of this invention. Embodiment 13 This embodiment performs etching by using a parallel plate type plasma etching apparatus, like the one in the Embodiment 12, with a third electrode 112 arranged close to the wall surface of the plasma chamber. This embodiment will be explained by referring to FIG. 12 . The third electrode uses a surface-treated SiC 112 , which is supplied by a power 119 to etch the SiC with a plasma. The SiC 112 is temperature-regulated by a heater 116 and a cooling pipe 117 . Other elements are similar to those of the Embodiment 12. With the etching rate of the pyrolytic graphite plate of the upper electrode 1202 varied from 100 nm/min to 400 nm/min, the SiC 112 wall supplied by the power 119 to measure changes in the etching rate of the resist, silicon oxide film, silicon film and silicon nitride film on the wafer according to the etching rate of the SiC wall electrode. It was found that as the etching rate of the SiC electrode increased. the etching rate of the oxide film changed from 500 nm/min to 1500 nm/min and the etching rate of the resist film changed from 300 nm/min to 60 nm/min. In other words, the etching rate of the resist was able to be adjusted by the etching rate of the SiC wall electrode to keep the selectivity high. The etching rate of the silicon film also changed in the similar manner to that of the resist. It is also found that to realize the most selective etching of the silicon nitride film requires increasing the etching rate of the SiC wall electrode. This embodiment has demonstrated that the silicon oxide film can be etched at a high etching rate with a plasma of gas not containing carbon by including carbon in the solid surface in contact with the plasma and by causing an etching reaction on the solid. The effectiveness of this invention is therefore verified. For applying power to the wall of the plasma chamber, there are some effective means. Among them is a method that divides the wall electrode into a few blocks and applies different bias powers to them. A second method is to share the bias power source of the wafer with the wall electrode by setting two powers in different phases. The second method also has proved effective. Even when the distance between the upper and bottom electrodes is as small as 30 mm or less, the bias application to the wall electrode proved effective. To control the etching rate of the wall electrode with high precision, the waveform and frequency of the bias power applied to the wall electrode must also be controlled. With this precise control, it is possible to make precise, uniform setting of the ion energy distribution for desired etching. Embodiment 14 The silicon oxide film etching in a parallel plate type etching apparatus using a magnetic field, or magnetron RIE equipment, will be explained by referring to FIG. 19 . In this embodiment, the electrode 1202 opposite the wafer 106 was a pyrolytic graphite plate. The discharge gas was a gas mixture of Ar and SF 6 . This gas mixture was supplied from the top of the chamber through a gas introducing opening in the pyrolytic graphite plate. The total gas flow was set at 20-500 sccm and SF 6 was varied in the range of 1-10 sccm. The discharge pressure was set at 0.1-5 Pa. The distance between the upper and bottom electrodes was set at 10-200 mm. A surface-treated SiC 112 was installed close to the wall surface. Applying power to the SiC causes the SiC to be etched with the plasma. Other elements are similar to those of the Embodiment 12. With the etching rate of the pyrolytic graphite plate of the upper electrode being varied from 50 nm/min to 600 nm/min, power was applied to the SiC electrode to measure changes in the etching rates of the resist, silicon oxide film, silicon film and silicon nitride film on the wafer according to the etching rate of the SiC electrode. From the measurements it was found that as the etching rate of the SiC wall electrode increases, the etching rate of the oxide film changes from 400 nm/min to 1600 nm/min and the etching rate of the resist film changes from 500 nm/min to 60 nm/min. In other words, the etching rate of the resist was able to be adjusted by the etching rate of the SiC wall electrode to maintain a high level of selectivity. The etching rate of the silicon film also changed in the similar manner to that of the resist. It was also found that to realize the most selective etching of the silicon nitride film requires increasing the etching rate of the SiC wall electrode. This embodiment has demonstrated that the silicon oxide film can be etched at a high etching rate with a plasma of gas not containing carbon by including carbon in the solid surface in contact with the plasma and by causing an etching reaction on the solid. The effectiveness of this invention is therefore verified. For applying power to the wall of the plasma chamber, there are various effective means, such as explained in the Embodiment 2. Among them is a method that divides the wall electrode into a few blocks and applies different bias powers to them. A second method is to share the bias power source of the wafer with the wall electrode by setting two powers in different phases. The second method also proved effective. Even when the distance between the upper and bottom electrodes is as small as 30 mm or less, the bias application to the wall electrode proved effective. These methods were particularly effective for the electrode distance of more than 30 mm. Embodiment 15 This embodiment has a temperature adjusting system 48 added to the Embodiment 14 and performs etching by controlling the temperature of the electrodes. This embodiment will be explained by referring to FIG. 15 . The temperatures of the upper and lower electrodes and the wall electrode were varied from −60° C. to 250° C. to examine the effect the electrode temperatures have on the etching performance. The result of measurement shows that selective etching on the silicon oxide film with respect to the silicon nitride film can be achieved by setting the wafer electrode temperature as high as possible. A particularly desirable temperature was found to be 0° C. or higher. The temperature of the upper electrode was found to be one of the factors that determine the etching rate on the electrode surface. Hence, it is necessary to keep the electrode temperature as constant as possible. In addition, it was found that the higher the temperature, the faster the etching rate and that setting the temperature low degrades the efficiency of the transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature range, a desired etching rate can be set. As for the wall electrode, reaction products easily deposit on its surface at low temperatures. As in the case of the upper electrode, the temperature was found to constitute one of the factors that determine the etching rate on the electrode surface. Hence, the temperature needs to be kept as constant as practically possible. It is also found that the higher the temperature, the faster the etching rate and that setting the temperature low reduces the efficiency of transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature ranges, a desired etching rate can be set. This embodiment has thus demonstrated that when a gas plasma not containing carbon is used, this invention can etch a silicon oxide film at a high etching rate by including carbon in a solid surface in contact with the plasma, by causing this solid to perform an etching reaction, and by controlling the temperature of the solid in a range of −60° C. to 250° C. Embodiment 16 The silicon oxide film etching in an induced coupling type RF wave discharge etching apparatus according to this invention will be explained by referring to FIG. 13 . The wafer 106 is placed on a wafer table 107 that also serves as a lower electrode for bias RF wave application. The wafer table 107 is connected to a bias RF wave power supply 110 . In this embodiment, unlike Embodiments 12-15, there is no electrode opposite the wafer, but an insulation window 51 is provided. SiC as the radical control material 112 is arranged close to the wall. The SiC is connected to a bias power supply 119 . As in the Embodiment 14, the total gas flow was set at 20-500 sccm and SF 6 was varied in the range of 1-10 sccm. The discharge pressure was set at 0.3-5 Pa. The RF power is supplied from a plasma discharge RF wave power supply 54 to a turn antenna in the discharge section in the plasma chamber to generate a plasma inside a discharge window plate 58 or discharge tube made of alumina or quartz. Other conditions are similar to those of Embodiment 14. In the above experiment, it was found that, as in the case of Embodiment 14, the etching rate of the resist can be adjusted by the etching rate of the SiC wall electrode to keep a high level of selectivity. The etching rate of the silicon film also changed in a similar manner to that of the resist. It was also found that to realize the most selective etching of the silicon nitride film requires increasing the etching rate of the SiC wall electrode. Another important finding is that, as in the Embodiment 15, selective etching of the silicon oxide film with respect to the silicon nitride film can be achieved by setting the temperature of the wafer electrode as high as possible. Embodiment 17 The silicon oxide film etching in an UHF wave plasma etching apparatus using no magnetic field, according to this invention will be explained by referring to FIG. 11 . This embodiment uses a pyrolytic graphite for the electrode 71 opposite the wafer. The introduced gas was a mixture of SF6 and Ar; the total gas flow was set at 50-500 sccm; and SF 6 was varied in the range of 1-10 sccm. The discharge pressure was set at 0.5-5 Pa. The distance between the upper and lower electrodes was set at 10-200 mm. Surface-treated SiC 76 was arranged close to the wall of the plasma chamber as the radical control mechanism. Supplying power to the SiC causes the SiC to be etched with the plasma. The wafer to be etched has a silicon nitride film, a silicon film, a silicon oxide film and a photoresist formed in layers over a substrate. With the etching rate of the pyrolytic graphite of the upper electrode being varied from 50 nm/min to 600 nm/min, the etching rate of oxide film changed from 400 nm/min to 1400 nm/min and the etching rate of the resist film changed from 600 nm/min to 60 nm/min. That is, the etching rate of the resist can be adjusted by the etching rate of the SiC wall electrode to increase the selectivity. The etching rate of the silicon film also changed in the same way as that of the resist. It was found that the etching rate of the SiC wall electrode must be increased to perform the most selective etching of the silicon nitride film. It is also found that, as with the Embodiment 15, the selective etching of the silicon oxide film with respect to the silicon nitride film can be realized by setting the temperature of the wafer electrode as high as possible. Embodiment 18 Effective use of gas according to this invention will be explained by referring to FIG. 11, for an example of etching a silicon oxide film in an UHF wave plasma etching apparatus using a magnetic field. This embodiment uses ClF 3 as a gas not containing carbon. The inert gas used is a mixture of Ne, Ar, Kr and Xe. ClF 3 , which has a high greenhouse effect coefficient and a long lifetime and is thus not desirable as with the fluorine-containing gas, has the advantage of requiring only a very small consumption. Other conditions are similar to those of Embodiment 17. The experiment with this embodiment has indicated that even when ClF 3 is used, the silicon oxide film can be etched at a high etching rate by controlling the temperature of the radical control material in the range of −60° C. to 250° C., as in the case of the Embodiment 17. Embodiment 19 This embodiment uses a small amount of carbon in addition to ClF 3 as the etching gas for etching a silicon oxide film in induced coupling type RF discharge plasma etching equipment. Because this embodiment is of the induced coupling type, no electrode is placed opposite the wafer. The use of SiC for the electrode 112 near the wall (FIG. 13) is found to improve the etching performance. However, it is very difficult to perform selective etching of the silicon oxide film with respect to the silicon nitride film. This embodiment is intended to compensate for this drawback. The carbon-containing gas need only include H, F or Cl in addition to C. The total gas flow was set at 20-500 sccm and ClF 3 was varied in the range of 0-10 sccm. A trace amount of chloroform was used as an additive gas and the amount of chloroform introduction was set at a level not exceeding the amount of ClF 3 . The discharge pressure was set at 0.3-5 Pa. RF power was supplied to a turn antenna in the discharge section in the plasma chamber to generate a plasma inside the discharge window plate or discharge tube made of alumina or quartz. The wafer electrode was supplied with an RF power to accelerate ions in the plasma. The wafer used has a silicon nitride film, a silicon film, a silicon oxide film and a photoresist formed in layers over a substrate. When the etching rate of SiC was varied from 50 nm/min to 600 nm/min, the etching rate of the oxide film changed from 400 nm/min to 1600 nm/min and the etching rate of the resist film changed from 500 nm/min to 60 nm/min. The etching rate of the silicon nitride was 40-200 nm/min. Adding chloroform improved the selectivity by more than 20%, demonstrating the significant effect that a small amount of gas additive has on the etching performance and also the effectiveness of this invention. That is, by adding a small amount of carbon-containing gas, the etching rate of the resist can be adjusted, thereby increasing the selectivity. The effective range of the carbon-containing gas flow is 1% or less, preferably about 0.4-0.8%, of the total gas flow. That is, this embodiment can produce the above-mentioned effect if 5 sccm or less of the carbon-containing gas is introduced. The etching rate of the silicon film also changed in a similar way to that of the resist. The silicon nitride film was able to be etched very effectively and selectively. Under this condition, the temperatures of the upper and lower electrodes and the wall electrode were varied from −60° C. to 250° C. to investigate the effect the temperature has on the etching performance. The investigation has found that, for the silicon oxide film to be etched selectively with respect to the silicon nitride film, the temperature of the wafer electrode may be about 10° C. lower when the carbon-containing gas is introduced than when it is not. A particularly preferred temperature was −10° C. or higher. The temperature of the upper electrode was one of the factors that determine the etching rate of the electrode surface. Hence, the temperature must be kept as constant as practically possible. Further, it was also found that the higher the temperature, the faster the etching rate and that setting the temperature low degrades the efficiency of the transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature ranges, a desired etching rate can be set. As for the wall electrode, reaction products easily deposit on its surface at low temperatures. As in the case of the upper electrode, the temperature was found to constitute one of the factors that determine the etching rate on the electrode surface. Hence, the temperature needs to be kept as constant as practically possible. It was also found that the higher the temperature, the faster the etching rate and that setting the temperature low reduces the efficiency of the transformation reaction by the upper electrode of the reactive species. Thus, in the above temperature ranges, a desired etching rate was able to be set. This embodiment has thus demonstrated that when ClF 3 is used as a gas not containing carbon and H, F or Cl is used in addition to C as a carbon-containing gas, this invention can etch a silicon oxide film at a high etching rate with a high selectivity by including carbon in a solid surface contacting the plasma, by causing this solid to perform an etching reaction, and by controlling the temperature of the solid in a range of −60° C. to 240° C. This has verified the effectiveness of this invention. Embodiment 20 Effective use of gas according to this invention will be explained for an example of etching a silicon oxide film in an induced coupling type RF discharge plasma etching apparatus. This embodiment uses ClF 3 as an etching gas and also an oxygen-containing gas, such as O 2 . In addition to these gases, a small amount of carbon-containing gas used in the Embodiment 19 may also be used. The inert gas used is a mixture of Ne, Ar, Kr or Xe. As a fluorine-containing gas OF 6 , NF 3 and ClF 3 may be used. A key point of this embodiment is that O 2 , CO, CO 2 , NO, NO 2 and H 2 O can he used. It was observed that the use of a pyrolytic graphite for the wall electrode has contributed to an improved etching performance. It is, however, very difficult to perform selective etching on the silicon oxide film with respect to the silicon nitride film. This embodiment is intended to compensate for this drawback. The carbon-containing gas may be a gas containing H, F or Cl in addition to C. The total gas flow was set at 20-500 sccm and ClF 3 was varied in the range of 1-10 sccm. A small amount Of O 2 gas, not exceeding the amount of ClF 3 , was added. The discharge pressure was set at 0.5-5 Pa. RF power was supplied to a turn antenna in the discharge section in the plasma chamber to generate a plasma inside the discharge window plate or discharge tube made of alumina or quartz. The wafer electrode was supplied with RF power to accelerate ions in the plasma. Unlike the preceding embodiments, this embodiment produces carbon oxide gases such as CO, CO 2 , C 3 O 2 , and C 5 O 2 as a result of the etching reaction. These gases are extremely desirable for selective etching of a silicon oxide film with respect to a silicon nitride film, further enhancing the effectiveness of this invention. The wafer used has a silicon nitride film, a silicon film, a silicon oxide film and a photoresist formed in layers over the substrate. With the etching rate of the graphite of the upper electrode varied from 50 nm/min to 600 nm/min, the etching rate of the oxide film changed from 400 nm/min to 1600 nm/min and the etching rate of the resist film changed from 500 nm/min to 60 nm/min. The etching rate of the silicon nitride film was 30-150 nm/min. The selectivity improved more than 15% by the addition of oxygen, verifying that a small amount of gas additives has a significant effect on the etching performance. This embodiment further demonstrated the effectiveness of this invention. In other words, the addition of a small amount of oxygen-containing gas can adjust the etching rate of the resist and increase the selectivity. The etching rate of the silicon film also changed in the same manner as that of the resist. The silicon nitride film was able to be etched highly effectively and with high selectivity. While the above embodiment uses pyrolytic graphite and SiC as the carbon-containing materials, other carbon-containing materials may be used, such as organic resin film, SiCN, diamond plate, Al 4 C 3 and boron carbide. Similar effects were obtained when these carbides were formed on the surface of the chamber. Although the above embodiment uses Ar as a gas not containing carbon, other inert gases may be used, such as Ne, Kr and Xe. The above embodiment uses SF 6 and ClF 3 as a fluorine-containing gas. These gases, though they have a high greenhouse effect coefficient and a long lifetime and are thus not desirable, have an advantage of requiring only a very small amount of consumption. Other gases that may be used include F 2 , HF, XeF 2 , PF 3 , BF 3 , NF 3 , SiF 4 , and halides such as fluorine chloride ClF, fluorine bromides BrF, BrF 3 and BF 5 and fluorine iodide IF 5 . Effect of the Invention Advantages of this invention may be summarized as follows. Without using PFC and HFC gases, it is possible to generate reactive species necessary for etching and perform etching of a silicon oxide film while maintaining the same level of selectivity as offered by the conventional etching equipment. In the silicon oxide film etching process, fluorine in the plasma is converted into CF 2 , transforming reactive species in the plasma into one desired species. The use of this plasma with a single reactive species enhances selectivity, whereby etching proceeds on the silicon oxide film with reaction products evaporated, whereas, on the silicon nitride film, etching is stopped by residual matters. This eliminates a problem of shoulder erosion in the nitride film due to deteriorated selectivity and of increased process margin. Further, the density of a reactive species can be maintained nearly constant between different materials during metal etching, minimizing localized abnormal deformations or notching. Because deposits on the plasma boundary surface can be removed, variations in etching characteristic can be minimized, assuring high throughput and a satisfactory stable etching characteristic.
Because of environmental pollution prevention laws, PFC (perfluorocarbon) and HFC (hydrofluorocarbon), both etching gases for silicon oxide and silicon nitride films, are expected to be subjected to limited use or become difficult to obtain in the future. An etching gas containing fluorine atoms is introduced into a plasma chamber. In a region where plasma etching takes place, the fluorine-containing gas plasma is made to react with solid-state carbon in order to produce molecular chemical species such as CF 4 , CF 2 , CF 3 and C 2 F 4 for etching. This method assures a high etch rate and high selectivity while keeping a process window wide.
7
RELATED APPLICATION DATA This application is a continuation-in-part of application Ser. No. 08/921,931, filed Aug. 27, 1997 (now U.S. Pat. No. 6,226,387), which claims priority to provisional applications No. 60/050,587, filed Jun. 24, 1997, and 60/024,979, filed Aug. 30, 1996. This application is also a continuation-in-part of application Ser. No. 08/918,126, filed Aug. 27, 1997 (now U.S. Pat. No. 6,272,634), which claims priority to provisional applications No. 60/050,587, filed Jun. 24, 1997, and 60/024,979, filed Aug. 30, 1996. This application is also a continuation-in-part of application Ser. No. 08/918,125, filed Aug. 27, 1997 (now U.S. Pat. No. 6,282,299), which claims priority to provisional applications No. 60/050,587, filed Jun. 24, 1997, and 60/024,979, filed Aug. 30, 1996. This application resulted from conversion of provisional application No. 60/287,873 to a non-provisional application, in accordance with the provisions of 37 CFR 1.53(c)(3). RELATED FILES This application is related to cofiled, copending and coassigned application entitled “SYSTEMS AND METHODS FOR INTERCEPTING MEDIA DATA, INCLUDING WAVEFORM DATA”, Ser. No. 09/846,686, which is hereby incorporated by reference herein for all purposes. GOVERNMENT RIGHTS STATEMENT The inventions detailed in applications 08/918,125, 08/921,931, and 08/918,126 were made with government support by AFOSR under grant AF/F49620-94-1-0461, NSF under grant NSF/INT-9406954 and ARPA GRANT No. AF/F49620-93-1-0558. The Government has certain rights in those inventions. FIELD The invention relates to digital watermarking. COPYRIGHT NOTICE/PERMISSION A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever. The following notice applies to the software and data as described below and in the drawings hereto: Copyright @ 2001, Cognicity, Inc. All Rights Reserved. SUMMARY OF THE INVENTION One aspect of the invention is a method of detecting a digital watermark embedded in a host signal. The method receives the host signal including a media signal and a digital watermark that has been perceptually adapted to the media signal in frequency and non-frequency domains. The method processes the host signal with a representation of the digital watermark to compute a measure of the digital watermark. Based on the measure of the digital watermark, the method extracts the digital watermark from the host media signal. The host signal has autocorrelation properties that enable synchronization of the digital watermark despite temporal or geometric distortion of the host signal. Another aspect of the invention is a method of digital watermarking a media signal. This method derives a first key that is a function of the media signal, generates a digital watermark signal that is a function of the first key and a second key that is not dependent on the media signal, and embeds the digital watermark in the media signal. Another aspect of the invention is a method of detecting a digital watermark in a host signal. This method obtains a first key that is a function of the host signal, generates a representation of a digital watermark from the first key and a second key that is not dependent on the host signal, and processes the host signal with the representation of the digital watermark to extract the digital watermark from the host signal. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of the hardware and operating environment in which different embodiments of the invention can be practiced; and FIG. 2 is a diagram illustrating a system level overview of an exemplary embodiment of a media interception system. FIG. 3 is a diagram illustrating one approach of a digital rights management system. FIG. 4 is a diagram illustrating another approach of a digital fights management system. DETAILED DESCRIPTION The detailed description describes systems, clients, servers, methods, and computer-readable media of varying scope. In the following detailed description, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific exemplary embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that logical, mechanical, electrical and other changes may be made without departing from the scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense. In the Figures, the same reference number is used throughout to refer to an identical component which appears in multiple Figures. Signals and connections may be referred to by the same reference number or label, and the actual meaning will be clear from its use in the context of the description. The detailed description is divided into multiple sections. In the first section the hardware and operating environment of different embodiments. In the second section, the software environment of varying embodiments. In the final section, a conclusion is provided. Hardware and Operating Environment FIG. 1 is a diagram of the hardware and operating environment in conjunction with which embodiments of the invention may be practiced. The description of FIG. 1 is intended to provide a brief, general description of suitable computer hardware and a suitable computing environment in conjunction with which the invention may be implemented. Although not required, the invention is described in the general context of computer-executable instructions, such as program modules, being executed by a computer, such as a personal computer or a server computer. Generally, program modules include routines, programs, objects, components, data structures, etc., that perform particular tasks or implement particular abstract data types. Moreover, those skilled in the art will appreciate that the invention may be practiced with other computer system configurations, including hand-held devices, multiprocessor systems, microprocessor-based or programmable consumer electronics, network PCs, minicomputers, mainframe computers, and the like. The invention may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote memory storage devices. As shown in FIG. 1 , the computing system 100 includes a processor. The invention can be implemented on computers based upon microprocessors such as the PENTIUM® family of microprocessors manufactured by the Intel Corporation, the MIPS® family of microprocessors from the Silicon Graphics Corporation, the POWERPC® family of microprocessors from both the Motorola Corporation and the IBM Corporation, the PRECISION ARCHITECTURE® family of microprocessors from the Hewlett-Packard Company, the SPARC® family of microprocessors from the Sun Microsystems Corporation, or the ALPHA® family of microprocessors from the Compaq Computer Corporation. Computing system 100 represents any personal computer, laptop, server, or even a battery-powered, pocket-sized, mobile computer known as a hand-held PC. The computing system 100 includes system memory 113 (including read-only memory (ROM) 114 and random access memory (RAM) 115 ), which is connected to the processor 112 by a system data/address bus 116 . ROM 114 represents any device that is primarily read-only including electrically erasable programmable read-only memory (EEPROM), flash memory, etc. RAM 115 represents any random access memory such as Synchronous Dynamic Random Access Memory. Within the computing system 100 , input/output bus 118 is connected to the data/address bus 116 via bus controller 119 . In one embodiment, input/output bus 118 is implemented as a standard Peripheral Component Interconnect (PCI) bus. The bus controller 119 examines all signals from the processor 112 to route the signals to the appropriate bus. Signals between the processor 112 and the system memory 113 are merely passed through the bus controller 119 . However, signals from the processor 112 intended for devices other than system memory 113 are routed onto the input/output bus 118 . Various devices are connected to the input/output bus 118 including hard disk drive 120 , floppy drive 121 that is used to read floppy disk 151 , and optical drive 122 , such as a CD-ROM or DVD-ROM drive that is used to read an optical disk 152 . The video display 124 or other kind of display device is connected to the input/output bus 118 via a video adapter 125 . A user enters commands and information into the computing system 100 by using a keyboard 40 and/or pointing device, such as a mouse 42 , which are connected to bus 118 via input/output ports 128 . Other types of pointing devices (not shown in FIG. 1 ) include track pads, track balls, joy sticks, data gloves, head trackers, and other devices suitable for positioning a cursor on the video display 124 . As shown in FIG. 1 , the computing system 100 also includes a modem 129 . Although illustrated in FIG. 1 as external to the computing system 100 , those of ordinary skill in the art will quickly recognize that the modem 129 may also be internal to the computing system 100 . The modem 129 is typically used to communicate over wide area networks (not shown), such as the global Internet. The computing system may also contain a network interface card 53 , as is known in the art, for communication over a network. Software applications 136 and data are typically stored via one of the memory storage devices, which may include the hard disk 120 , floppy disk 151 , CD-ROM/DVD-ROM 152 and are copied to RAM 115 for execution. In one embodiment, however, software applications 136 are stored in ROM 114 and are copied to RAM 115 for execution or are executed directly from ROM 114 . In general, the operating system 135 executes software applications 136 and carries out instructions issued by the user. For example, when the user wants to load a software application 136 , the operating system 135 interprets the instruction and causes the processor 112 to load software application 136 into RAM 115 from either the hard disk 120 or the optical disk 152 . Once software application 136 is loaded into the RAM 115 , it can be used by the processor 112 . In case of large software applications 136 , processor 112 loads various portions of program modules into RAM 115 as needed. The Basic Input/Output System (BIOS) 117 for the computing system 100 is stored in ROM 114 and is loaded into RAM 115 upon booting. Those skilled in the art will recognize that the BIOS 117 is a set of basic executable routines that have conventionally helped to transfer information between the computing resources within the computing system 100 . These low-level service routines are used by operating system 135 or other software applications 136 . In one embodiment computing system 100 includes a registry (not shown) which is a system database that holds configuration information for computing system 100 . For example, Windows® 95, Windows 98®, Windows® NT, Windows 2000® and Windows Me® by Microsoft maintain the registry in two hidden files, called USER.DAT and SYSTEM.DAT, located on a permanent storage device such as an internal disk. Software Environment This section describes a software environment of systems and methods that provide for interception of media data. FIG. 2 is a block diagram describing the major components of a media interception system 200 according to an embodiment. In one embodiment, media interception system includes a media player/recorder application 202 , media SDK (Software Development Kit) 206 , media device driver 208 and interception layer software 204 . Media player/recorder application 202 is an application that can playback and/or record audio, video or other multimedia data using hardware on a computer system, such as computer 100 ( FIG. 1 ). Examples of such applications include the RealPlayer and RealJukebox applications from RealNetworks Inc., the Winamp player from Nullsoft, Inc., and the Windows Media Player application from Microsoft Corp. In general, a media player/recorder application 202 is capable for reading and/or writing at least one type of media data stream 220 . An example of a particular media type is the waveform audio type. Waveform audio data can be stored in multiple formats. One popular format is the WAV (Microsoft RIFF format), which stores the audio data in a non-compressed form. Other waveform formats store the data in compressed form. These formats include the Microsoft Windows Audio format (wm, .wma), Real Audio format (.ra), the Sun Audio format (.au) and the MP3 (.mp3) format. These formats are listed as exemplary formats; the invention is not limited to any particular format. The media data streams 220 can be stored in a number of ways. For example, the data streams can come from a file that resides on a hard drive, a CD-ROM, or a DVD-ROM. Alternatively, the data streams can reside on a remote system, and can be transferred to the application over a network such as the Internet. The invention is not limited to any particular source for the data stream. Some audio systems add an additional encryption layer to the compressed audio data for copyright protection purposes. Despite the fact that the audio data may be encrypted, compressed or even specially processed, the audio data that goes to the media SDK 206 has to be in wave format. It is the application responsibility to convert the compressed/encrypted/processed audio data to regular wave format. Media SDK 206 comprises a collection of modules that provide an API (Application Program Interface) that enables software developers to develop applications that play and/or record media data streams, such as audio or video data streams. In one embodiment, the media SDK 206 is a waveform Software Development Kit (SDK) from Microsoft Corporation that enables software applications developers to develop applications that receive waveform input data from audio devices and play the waveform audio data through the output audio device. Software developers can use the waveform SDK to add sound effects to applications and capture the audio input from the microphone, sound card line-in and any audio input device. For both waveform input and waveform output services, the waveform SDK uses the standard wave format to represent the audio data. In some embodiments, this wave format is defined using the WAVEFORMATHDR and WAVEFORMATEX data structures defined by the SDK. Applications 202 can communicate with SDK 204 either by direct function calls to the SDK APIs or through sending messages to the SDK to request the proper operation. It should be noted that FIG. 2 has illustrated a single media player/recorder application 202 . However, in some embodiments of the invention, media SDK 206 can support playing waveform buffers from a plurality of different instances of an application 202 simultaneously as well as capturing input from the audio in devices. Thus, the invention is not limited to any particular number or type of media player/recorder applications. Media device driver 208 provides an interface to control a particular type of media hardware 210 . For example, media device driver 208 can be a sound card device driver for controlling input and input for a particular brand of sound card in a computer system. Interception layer software 204 intercepts, collects, filters and controls media input and output data. In one embodiment, the interception layer software 204 controls waveform audio data. The interception layer software 204 logically resides between a media player/recorder application 202 and the media SDK 206 , and emulates the API calls and message handling of a media SDK. In addition, media SDK 206 can emulate callback functions on behalf of an application 202 . Thus, to media player/recorder application 206 , the interception layer appears as a media SDK, and to media SDK, the interception software layer appears to be an application. The interception layer software 204 can apply its functions to any media player/recorder application 202 . In some embodiments, these media player/recorder applications 202 are capable of running under any or all Microsoft Windows platforms. In one embodiment, the interception layer software 204 collects and controls the waveform input data as it goes from the audio input device before it reaches the application and collects and controls the waveform output data as it goes from the application and before it reaches the audio output device 210 via media SDK 206 . In some embodiments, particularly those embodiments that operate in a Microsoft Windows environment, the interception software 204 includes a replacement kernel module 214 that can replace a previously existing kernel 32 .dll. The replacement kernel module 214 provides all the services that the original kernel 32 .dll exports to other system modules and applications. In addition, replacement kernel module 214 provides additional processing as described below. In various embodiments, the interception software layer 204 must be installed before it will operate. In embodiments that operate on Windows 95, Windows 98 and Windows Me platforms, during the software installation process, a windows-modules-patching component patches the winmm.dll file and changes the reference of the Windows kernel 32 .dll to refer to the replacement kernel module 214 . This type of system file patching forces the Windows applications loader to load the interception layer software 204 in the address space of any application 202 that imports services from winmm.dll. In some embodiments, during the loading of any media player/recorder application 202 , if the winmm.dll is used by application 202 or any one of its referenced modules, then the Windows platform loads the interception software layer 204 , including the replacement kernel module 214 in the address space of the application 202 . As mentioned earlier, this is because winmm.dll has been patched to refer to the replacement kernel module 214 instead of the original windows kernel 32 .dll. Loading the interception layer software 204 by the replacement kernel module 214 ensures that the software 204 will be active in the address space of any application that uses services exported from winmm.dll. This is desirable, because doing so provides optimal system performance, as the software 204 is active only when there is a request for a winmm.dll service. In embodiments that operate on the Windows NT and Windows 2000 platforms, the installation software places standard entries in the Windows registry database that forces the loading of the interception layer software 204 inside the address space of any running media player/recorder application 202 . Thus in embodiments that operate on Windows NT or Windows 2000, Windows loads the replacement kernel software 214 as it loads a media player/recorder application 202 . During the application loading process for a media player/recorder application 202 , the new kernel software 214 checks if the winnmm.dll is loaded or not. If it is not loaded, it then activates the interception layer software 204 for this application's address space. Otherwise it stays passive and listens to application requests. If there is a new request for a winmm.dll service, then the software switches back to the active mode. This ensures the best system performance, as the software is active only when there is a request for a winmm.dll service. In further alternative embodiments that operate under all Windows platforms, while the replacement kernel software 214 is active, it installs a “Module-Load-Monitor” thread 212 that monitors the loading of any module by the application 202 . If the application is loading the winmm.dll or requesting a service from the winmm.dll then the software changes the reference to winmm.dll or the winmm.dll service to call another module provided by the interception layer software 204 . The replacement kernel module 214 intercepts all the calls and messages that go from the application 202 to the media SDK (e.g. winmm.dll) and dispatches them to interception layer 204 . Therefore, the interception layer software 204 module receives all the requests for waveform input and output services. In some embodiments, the interception layer software 204 includes two controllers: the first controller is the Wave-Out Audio Controller that manages the requests for audio output services and the second controller is the Wave-In Audio Controller that manages the requests for audio input services. In general, the Wave-Out Audio Controller is capable of doing the following functions: collect all the audio data that goes from the application to the windows Wave-Out system. collect the audio data of each Wave-Out session in a different buffer filter some audio output buffers before being dispatched to the output sound device. process the output of the audio data, which includes applying an external audio processor before sending the audio output data to the sound card. For example, the interception layer can provide “mixer” functions or “3D” effects. Monitoring listeners' behavior (Wave-Out): the software can detect the start date and time of each Wave-Out session as well as the date and time duration the session has ended. Therefore, it can define exactly how long any song was played by the system. Audio filtering: The software can filter the whole Wave-Out/Wave-In session and can filter specific parts of the audio input/output. It can filter the content based on the time duration or as a results of applying any external audio processor. Audio recording: The software records the audio input and output waveform data to external files. It saves the data in Windows WAV file format. The software is capable also of encoding the output waveform data into different types of popular commercial audio file formats. It is well integrated with different sets of CODEC SDKs and can encode the output files to Real Audio format, Windows Audio format and MP3 format. It is prepared to support any file format encoder. Deferred audio delivery: For waveform output, the software is capable of collecting the audio data from the application without sending it to the output device. This is done transparently from the application. Therefore, the application continues sending more data and does not stop as it has a fake sense that the output sound device plays the output audio data. For Waveform input, the software is capable of collecting the audio input data from the input device without sending them to the application the moment they are they are received. After then, it can send them to the application as even they have been just received from the input device. This requirement is very important for many audio processors that require processing the audio content as a whole before the application for audio input and before the sound card for audio output. In general, the Wave-In Audio Controller is capable of performing the same types of functions provided by the Wave-Out Audio Controller except that it applies it to input audio data. This section has described the various software components in a system that provide for the interception of media data, including waveform audio data. As those of skill in the art will appreciate, the software can be written in any of a number of programming languages known in the art, including but not limited to C/C++, Java, Visual Basic, Smalltalk, Pascal, Ada and similar programming languages. The invention is not limited to any particular programming language for implementation. CONCLUSION Systems and methods that provide for the interception of media data streams are disclosed. The embodiments provide numerous advantages over previous systems, and various embodiments include various combinations of the following features: Unified audio format: the software collects all the audio input and output data in the standard waveform format regardless of the input audio file format used by the application to store the audio data. Session based: The software establishes a separate audio collection session for each waveform audio input and output session performed by the application. Application neutral: The software implementation is transparent to the implementations details of the application. It can collect the waveform output data from any Windows applications as long as it uses the Microsoft waveform SDK. Application awareness: the software provides separate audio collection sessions for each application. This enables the software to define the application interacts with the waveform SDK for both audio input and output. It enables the software to provide different set of customized audio management features per application. Sound driver neutral: the software is independent of the sound driver implementation therefore it works with any sound driver installed in the user windows system. User transparent: All the software operations are hidden to the user who can not disable the software operations except by uninstalling the software itself through the software uninstall program. Persistent installation: The software provides several techniques to force itself to be always active regardless of any tool that is installed on the system and tries to uninstall or deactivate the software. Consistent functionality over any Windows 32 platform whether it is Windows NT or Windows 95 based platform. Upward compatibility for windows operating systems. Hidden from the user and the user has no control over it. Safety and Robustness: The software component that does not conflict with other system monitoring tools. Additonally, the interception software does not affect any other application running in the system outside the address space of the audio player. In addition to the aspects described above, Appendix A provides a description of an embodiment that includes components described above to provide a digital rights management system. Furthermore, Appendix B provides details of an alternative digital rights management system according to an embodiment. The discussion provided in Appendix A and Appendix B refers to watermarking. While any general file watermarking can be adapted to the embodiments described above, specific methods of watermarking are described in the following patents and patent applications, all of which are hereby incorporated by reference herein for all purposes. Ser. No. Filed Title Status 08/918,122 Aug. 27, 1997 Method and Ap- Issued: Feb. 29, 2000 paratus for Em- U.S. Pat. No. bedding Data, In- 6,031,914 cluding Water- marks, in Human Perceptible Images 08/918,891 Aug. 27, 1997 Method and Ap- Issued: May 9, 2000 paratus for Em- U.S. Pat. No. bedding Data, In- 6,061,793 cluding Water- marks, in Human Perceptible Sounds 08/918,125 Aug. 27, 1997 Method and Ap- Issued: Aug. 28, 2001 paratus for U.S. Pat. No. Video 6,282,299 Watermarking 08/921,931 Aug. 27, 1997 Method and Ap- Issued: May 1, 2001 paratus for Scene- U.S. Pat. No. Based Video 6,226,387 Watermarking 08/918,126 Aug. 27, 1997 Digital Water- Issued: Aug. 7, 2001 marking to Re- U.S. Pat. No. solve Multiple 6,272,634 Claims of Ownership 09/228,224 Jan. 11, 1999 Multimedia Data Issued: Aug. 27, 2002 Embedding U.S. Pat. No. 6,442,283 09/481,758 Jan. 11, 2000 Transaction Issued: Jul. 5, 2005 Watermarking U.S. Pat. No. 6,951,481 09/480,391 Jan. 11, 2000 Degradation Abandoned Watermarking 09/585,102 May 31, 2000 Persistent Linking Abandoned Via Watermarking 09/573,119 May 16, 2000 Systems And Abandoned Methods For Pro- viding Author- ized Playback And Tracking Of Multimedia Content Over Networks Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations of the present invention. The terminology used in this application is meant to include all of these environments. It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description and the attached appendices. APPENDIX A The Concept The basic idea is to have two audio files, the first file is a distributable audio file that will be available for public download to the end users community, (we will call this file, the Public Track) while the second audio file will be the complete secured track, (we will call this file the Private Track). The user can listen, play and distribute the Public track without any restriction. Each Public Track has a Track-Id that is used to identify the track at any time. The corresponding Private Track has also the same Track-ID. In addition to the Track-Id there is one bit that indicates the type of the Track. For the Public Track the bit value is zero and for the private Track the bit value is one. The Private Track will be encrypted and hosted and secured on a remote server not accessible by the end user. Each Private Track is encrypted with a unique encryption key. The Decryption Key for each Private Track is hosted securely also on a remote server. The Private Track will be hidden to the user. It will be handled in transparently to the user. The user can never have access to the Private Track file in an open non-encrypted form. If cognicity software is installed, then at any time there is an access to the Public Track then Cognicity software checks if the corresponding Private Track is installed to the user local hard disk or not. If the Private Track is installed then the software transparently switches the file access operation to point to the Private Track. The Private Track is still encrypted and not available in a decrypted form. If the Private Track is not available on the user machine then the software establishes a secure connection with the server to download both the Private Track and the Decryption Key (required to decrypt this specific Private Track). During file reading operations, the software uses the Decryption Key and decrypt the Private Track data on the fly as being read by the application. Theoretically, the Public Track can contain any audio data. The Private Track does not have to have a direct match or overlap with the data used for the Private Track. However, for the purpose of Cognicity application the Public Track audio data was prepared by cutting the proper audio data from the Private track. While editing the Public Track a promotional audible message is added near the end of the track to encourage the end user to download the software to listen to the full track (Private Track). Implementation Details A system level file system controller has been developed. This file system controller provides a full control on the application level for all the types of file access operations done by the application. The following types of controls have been provided: monitor and control the application file open operations. monitor and control the application file read/write operations. monitor and control the application creation of any new file monitor and control the access of the memory mapped files monitor and control all the file operations that enables the application to retrieves the file information and in particular the file size. Cognicity watermarking technology is used to encode the watermark value inside both the Private Track and the Public Track. The watermark value used is equal to the Track-Id designed for each Track. As mentioned earlier, there is on added bit that indicates the type of the track. An system level audio interceptor has been developed to collect the audio data as being played by the application. The system audio collector collects the audio data as being played by the application in a raw PCM format. It interacts with Cognicity watermark decoder to decode the watermark on the fly while the track is being played by the application. The system level audio interceptor and detector can collect any audio data played by the application whether the application is using the Windows Wav-out SDK or using the Direct Sound SDK to play the audio tracks. The software supports four basic media file formats: WAV , Real Media, Windows Media and MP3 formats. For each format, a format decoder has been implemented. The basic function of each format CODEC is as follows: 1. decode the audio content of any file. This is required to decode the watermark directly from the file 2. extract the value of any attribute. This is used to extract the values of the attributes the software uses to store the Track-Id 3. modify the value of any attribute and add the attribute if the attribute does not exist. The Public Track and Private tracks are encoded in three audio file formats Real Media, Windows Media and MP3. While encoding the Private Track a format-specific attribute is added to define the track-id of the Public Track. There is format attribute used for the Private Track as the file is not available to the end user. The software uses some DRM rules to allow the substitution of the Public Track with the Private Track. The DRM rules are hosted on a remote secure server and retrieved from the server as the Private Track is downloaded from the server. The DRM rules specifies the following: 1. How many times the user can listen to the full track (how many times the software will substitute the Public Track with the Private Track) 2. The Track expiration data and time. The date and time are specified as referenced to the user machine local time or referenced to Greenwich local time. Internal System Operations 1—Upon file open: the software checks the file format, if the file is an audio file in one of the formats supported by the software (Real Media, Windows Media and MP3) then the software staffs by trying to extract the format attribute value that corresponds to the Track-Id. If the value does not exist in the format attribute then the system starts to decode the first 10 seconds of the audio format and starts to decode the watermark value that corresponds to the track-id if available. If the track-id was extracted successfully (whether from the format attribute or through the watermark decoding) then the software knows that this is a Public Track. The software can verify this fact by checking the bit that defines the type of the track. The software locates the DRM rules for this Public Track if the rules allow the play of the Private Track then the software starts to locate the Private Track. If the Private Track is available then the software opens the Private Track and return the file handle to the application. If the Private Track is not available then the software lets the Public Track to be played with no substitution and starts to download the Private Track and the Decryption Key through a background process. 2—During file reading operations, the software checks if the handle passed In the file read operation is one of the handles created for Private Tracks. If the handle corresponds to a Private Track then the software read the proper data from the Private Track file and decrypts those data then copy the data back to the application buffer. This step requires an accurate file read synchronization as the application block size for reading data is not equal to the block size used to decrypted the Private Track. 3—During any kind of file information enumeration or retrieval done by the application; the software checks each file to define whether it is a Public Track or not. The check used is similar to that described in point 1 . If the file corresponds to a Public Track then the software locates the corresponding Private Track and retrieve the required information for the Private Track then copy the result back to the application return buffer. This step ensures that the applications allocates memory buffers sufficient to read the content of the Private Track not the Public Track. It also ensures that the application display the play duration time in the application user interface that corresponds to the length of the Private Track and not the Public Track. 4—Upon audio play operations, the audio system interceptor decodes the watermark if any. If there is a watermark, then the software staffs checks the bit that indicates the type of the track. If the bit indicates a Private Track then the interceptor increases the play count of this track. This play count is used in step 1 as part of the DRM rules. Protecting the Write Back of the Private Track There are different techniques that enable the end user to save any audio content back to a file while the file is played by any application on his machine. If there is no secured protection for this techniques then the end user can install the software, get the proper DRM rules as a regular user, listen to the Private Track and then use any audio write-back tool to get the content of the Private Track in an open format. The software provides solutions on different levels to secure the audio write-back case. The application apply solutions on different levels as follows: 1. Having a list of trusted applications that can receive the decrypted content of the Private Track: The software does not only apply DRM rules per the end user but it also apply a concept of trusted applications. The software has a list of the applications that are trusted for not to distribute the content by any illegal way and read the content to play the content only. As case examples, if an application reads the content and plays the content as usual but sends the content transparently through an email or so then the application will be classified as non-trusted application. Before substituting the Public Track with the Private Track the software verifies the caller application. If the application is not trusted then it will not do the substitution. 2. Some audio player applications provides a standard feature to the end user to encode the audio files to different file formats. Those audio players are trusted and do not do hidden operations. For those trusted applications the software does the substitution if the user is playing the Public Track, however, if the user is encoding the Public Track to another file format then the software detects the case and do not do the substitution. 3. There are some tools available today in the market like “Total Recorder” that enables the user to record the music played by any application back to a file. A legal user can play the Private Track by a trusted application and uses Total recorder to save the content back to a file. The software has a smart sensors that detects this kind of write-back actions and erases the files as they are saved by the user to a local file. Tracks Prodution Phase The production phase starts by having the PCM data corresponds to both the Private Tracks and the Public Track. The operator defines the Track-Id used for this pair of tracks. It then encode the watermark into both tracks with the bit that indicates the track type added to the watermark value. After then, both Tracks are encoded to the proper file format (RealAudio, Windows Audio or MP3). The format attribute that's equivalent to the watermark value is added also to encoded tracks. Then, the production software starts to encrypt the Private Track and generate the Decryption Key. The system operator takes the Private Track, Decryption Key, Public Track as well DRM rules and upload them to the proper location on the designated server. Generalization of the Concept The same idea can be applied easily to any media content whether it's for audio content or video content or even mixed content. The same watermark technology can be used as well as the file format attributes. A “DRM” like solution that is format agnostic. The objective, of course, is to strongly motivate the listeners to download our software, thereby allowing a media provider to get the information you seek in return for the free music. Described below are two approaches to Digital Rights Management. Both effectively and easily solve the problem of allowing: non-users of media player software to be able to play NO more than 30 seconds of audio NO MATTER HOW they get the audio tracks. Approach 1 is illustrated in FIG. 3 In this approach shown in FIG. 3 , the file consists of clean first 30 seconds plus a corrupted remainder. The corruption takes the form of many audible noise clips inserted at random locations within the track. Without our software player reads whole file, renders first 30 seconds perfectly and renders all noise clips in remainder of the track resulting in an unusable remainder. With our software Our software can read the watermarks in the random insertions and block the rendition of these clips. Result: a pristine file. Comments a. Non-user hears 30 seconds and plus corrupted sound of variable duration. b. File forwarded by a listener is as long as original. c. If I forward a track to someone who has our software, he or she can play the pristine version with no additional download, even if I changed the format of the file. d. Solution is format agnostic and survives format changes. Approach 2 is illustrated in FIG. 4 In this approach shown in FIG. 4 , a file is broken into 2 or more separate files. The first 30 seconds are in one file that is clearly named and can easily be forwarded to others. The rest of the file is inserted at a random location within a larger “auxiliary file” that resides on the user hard drive. A watermark extracted from the first 30 seconds points to the location of the rest of the file in the auxiliary file. For added security, the rest is broken into several pieces, each inserted at a random location and each containing a watermark pointer to the piece that comes after it. Without our software Listener can only play first 30 seconds. Listener will not play a corrupted remainder. With our software File is seamlessly assembled for player. Listener can hear the full song. Listener can only forward the first 30 seconds. (Listener can also forward the auxiliary file. However, that file will be large and cannot be properly played without the watermark extraction as it consists of randomly ordered blocks from many tracks.) Comments a. Non-user hears only 30 seconds and no corrupted sound. b. File forwarded by listener is always the 30 second version. c. If I forward a track to someone who has our software, he or she will need an additional automatic download to play the pristine version. d. Solution is format agnostic and survives format changes. A format change requires further processing by our software.
A digital watermark detection method exploits autocorrelation properties of the watermarked signal that enable synchronization of the digital watermark despite temporal or geometric distortion of the host signal. Other watermark methods employ keys, including a key dependent on the content in which the watermark is embedded and another key that is not dependent on the content.
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BACKGROUND OF THE INVENTION [0001] The present invention relates to toys or performance devices. More specifically, the invention is directed to toys or performance devices that allow a user to create by manipulative movements, various configurations of the device such as those used in rhythmic gymnastics. [0002] Various toys or performance devices that use cords and/or ribbons exist, such as U.S. Pat. No. 6,688,941 to Hooten and U.S. Pat. No. 5,890,946 to Bloomfield. Streamers, a common apparatus used in rhythmic gymnastic performances, are also known. However, it is not believed that the prior art provides the streamer, cord, or ribbon with a retraction and/or expansion feature. It would be advantageous to provide such a feature that permits the user to vary the length of the streamer or cord without stopping the movement of the performance. Such a feature would also be advantageous for storing the device as it would limit the amount of cord or streamer that could entangle itself. [0003] Accordingly, it is an object of the present invention to provide a retractable and expandable performance toy or device for use in performances such as rhythmic gymnastics. It is a further object of the present invention to provide a performance toy or device with a weighted assembly attached to the retractable device, providing more speed when using the device and/or to better direct the streamer or cord, allowing more variations of ribbon configurations and/or enhanced flexibility in manipulating the device as compared to prior devices. SUMMARY OF THE INVENTION [0004] The apparatus of this application may be a children's toy or an improvement to a performance device such as the ribbons used in rhythmic gymnastics. [0005] The device provides the user with a handle and cord emanating from the top. At the other end of the cord, a weight and/or ribbon assembly may be attached. A ribbon assembly may include ribbons or streamers radiating from the cord. A variety of items may be used as a weight that provide extra visual effects, such as a rubber ball, a colored disc, etc. A whistle or bells may be located on the weight, cord, ribbon, or streamer to provide an audible effect to the performance device. [0006] In one embodiment, it is preferable to use a ball as a weight. When a ball with attached cord is used, the user can swing the handle and the ball may fly quickly through the air. The user may even choose to strike the ball against a surface which creates extra visual effects with the ribbons and streamers. [0007] The device may have reeling means located within the handle or on its exterior. This reeling means allows the user to increase or decrease the length of the cord, moving the weight and ribbon assembly closer or further from the handle. This changes the visual displays produced by the device. The reeling means may be automatically or manually activated depending on what type of control the user desires. [0008] In one embodiment, the reeling means may be a tape spring located inside the handle. The cord may be anchored to the handle. When the user twirls the device, the cord unravels from within the handle. The user may stop the extension of the cord by depressing the tape spring from the exterior of the handle, clamping onto the cord. The user may also automatically reel in the cord by depressing a button communicating with the tape spring. BRIEF DESCRIPTION OF THE DRAWINGS [0009] FIG. 1 is a perspective view of one preferred embodiment of the performance device; [0010] FIG. 2 is vertical sectional view taken along reference line 2 - 2 of FIG. 1 ; [0011] FIG. 3 is top and side perspective view of a preferred embodiment of the performance device; [0012] FIG. 4 is a perspective view of the performance device in use; [0013] FIG. 5 is an enlarged sectional view taken along reference line 5 - 5 of FIG. 4 ; [0014] FIG. 6 is a side perspective view showing the two interior sides of the handle of the performance device opened at its vertical axis; and [0015] FIG. 7 is an enlarged perspective of a winding mechanism shown in FIG. 6 . DEFINITION OF CLAIM TERMS [0016] The terms used in the claims of the patent as filed are intended to have their broadest meaning consistent with the requirements of law. [0017] “Ribbon assembly” means a part of a performance device that provides the majority of the visual display, such as at least one ribbon and/or streamer. In addition, it may include anything that may add to a visual display, such as a light, whistle, webbing, decoration, glow-in-the dark material, etc. [0018] “Reeling means” means a part of the performance device that allows a user to extend or contract the cord automatically. [0019] Where alternative meanings are possible, the broadest meaning is intended. All words used in the claims are intended to be used in the normal, customary usage of grammar and the English language. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0020] Set forth below is a description of what are believed to be the preferred embodiments and/or best examples of the invention claimed. Future and present alternatives and modifications to this preferred embodiment are contemplated. Any alternatives or modifications which make insubstantial changes in function, in purpose, in structure, or in result are intended to be covered by the claims of this patent. [0021] Referring to FIGS. 1 and 2 , a preferred embodiment of the present invention, performance device 17 , may be manufactured for use as a children's toy, or as an improvement to a performance device, such as may be used in rhythmic gymnastics. Device 17 may have a handle 1 with a first end 2 a ( FIG. 7 ) of cord 2 inserted within interior channel 31 of handle 1 . In this embodiment, means for varying the length of cord 2 may be located on the exterior of handle 1 , such that a user may wrap or unwrap cord 2 around anchor 5 , having sides 5 a and 5 b and narrowed radial portion 5 c . A second end 2 b ( FIGS. 1 and 5 ) of cord 2 may be attached to at least one weight, such as ball 3 , and a ribbon assembly that may include radiating ribbons 4 and/or streamers attached to the top of the ball 3 using rivet 6 ( FIG. 5 ) to provide a radiating effect. A user may manipulate the device 17 by holding handle 1 (see FIG. 4 ) and twirling it around so that cord 2 floats in the air in a direction proscribed by the movement of ball 3 , while the ribbon or streamer assembly 4 creates visual effects in the air. [0022] Referring to FIGS. 3 , 4 , 6 , and 7 , preferred embodiments of the present invention, cord 2 may include automatic reeling means. Unused cord 2 may be located within handle 1 by running through channel 31 and wrapping around anchor 34 within interior space 32 of handle 1 . [0023] Referring to FIG. 4 , in one preferred embodiment, a user may control the length of cord 2 by depressing button 11 located over a spring loaded handle. When button 11 is pushed it clamps cord 2 and prevents its release. If the user releases button 11 , the pressure on cord 2 is released, and upon twirling cord 2 can further release from coil spring 15 and increase in length. This embodiment may but need not utilize spring-loaded means located in the handle (such as used in a tape measure, for example) for automatically retracting the cord, and for releasing it under force, as will be understood by those of ordinary skill in the art. For example, if the user pushes button 11 without twirling (i.e., without providing an opposing force directed in a radially outward direction along the cord), cord 2 , driven by a spring (not shown), will contract back into handle 1 automatically and wind around anchor ( FIG. 7 ). [0024] Referring now to FIGS. 6 and 7 , a user may control the length of cord 2 by depressing clamping mechanism 33 a located over a spring-loaded handle. When a user simultaneously twirls device 17 , this causes cord 2 to be released from interior space 32 as the momentum of ball 3 and ribbons 4 pull on cord 2 as centrifugal force is generated by the swinging. The user may exert a clamping force on ribs 33 with his/her thumb to stop the release of cord 2 using a spring mechanism as discussed above. When the cord is free of clamping, the cord may be permitted to automatically wind back into handle 1 and around anchor 34 using spring means, not shown. Clamping means 33 a (e.g., a linear piece of plastic or metal) carrying ribs 33 may be anchored to the handle by tab 36 to prevent clamping means 33 a from moving relative to cord 2 . [0025] Referring to FIG. 3 , in another embodiment, cord 2 may be affixed to an anchor (not shown) within handle 1 . Foldable handle 35 may be attached to the exterior of handle 1 . The user may wind foldable handle 35 to contract cord 2 back within handle 1 . Foldable handle 35 may lock into place on handle 1 by folding it in the direction shown by arrow Y so that handle projection 35 a fits within recess 48 on the handle. [0026] Referring again to FIG. 1 , it is desirable to use a cord 2 that will not break with repeated use. A material like nylon may be used. In an alternative embodiment, the cord may be a rubber-band-like material. Such a composition would create a completely different visual effect when the device is moved by the user. Also, a user may desire extra visual effects. In another preferred embodiment ( FIG. 1 ), cord 2 may have lights 16 (e.g. LEDs) attached, and/or may be made of or sprayed with glow in the dark attributes, which may add to the visual effects when the device is in use. [0027] Referring to FIGS. 4 and 5 , in a preferred embodiment the weight of the performance device may be provided by a variety of objects, such as ball 3 . With a weight, such as ball 3 attached to cord 2 and the streamers 4 attached to the cord or weight, the ribbon assembly can achieve speed that is difficult to achieve without the weight, enabling additional configurations to be used within the air. When using the device, the user may swing the ball 3 on the cord 2 by the handle 1 , striking and bouncing the ball against a surface. This adds an extra visual and performance feature. In another preferred embodiment, the ball may have a light within it (not shown). [0028] Referring again to FIG. 6 , in another preferred embodiment, a whistle 13 may be attached to cord 2 . In yet another embodiment (not shown), whistle 13 may be the only weight attached to cord 2 . And in yet another embodiment not shown, bells may be coupled to cord 2 or ribbons 4 . When the device is whirled around in these embodiments, the whistle 13 or bells (not shown) may add pleasant (or piercing) sound to the visual display provided by the performance device. [0029] Referring again to FIGS. 4 and 5 , the ribbons or streamers 4 may be attached to each other by a rivet 6 . Rivet 6 may hold multiple ribbons or streamers 4 to each other. Alternatively, they may be secured to the device by a knot (not shown) in cord 2 . [0030] Other changes and modifications constituting insubstantial differences from the present invention, such as those expressed here or others left unexpressed but apparent to those of ordinary skill in the art, can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is, therefore, intended that such changes and modifications be covered by the following claims.
A streamer toy or a performance device, including a handle attached to a cord whose length can be varied and which can be extended or retracted. A weight, such as a ball, may be connected to the cord. The cord may have one or more ribbons or streamers attached to it. A user can perform various movements with the toy or performance device which cause the ribbons or streamers to make various configurations in the air, such as serpents, spiral, throws and catches, boomerangs, and flips. The invention may also include whistles, bells, and/or lights to further enhance the performance.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of co-pending application Ser. No. 10/827,141 filed Apr. 19, 2004, is a continuation-in-part of co-pending application Ser. No. 11/522,858 filed Sep. 18, 2006 and also claims priority from Provisional Application Ser. No. 60/833,968 filed Jul. 28, 2006. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not Applicable. REFERENCE TO A MICROFICHE APPENDIX [0003] Not Applicable. TECHNICAL FIELD [0004] This invention is directed to methods of clarifying industrial wastewater, specifically those wastewaters containing, soluble and insoluble organic compounds from a variety of sources including but not limited to industrial laundries, food manufacturing and processing, printing, and those industries where any organic matter is present in a wastewater matrix. BACKGROUND OF THE INVENTION [0005] In the industrial wastewater treatment field of solids/liquid separation, suspended and emulsified solids are removed from water by a variety of processes, including sedimentation, straining, flotation, filtration, coagulation, flocculation, and emulsion breaking among others. Additionally, after solids are removed from the wastewater they must often be dewatered. Liquids treated for solids removal often have as little as several parts per million (ppm) of soluble organic matter, or may contain several thousand ppm soluble organic matter. Solids being generated as sludge may contain anywhere from 0.1 to 6 weight percent solids prior to dewatering, and from 20 to 50 weight percent solids material after dewatering by a plate and frame press. Solids/liquid separation processes are designed to remove solids from liquids and the more solids generated in the process, the more costly its disposal. [0006] While strictly mechanical means have been used to effect solids/liquid separation, the modern methods often rely on mechanical separation techniques that are augmented by synthetic and natural polymeric materials to accelerate the rate at which solids can be removed from water. These processes include the treatment of wastewater with cationic organic and inorganic coagulants that coagulate suspended particulates to form larger particles that then may be brought together by an anionic flocculent to create particles large enough to be removed from the waste stream by mechanical means, i.e., flotation or clarification. These methods have marginal success in the removal of soluble organic matter in the form of biochemical oxygen demand, semi-volatiles or volatile organic compounds without the addition of downstream treatment facilities or filters specifically designed for such removal to make the effluent suitable for industrial reuse or disposal in compliance with local permit discharge requirements. [0007] In the industrial wastewater, the chemical treatment of wastewater to a typical municipal standard of 250 to 300 ppm of biochemical oxygen demand (BOD), (EPA method 304.5), 300 to 1200 chemical oxygen demand (COD), and the reduction of volatile and semi-volatile (henceforth called volatiles) compounds either individually or as an aggregate amount to the level of federal, state or local standards prior to the introduction of this invention has been: the hydraulic equalization of untreated wastewater followed by the metered flow of the wastewater through a pipe or tanks to provide for retention time for the injection of a variety of chemicals including combinations and individually, both organic and inorganic coagulants and aids, followed by an organic component flocculent to produce coagulation and flocculation. However after treatment by the above methods in streams containing sufficient amounts of influent BOD, COD and volatiles, treatment methods at times have not been sufficiently adequate to reduce these agents to acceptable discharge standards by either a surchargable or absolute standards. [0008] Chemical treatment generally refers to the removal of non-settleable material by coagulation and flocculation. Chemical treatment for wastewater clarification is typically employed when colloidal and micro emulsified solids need to be removed so that the total petroleum hydrocarbons (TPH), fat, oil and grease (FOG), (BOD), (COD), volatiles total suspended solids (TSS), and other contaminants being discharged to a receiving stream need to be minimized. Typically, such treatment comprises using a cationic coagulant with one or more inorganic components, injected in combination or individually, followed by an anionic flocculent. Coagulation is the process of destabilization of the colloid waste particle by causing the coagulant (at 50-1000 ppm) to absorb by means of charge neutralization to form microfloc and impart residual cationic surface charge of the coagulated particles. The second step is to introduce a coagulant aid, i.e., ferric chloride, aluminum sulfate, ferrous sulfate, calcium chloride, polyaluminum chloride, typically at a rate of 75-700 ppm depending on the species, to increase the ability to form a more highly cationic surface that will cause the further adsorption of the coagulated particles onto the surface of an additional chemical, usually bentonite clay, at 200-900 ppm through a “sponge” effect. Flocculation occurs when the highly charged anionic flocculent bridges the previously formed cationic particles. Once neutralized, particles no longer repel each other and can come together to form larger agglomerated solids or sludge, which may then be removed from the water. [0009] Clarification chemicals are typically utilized in conjunction with mechanical clarifiers including dissolved air flotation systems (DAF's) induced air flotation systems (IAFs), and settlers for the removal of solids from the treated water. The clarification chemicals coagulate and/or flocculate the suspended solids into larger particles, which can then be removed from the water by gravitational settling, flotation, or other mechanical means. [0010] Processes for the preparation of high molecular weight cationic dispersion polymer flocculants are described in U.S. Pat. Nos. 5,006,590 and 4,929.655. High molecular weight, high active polymer cationic solution polymers for water clarification, dewatering and retention and drainage are disclosed in U.S. Pat. No. 6,171,505. BRIEF SUMMARY OF THE INVENTION [0011] The invention is directed to methods of clarifying industrial wastewater, specifically industrial laundry wastewater, to produce a compliant effluent reductions of COD, DOD and volatiles heretofore unrealized with only chemical treatment using a two part system of wastewater coagulants (blended and non-blended pDADMAC, polyamine or starch based coagulants) followed by a poly(acrylamide-co-acrylate) flocculent. Furthermore, the sludge produced using this invention will dewater in a typical plate and frame press, belt press or vacuum filter with or without the use of any other organic or inorganic compounds added to the waste stream or sludge. The use of substances such as slurried bentonite clay, ferric chloride or other stand alone metal salts can be used as a coagulant aids without departing from this invention. [0012] This invention pertains to the use of a cationic aqueous coagulants solutions containing polydiallydimethylammonium chloride (pDADMAC), poly quantinary amine (poly amine), or starch based organic polymers non blended or blended with either each other or inorganic metal salts including but not limited to ferric chloride, ferrous sulfate, aluminum sulfate, aluminum chlorohydrate (also known by other names i.e. ACH, also known as partially neutralized polyaluminum chloride) and poly aluminum chloride. These inorganic metal salts may also be introduced into the wastewater matrix separately from the coagulants. These coagulants and metal salts are used to produce, in the chemical demulsification of industrial wastewater, catatonic charged particles. [0013] In accord with this invention powered activated carbon (herein PAC) is also mixed in the coagulant solution. The PAC is utilized in the treatment of the wastewater to further treat in situ the wastewater for BOD, COD and volatile removal. The PAC does not interfere with the primary reaction created by the coagulants and metal salts for the primary treatment of the industrial wastewater. The PAC reacts with the BOD, COD, and volatile compounds remaining after the first micoflocculation. It is the properties of PAC that permit it to reduce these pollutants through secondary absorption reaction with organic compounds [0014] Once these particles are created and the wastewater is initially cleaned in a charge neutralization and absorption reaction by the coagulants with or without the metal salts and the secondary removal is created by the PAC premixed in the coagulant solution, the wastewater is cleaned using a low to high molecular weight low to very highly charged cationic solution coagulant (polymer) premixed with an inorganic aluminum species as one product, followed by a low to very high molecular weight anionic flocculent, i.e., poly(acrylamide-co-acrylate), (also known herein as sodium acrylate flocculent) with a 5% charge or higher (preferably 50% or higher), added in solution to produce particulate of sufficient size to be removed by physical means. The wastewaters, to which this invention is directed, may be produced by the food, ink & printing, pulp and paper processing industries along with the industrial cleaning of products, including but not limited to: uniforms, shop towels, ink towels, mats, rugs, bar mops, aprons, coveralls and coats, used to protect personnel from manufacturing or commercial wastes. [0015] The creation of the wastewater stream can be through the use of all available commercial equipment that is used by the above industries. These streams must then be collected in such a way as to promote the batch collection or intermittent or continuous flow of the stream. This collection of wastewater then may be further treated by batch or flow proportion as to allow for the injection and mixing of treatment chemicals by primary coagulation and flocculation only. This invention cleans the wastewater and increases the ability of the coagulant solution to remove BOD, COD and semi-volatile compounds by as much as 300% (depending on the analyte of concern). Furthermore, at the proper doses, this invention allows the sludge to be dewatered in equipment pertinent to this function with or without coagulant aids heretofore mentioned for improving dewatering characteristics [0016] The specific invention herein relates to the wastewater batch, or the in-stream use of the coagulant polymers (non-blended or blended with each other or metal salts) with PAC (blended coagulant with PAC which may be called a paculant) mixed directly into the coagulant solution as a finished product ready for field distribution. The field use paculant is injected into the wastewater stream in a diluted or an undiluted form, at any point prior to the sodium acrylate acrylamide flocculent injection with approximately ten (10) seconds interval (or more) between the injections. The paculant must be injected in the correct empirical quantity and given a sufficient predetermined time to begin and complete the microcoagulation of the waste particles, during the time the highly water miscible coagulant is “washed off” the PAC particle in the coagulant solution. The reaction time necessary for this to be accomplished varies depending on the various types of wastewater streams being treated, and also may be accomplished by the strength and/or dilution of coagulant solution by water. The PAC is then left in a state able to absorb remaining amounts of organic pollutant as to be of a reduction of these pollutants in the treated wastewater effluent. This reaction needs at least two (2) seconds and the flocculent must be injected in the correct empirical quantity and given sufficient time to begin and complete the flocculation of the coagulated particles prior to dewatering. The paculant and flocculent must be injected in sufficient quantity to create the appropriate conditions in the sludge that allow for the dewatering of the sludge generated by this process. These injection or dosing ratios are critical to the overall performance of the invention. [0017] The liquid, emulsified, or dry anionic flocculent is made into any solution strength (commonly between 0.05-0.5%, 0.2% being preferred), and injected post coagulant by at least a two (2) second interval (10 seconds being preferred) and in sufficient empirical quantities as to cause coagulated wastewater to form flocculated waste particles of sufficient size to settle in clarification or rise by flotation, as by dissolved/induced air or other means. [0018] The combination of the paculant and the flocculent in the wastewater stream produces an effluent that has been demonstrated to reduce organic compounds as much 300% from typical treatment schemes depending on the analyte of concern. The process testing of this invention has shown these reductions to be typical of the specific application of the invention disclosed herein. [0019] The flocculants of this invention must be of sufficient charge density, molecular weight and added in sufficient quantities, as to aid in all dewatering mechanisms, typically being a plate and frame press often found in typical plants. BRIEF DESCRIPTION OF THE DRAWING [0020] The novel features which are believed to be characteristic of this invention are set forth with particularity in the appended claims. The invention itself, however, both as to its organization and method of operation, together with further objects and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying drawing, which illustrates schematically an industrial laundry wastewater treatment system embodying features of this invention. DETAILED DESCRIPTION OF THE INVENTION [0021] In accordance with the present invention, methods are provided for removing contaminants from an aqueous solution. [0022] Methods are provided for removing: surfactants, phenolics, total petroleum hydrocarbons, fats oil and grease, TSS contributors, BOD contributors, COD contributors, TOC contributors, and organic soluble material from an aqueous solution. The surfactants, phenolics, total petroleum hydrocarbons, fats, oil and grease (FOG), TSS contributors, BOD contributors, COD contributors, and TOC contributors from an aqueous solution are removed by adsorption onto a carrier precipitate which is formed in situ within the aqueous solution. In each of the embodiments of the invention the preferred method involves rapidly forming the precipitate. [0023] The method of the invention can be used to remove the following contaminants from the industrial wastewater stream: TSS contributors, BOD contributors, COD contributors, TOC contributors, and/or fats, oil and grease (FOG). The invention will now be described first with respect to FOG, TSS contributors, BOD contributors, COD contributors, and TOC contributors. Unless otherwise stated, all process and apparatus parameters disclosed for FOG removal are equally effective for the removal of the other contaminants as well. Likewise, unless otherwise stated, all process and apparatus parameters disclosed for the removal of the other non-volatile contaminants are equally effective for heavy metal removal as well. [0024] “Coprecipitation” as used with respect to the invention described herein refers to the chemical phenomenon where, within an aqueous solution containing a cationic carrier precipitate precursor, an anionic carrier precipitate precursor, and one or more coprecipitant precursors, the cationic and anionic carrier precipitate precursors are caused to chemically react and precipitate out of the aqueous solution as carrier precipitate particles; and, as the carrier precipitate particles are formed, coprecipitant precursors are removed from the aqueous solution by adsorption onto the surface of the carrier precipitate particle and/or by occlusion within the interior of the carrier precipitate particle. [0025] The coprecipitant reaction is very rapid. Typically, more than 85 weight percent, and usually more than ninety-nine (99) weight percent, of the oil and grease are removed from the waste solution within about 10 seconds after the formation of the agglomerated particle. [0026] Finally, the methods of the invention are superior to conventional precipitation methods in that these methods treat the organic soluble material remaining in the water after the initial microflocculation has taken place. The aqueous polymeric coagulants and metal salts used in creating blends used in the methods of this invention are made by several manufacturers. The PAC used in the methods of this invention is manufactured by several manufacturers. The first chemical used in the invention is mixed in controlled conditions with a percent by weight of PAC ranging from 0.5% to 25%. [0027] By accepted definition, powdered activated carbon is activated Carbon that is smaller than 80 mesh. Representative sizes for the activated carbons sold include 50-60% 200 mesh to 600 mesh, 60% less than 325 mesh, and 90% less than 325 mesh. Though even finer grinds can be used, its source can be any of the materials used to make activated carbon-wood, sawdust, bituminous and sub bituminous coals, anthracite, coconuts, lignite, peat, or petroleum stocks. The characteristics of the activated carbon are the direct result of the type of material used. The majority of powdered carbons sold in the world are those derived from wood, lignite, and coals. On the basis of the source for the activated carbon, the carbons are made into powder and will vary according to their density, ash content, pore volume distributions, and adsorptive properties, representative of their total surface areas. For this invention one such property of the carbon is the iodine number, which measures surface area and pores less than 28 angstroms in size, and it is used to grade carbons used in the water field. Another such property is the molasses number, which is a measure of macroporosity and the availability of transport pores. The materials used to make the powder can also be acid washed to lessen their ash content prior to grinding. Acid washed materials generally show a slight increase in apparent density, and a lessening of their iodine number of between 50 and 100 points. For the purpose of this invention the PAC used may have the characteristic properties of being both water-soluble and non-water soluble. [0028] The size of the pores on the PAC allow it to be placed iii the coagulant mixture without the coagulant being absorbed in a quantity to render the PAC ineffective in the absorption of soluble organic material remaining after reaction. The larger size organic molecules (>1000 angstroms) of the coagulant are too large in size to fill the pores of the PAC particles. This then allows the PAC particle to remain in suspension in the primary coagulant mixture without significant change of the PAC soluble organic reduction properties. [0029] This completed PAC and coagulant mixture or paculant is injected into the waste stream in empirical quantities of typically 50-700 parts per million (ppm), depending primarily on stream flow rate, mix times, or strength, to cause the coagulation of negatively charged waste particles. The characteristic of water-soluble coagulants to disperse within an aqueous solution rapidly causes release of the surrounded PAC particle by allowing it to be “washed” of coagulant by the surrounding wastewater. As the pore sites on the PAC become available, these sites then are able to become the locations at which soluble organic compounds are then attached. [0030] The resulting coagulated particle then has sufficient mass and residual cationic charge to react with the subsequent addition of the pre-described, water dispersed anionic flocculent to create an agglomerated particle of sufficient size for removal by mechanical means. It is during the step of flocculation that the pollutant laden PAC particle is caught in a sweep reaction during this agglomeration. The flocculent is injected into the waste stream after a predetermined time to permit the cationic blend to substantially complete the coagulation of the particles by at least two (2) seconds after the injection of the coagulant blend in empirical quantities of 1-50 ppm. The time interval for the coagulant to sufficiently absorb the waste particles prior to injection of the flocculent must be no less than two (2) seconds but longer time may be required. Sufficient passive or active mechanical action must take place between the wastewater and the coagulant to allow the intimate commingling of the waste particles with the coagulant prior to addition to the flocculent. [0031] The anionic flocculent must be of a molecular weight, as termed in the industry, low to “very high” and of a charge density of no less than five percent (5%) and up to 100% but usually around fifty percent (50%). Again depending on wastewater stream strength the preferred range of 7-30 ppm of flocculent is needed to flocculate the coagulated particles to a level where the additional use of other coagulant aids and/or dewatering aids is not necessary, but may be used if desired. [0032] Using this invention has shown to aid in the reduction of soluble organic compounds by as much as 300% depending of the analyte of concern. [0033] The following examples are set forth to illustrate this invention and render same more understandable but are not intended to limit the scope of the herein disclosed and claimed invention. EXAMPLE ONE [0034] Laundry plant #1 has a daily average water usage of 65,000 gallons per day with 50% of the input product being shop towels, mats, ink wipers and other heavy soils. The prior existing program being used for industrial pretreatment was a poly (diallydimethylammonium chloride) mixed with aluminum chlorhydrate solution with a dose rate of 200-500 ppm residence time for each chemical being 15-20 seconds at 125 gpm flow. This created coagulated particles that were then flocculated with a 0.2% polyacrylate flocculent at 6-8 ppm to produce particles able to be floated through mechanical means. The plate and frame press produced dewatered sludge cakes amounting to 60 cubic feet per day. Typical BOD results from effluent analysis ranged from 450 ppm to over 2000 mg/l. [0035] The method of this invention was used to replace the prior existing program with a dose rate of 200-400 ppm of paculant [PAC and a poly (diallydimethylammonium chloride) mixed with aluminum chlorhydrate solution being the primary coagulant] using a mix time of approximately 20 seconds, and the application of the flocculent at 20-30 ppm using a mix time of approximately 40 seconds, resulting in floc that was floated through mechanical means. [0036] Effluent BOD analysis showed that during operation effluent BOD ranged from >150 to 295 mg/l. No change in the amount of sludge generated was seen nor degradation in other effluent quality parameters. EXAMPLE TWO [0037] Laundry plant #2 with a daily average water usage of 80,000 gallons per day with 40% of the input product being shop towels, mats, ink wipers and other heavy soils. The prior existing program being used for industrial pretreatment was a poly (diallydimethylammonium chloride) mixed with aluminum chlorhydrate solution with a dose rate of 200-700 ppm residence time for each chemical was approximately six minutes for the first chemical and 10 seconds for the second chemical at 60 gpm flow. This created coagulated particles that were then flocculated with a “wetted” 0.2% polyacrylate flocculent at 6-8 ppm to produce particles able to be floated through mechanical means. Typical COD results from effluent analysis ranged from 800 ppm to over 2000 mg/l. [0038] The method of this invention was used to replace the then existing program with a dose rate of 200-700 ppm of paculant using a mix time of approximately six minutes, and the application of the flocculent at 20-30 ppm using a mix time of approximately 40 seconds, resulting in floc that was floated through mechanical means. [0039] Effluent COD analysis showed that during operation effluent COD ranged from >150 to 295 mg/l. No change in the amount of sludge generated was seen nor degradation in other effluent quality parameters. DRAWING [0040] Enclosed on a Separate Sheet. SEQUENCE LISTING [0041] Not Applicable.
Methods are described for removing contaminates from aqueous industrial wastewater process streams, to yield a less contaminated aqueous specifically in the area of soluble organic containing effluent for discharge. A premixed medium/high molecular weight and medium/high charged cationic coagulant solution polymer and a powered activated carbon (PAC) is injected into the wastewater, and after a delay on the order of about ten seconds or greater, a high molecular weight highly charged anionic flocculent polymer solution is injected into the wastewater which reduces oil and grease (FOG), (BOD). (COD), volatiles total suspended solids (TSS), and other contaminants.
2
BACKGROUND OF THE INVENTION The present invention is directed to image-processing systems, particularly those in which updated image values are generated as functions both of previous values and of new data. In many image-processing systems, the raw data must be subjected to various types of transformations. Some of the transformations depend only on the values of the current input signals. For instance, some image processing involves so-called gamma correction, which compensates for the non-linear relationship between a camera output and the intensities to which the camera responds. Other forms of transformation depend not only on the data currently being obtained but also on the data previously stored. For instance, systems for detecting changes in an image may subtract current pixel (picture-element) values from stored pixel values to detect movement in the image. Another example of processing that uses both stored data and newly generated data is noise reduction by averaging over a plurality of successive scans of an image. These separate functions are commonly provided by separate specialized circuits or by generalized arithmetic logic units. Both of these approaches can be relatively expensive, and the time that it takes a generalized arithmetic logic unit to perform certain real-time applications may be prohibitive. An object of the present invention is to provide a variety of image-processing features in fast and relatively simple and inexpensive circuitry. SUMMARY OF THE INVENTION The foregoing and related objects are achieved in an image-processing system in which a multiplexer supplies address signals to a look-up table whose resulting output is applied as data to a frame buffer. The frame buffer is a memory having a plurality of memory locations, each of which is associated with a different pixel in an image. The multiplexer selects the bits of the address signals from bits of output data signals of the frame buffer and from output data signals of an image-signal source, such as an analog-to-digital converter that converts the output of a video camera to digital values. By changing selection signals applied to the multiplexer, it is possible to use this same system alternately for transformations dependent only on newly generated data, transformations dependent only on stored data, and transformations dependent on both. BRIEF DESCRIPTION OF THE DRAWING These and further features of the present invention are described in connection with the accompanying drawing figure, which is a simplified block diagram of an image-processing system employing the teachings of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The drawing depicts an image-processing system 10 for performing any one of several operations on images processed in the form of digital words representing information concerning individual picture elements ("pixels") of an image. The image is stored in a frame buffer 12. In the illustrated embodiment, the frame buffer is organized in 512 rows and 512 columns of locations, each of which contains a 12-bit data word. Each of the locations is associated with a separate pixel. It should be understood that the association between pixels and memory locations may well be dynamic; the frame buffer typically is being rewritten continually, and the pixel with which a location is associated during one scan through the memory may be different from that with which it is associated in a subsequent scan. The data output bus 14 of the frame buffer 12 in this embodiment consists of twelve parallel lines carrying, at any given time, signals representing the twelve-bit contents of a single frame-buffer location. A typical use of the data output of the frame buffer 12 is transmission to a digital-to-video converter 16 for presentation on a cathode-ray tube 18. However, there are many uses for images that do not require presentation to a human operator, so the system of the present invention is not restricted to systems having cathode-ray tubes or similar display devices for human use. The ultimate source of the images stored in the frame buffer 12 is typically some type of transducer such as a video camera 20, whose analog output is converted into digital form by an analog-to-digital converter 22. Another typical source is a second frame buffer. In the illustrated embodiment, the analog-to-digital converter 22 has eight bits of resolution, producing eight parallel bits AD7:0. These analog-to-digital-converter data are applied to a multiplexer circuit 24 that includes four individual multiplexers 26, 28, 30, and 32. The purpose of the multiplexer circuit 24 is to generate an address signal MU11:0 for application to a look-up table 34. The look-up table 34 is typically a random-access read/write memory although it can in principle be a read-only memory. The manner in which the multiplexer circuit 24 generates the address signals for the look-up table 34 is determined by signals on control lines 36 from a control circuit 38. The control circuit 38 in turn operates under directions from a host computer 40. Clearly, the look-up table 34 has more locations than are required by the resolution of the analog-to-digital converter 22. Specifically, there are 256 possible output values of the analog-to-digital converter 22, while there are 4,096 locations in the look-up table 34; i.e., there are 16 times as many look-up-table locations as there are possible analog-to-digital-converter output values. This makes it possible to store, for instance, different correction functions for each of sixteen different combinations of camera and display device. The computer 40 initially writes the sixteen correction functions into the look-up table 34 and deposits a code designating the desired correction function into a register 42, which is the third source from which the multiplexer circuit 24 draws signals in the illustrated embodiment. Of course, combinations of sources different from the three in the illustrated embodiment may be used in other versions of the present invention. The signals on lines 36 select sources for the bits of the look-up-table address MU11:0 by selecting one of two states of each of the multiplexers 26, 28, 30, and 32. Through the operation of an AND gate 44, the state of multiplexer 32 depends on the states of multiplexers 28 and 30. As a consequence, there are eight possible states of multiplexer circuit 24. In the illustrated embodiment, however, only six of these states are intended to be used. In the first state, multiplexer 26 forwards the register output RG3:0, multiplexer 28 forwards the two most-significant bits AD7:6 of the analog-to-digital-converter output, and multiplexer 30 forwards the output of multiplexer 32, which output is the remaining analog-to-digital-converter output bits AD5:0. Thus, the address signals sent to the look-up table 34 consist of the four register bits and the eight analog-to-digital-converter output bits. In this multiplexer setting, the system 10 may, for instance, be used for gamma correction, in which the value to be stored is typically a fractional power of the value represented by the analog-to-digital-converter output AD7:0. A given value from the analog-to-digital-converter 22 causes the multiplexer 24 to designate a location in the look-up table 34 having an address of which eight bits represent that analog-to-digital-converter value and the other four bits designate one of sixteen possible values of gamma, the fractional power for the intended gamma correction. The contents of the look-up table 34 at that location are equal to the analog-to-digital-converter output value raised to gamma, so the value that the look-up table 34 sends to the frame buffer 12 is not the raw output of the analog-to-digital converter 22; it is a transformed output. In the second mode, the multiplexer circuit 24 supplies as address bits to the look-up table 34 the twelve-bit output of the frame buffer 12; multiplexer 26 forwards the four most-significant bits FB11:8 of the frame-buffer output, multiplexer 28 forwards the next two bits FB7:6, and multiplexer 30 forwards the remaining bits FB5:0. This mode can be used for a number of different functions, such as arithmetic or logic processing, window processing, and other types of image transformations. It should be noted that this mode in particular permits operations on data whose intensity resolution is high. In the first mode, in which the data source is the analog-to-digital-converter 22, the input data has only eight bits of intensity resolution, so only eight bits of the look-up-table contents would typically be significant; the other bits generated by the look-up table 34 and stored in the frame buffer 12 would not represent part of a pixel value. In this second mode, however, the contents of the frame buffer 12 could be obtained from some other, high-resolution source, so the entire contents of the frame buffer 12 could represent a pixel value. The third mode of operation is similar to the first except that the analog-to-digital-converter output is replaced by eight bits of the frame-buffer output. Specifically, multiplexer 26 forwards the register bits RG3:0, while multiplexers 28 and 30 together forward eight bits FB7:0 of the frame-buffer output. It should be noted that the frame-buffer bits FB7:0 were not referred to as the eight least-significant bits. This is because the higher-numbered bits FB11:8 would not typically contain bits of a pixel-value representation in this mode. Thus, the entire pixel value would be contained in bits FB7:0. This mode can be used for any type of application in which it is desired to transform a previously stored image in accordance with one of several possible transformation functions. It may be desired, for instance, to transform stored raw data into a form best suited to one of a number of different display devices. The particular display device currently in use, and thus the choice of transform function, is designated by the output of the register 42. Or an operator may cause the control circuit repeatedly to deposit different contents into the register 42 in order to find the most-satisfactory display. In the fourth mode, half of the address bits are drawn from the analog-to-digital converter 22 and half are drawn from the frame buffer 12. Specifically, multiplexers 26 and 28 forward six frame-buffer output bits FB11:6, while multiplexer 30 forwards the output of multiplexer 32. In this mode, the output of multiplexer 32 is analog-to-digital-converter output bits AD7:2 rather than AD5:0. The pixel values are stored in the halves of the frame-buffer locations that produce output bits FB11:6, while it is the other halves of the locations, those that result in FB5:0, that contain nonpixel-value information. This mode has a wide variety of uses. It may be used for subtraction--i.e., to subtract the pixel value of one frame from the corresponding pixel value of the subsequent or previous frame. For this purpose, the contents of each look-up-table location would equal the difference between the value represented by one half of its address bits and the value represented by the other half of its address bits. Another possible use of this mode is to reduce noise by exponential averaging. For exponential averaging, the contents of a look-up-table location might be equal to, say, seven-eighths of the value represented by the frame-buffer portion of its address plus one-eighth of the value represented by the analog-to-digital-converter part of its address. In the fifth mode, four bits of the address come from the frame buffer 12, while the remaining eight come from the analog-to-digital converter 22. Specifically, multiplexer 26 forwards frame-buffer bits FB11:8 while multiplexers 28 and 30 forward analog-to-digital-converter output bits AD7:0. This mode might be used for selective conversion in accordance with the position of the pixel in the image. The image might be divided into regions, for example, and the frame-buffer bits in each frame-buffer location corresponding to output bits FB11:8 might, instead of being part of a pixel value, identify the region to which the corresponding pixel belongs. The conversion function for the outputs of the analog-to-digital converter 22 would differ in accordance with the region to which the pixel belongs. For such an application, four look-up-table bits in each location corresponding to look-up-table output bits LU11:8 would be equal to four bits MU11:8 of its address so that the region information rewritten into the frame buffer would equal the region information read from it. The remaining bits of each location in the look-up table 34, i.e., those corresponding to its output bits LU7:0, would represent the transformation of the value represented by its address bits MU7:0 in accordance with the function designated by its other address bits MU11:8. In the final mode, the multiplexer circuit 24 draws the address bits MU11:0 from all three sources: the frame buffer 12, the analog-to-digital converter 22, and the register 42. Multiplexer 26 forwards the four register bits RG3:0, multiplexer 28 forwards two of the frame-buffer bits FB7:6, and multiplexer 30 forwards the output of multiplexer 32, which in turn forwards the five most-significant bits AD7:2 of the analog-to-digital-converter output. Like the fifth mode, the sixth mode is typically used to implement a region-dependent transform. Specifically, bits six and seven of the contents of each frame-buffer location would designate the one region to which that location belongs out of four possible regions in the image, while bits five through zero would contain the pixel value. The remaining bits typically would not contain meaningful information. The register bits RG3:0 would designate the one of sixteen possible combinations of four transform functions to be used. Thus, for each location in the look-up table 34, the contents of bits seven and six would be equal to bits seven and six of its address, while bits five through zero would equal the transform of the value represented by its address bits five through zero in accordance with the one transform function designated by its address bits seven and six out of the four-transform-function combination designated by its address bits eleven through eight. In operation, the computer 40 loads the look-up table 34 in accordance with the function to be performed. If necessary, the computer also places signals on lines 48 to load a value into register 42 that designates the portion of the look-up table 34 to be used. The computer 40 then sends appropriate control signals over lines 50 to the control circuit 38 to cause it to begin operation. The control circuit 38 sends synchronizing signals over lines 52 to the camera 20 and clocks the analog-to-digital converter 22 to convert the video signals into pixel values. At the same time, it sends address and control signals over lines 54 to the frame buffer 12 so that the frame buffer generates data signals representing the location associated with the pixel for which the analog-to-digital-converter 22 is currently generating a pixel value. As a result, the frame-buffer output signals, together with the signals presented by the register 42, are applied to the multiplexer circuit 24 at the same time as the output of the analog-to-digital converter 22 is so that the bits that the multiplexer circuit 24 draws from the different sources represent the same pixel. The control circuit 38 applies selection signals over lines 36 to the multiplexer circuit 24 to indicate the proper selection of bits for the look-up-table address. The multiplexer circuit 24 accordingly applies the desired address to the look-up table 34, and the control circuit 38 applies control signals to lines 56 that cause the look-up table 34 to generate signals LU11:0 representing the contents of the addressed look-up-table location. At this point, the control circuit 38 sends control signals and address signals representing the location associated with that pixel over lines 54 to the frame buffer 12 to cause it to read the look-up-table contents into the addressed location. Those skilled in the art will recognize that the pixel values are generated at a rapid rate. As a consequence, the operation just described in a simplified way is actually performed in a pipelined manner. That is, between the time at which data for a given pixel are initially produced by the frame buffer 12 and the analog-to-digital-converter 22 and the time when the results of those data are written into the frame-buffer 12, data for several subsequent pixels will have been generated and the resulting signals will have begun to propagate through the stages just described. Accordingly, data for a given pixel are read from the frame buffer 12 at approximately the same time as that at which data for another pixel several locations removed from the first pixel are being written into the frame buffer 12. If the image is to be monitored by the user while the processing occurs, the control circuit also sends control signals over lines 56 to synchronize the digital-to-video converter 16 with the frame-buffer reading operation so that the image is displayed properly on the cathode-ray tube 18. In order to change the function performed by the image-processing system 10, the computer 40 performs one or more of three operations. The computer 40 may load the register 42 with new contents. It may cause the control circuit 38 to change the selection signals on line 36 so that the multiplexer circuit 24 assembles the look-up-table addresses in the newly desired manner. And it may load the look-up table 34 with new contents. It then initiates operation of the control circuit 40, and the image-processing circuitry 10 now performs a different function. It is thus clear that, by practicing the invention described above, those skilled in the art can achieve a great degree of versatility with a minimum of processing hardware. The present invention thus constitutes a significant advance in the art.
Data to be stored in a frame buffer (12) that stores data representing an image are drawn from a look-up table (34). The look-up table (34) contains conversion data and is addressed by the output of a multiplexer circuit (24). The multiplexer circuit (24) receives its inputs from the data output port of the frame buffer (12), from a register (42), and from an analog-to-digital converter (22) that converts the output of a video camera (20) to digital signals. In response to different values on selection-signal lines (36), the multiplexer circuit (24) assembles the address that it applies to the look-up table (34) from different combinations of the outputs of the frame buffer (12), the register (42), and the analog-to-digital-converter (22). By changing the selection signals applied to the multiplexer circuit (24), it is possible to employ the same image-processing system (10) to perform different functions, such as gamma correction, contrast variation, iamge-from-image subtraction, and multiple-image averaging.
6
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] This invention is directed to drilling rigs; drilling rigs with an erectable mast; and to methods for erecting such a mast. [0003] 2. Description of Related Art [0004] The prior art discloses a variety of rigs used in drilling and wellbore operations and methods of rig assembly; for example, and not by way of limitation, rigs and assembly methods as disclosed in U.S. Pat. Nos. 2,857,993; 3,340,938; 3,807,109; 3,922,825; 3,942,593; 4,021,978; 4,269,395; 4,290,495; 4,368,602; 4,489,526; 4,569,168; 4,821,816; 4,831,795; 4,837,992; 6,634,436; 6,523,319; 6,994,171; 7,306,055; 7,155,873; and 7,308,953 and the references cited in these patents—all these patents incorporated fully herein for all purposes. [0005] In many drilling operations, drilling rigs and related systems, equipment, and apparatuses are delivered to a site, assembled and then disassembled. It is important that drilling rigs and their components be easily transported and assembled. Costs associated with land rigs and associated equipment, can be calculated on a per hour or per day basis, and, therefore, efficient assembly, takedown, transport, and setup operations are desirable. [0006] U.S. Pat. No. 3,922,825 discloses a rig with a stationary substructure base and a movable substructure base mounted thereon which is coupled to the stationary base and swings upright into an elevated position on a series of struts that are connected to the stationary base with swivel connections at each end. The movable base is otherwise stationary since neither the stationary base nor the movable base are mobile or repositionable without the use of an auxiliary crane or the like. The movable substructure base and the drill mast are raised with a winch mounted on an auxiliary winch truck. [0007] U.S. Pat. No. 3,942,593 discloses a mobile well drilling rig apparatus which has a trailerable telescoping mast and a separate sectionable substructure assembly with a rig base, a working floor, and a rail structure. The mast is conveyed to the top of the substructure by rollers and is raised by hydraulic raising apparatus to an upright position. With such a system the the mast assembly can be relatively long when transporting it and the mast can be unstable during raising. This system uses drawlines and winch apparatus to raise the mast onto the working floor. [0008] U.S. Pat. No. 4,021,978 discloses a telescoping mast assembly adapted for use with drill rigs and the like. The mast assembly has multiple sections, said sections being adapted for nesting one within the other in the telescoped-to-the-closed condition and each section has mutually convergent corner leg members which, when the mast assembly is extended, form concentric and in-line arrangements of the corner leg members from the base to the crown of the mast. Means are provided for connecting each mast section to its neighboring mast section upon extension thereof. In addition, means are also provided for indexing of the connector means upon extension of the mast assembly from its telescoped-to-the-closed condition. [0009] U.S. Pat. No. 4,821,816 discloses methods of assembling a modular drilling machine which includes a drilling substructure skid which defines two spaced parallel skid runners and a platform. The platform supports a draw works mounted on a draw works skid, and a pipe boom is mounted on a pipe boom skid sized to fit between the skid runners of the drilling substructure skid. The drilling substructure skid supports four legs which in turn support a drilling platform on which is mounted a lower mast section. The legs are pivotably mounted both at the platform and at the drilling substructure skid and a pair of platform cylinders are provided to raise and lower the drilling platform. A pair of rigid, fixed length struts extend diagonally between the platform and the substructure skid away from the platform such that the struts do not extend under the platform and obstruct access to the region under the platform. The pipe boom skid mounts a pipe boom as well as a boom linkage, a motor, and a hydraulic pump adapted to power the pipe boom linkage. The substructure skid is formed in upper and lower skid portions, and leveling rams are provided to level the upper skid portion with respect to the lower skid portion. Mechanical position locks hold the upper skid in relative position over the lower skid. In one aspect such a method for assembling an earth drilling machine includes the steps of: (a) providing a modular earth drilling machine comprising a drilling substructure skid, a draw works skid, and a pipe boom skid, the drilling structure skid having a collapsible drilling substructure platform and means for receiving the draw works skid and the pipe boom skid, the draw works skid having a draw works winch, and the pipe boom skid having a pipe boom pivotably mounted to the pipe boom skid for rotation about a pivot axis, at least one hydraulic cylinder coupled between the pipe boom and the pipe boom skid to rotate the pipe boom about the pivot axis, a hydraulic pump mounted to the pipe boom skid and coupled to the hydraulic cylinder by a closed hydraulic fluid circuit, and a pipe boom skid winch; the pipe boom skid, pipe boom, hydraulic cylinder and hydraulic pump forming a modular unit which is transportable as a single unit without any disconnection of the closed hydraulic fluid circuit; (b) positioning the substructure skid at a desired drilling position; (c) utilizing the pipe boom skid winch to pull the pipe boom skid into position with respect to the substructure skid; (d) utilizing the pipe boom skid winch to pull the draw works skid into position with respect to the substructure skid; and, in one aspect, the method further including raising the collapsible drilling structure platform, including utilizing the pipe boom skid winch to lift the drilling structure platform during at least an initial stage of the raising step. [0010] U.S. Pat. No. 4,831,795 discloses drilling derrick assemblies which provide for the elevation above ground level of the assembly's working floor which supports both the mast and the drawworks. Prior to erection, the elevatable equipment floor is carried on a supporting substructure, and a mast is pivotally connected to the elevatable floor in a reclining position. When the assembly is erected, the mast is pivotally raised and attached in place, and other rigging steps can be carried out. Through the use of an integrally mounted sling and winch assembly or, alternatively, through operation of the assembly's traveling block, the entire equipment floor is elevated to the desired level. In one aspect, a drilling structure is disclosed that has: a substructure for supporting the drilling structure on the surface through which drilling is to occur, an elevatable floor assembly which rests on the substructure in its lowered position, a reclining mast pivotally connected to the elevatable floor, a gin pole assembly mounted on the elevatable floor assembly rearwardly of the point at which the mast is pivotally connected to the elevatable floor and arranged to receive line for raising the mast, whereby the mast is raised prior to raising the elevatable floor assembly, a collapsible vertically standing elevating frame assembly mounted on the substructure and forwardly of the mast, when raised, and the forwardmost end of the elevatable floor assembly, winch means rotatably mounted in and arranged adjacent the forwardmost end of the substructure, a first elevating block means mounted in the elevatable floor and rearwardly of the elevating frame assembly, a second elevating block mounted on the elevating frame assembly at a vertical point corresponding with the level to which the elevatable floor is to be raised, an elevating line extending from the winch means and reeved about the elevating block so that motion of the winch means in one direction causes the second elevating block to move toward the first elevating block raising the elevatable floor vertically and forwardly, motion of the winch means in another direction lowering the elevatable floor vertically and rearwardly, and a brace member on each side of the drilling structure, each brace member being pivotally connected at its ends, respectively, to the substructure and the elevatable floor, the brace members being arranged in pairs forming parallel linkages thereby causing the elevatable floor assembly to be raised in an arc-like motion. [0011] U.S. Pat. No. 6,994,171 discloses two section masts with self-aligning connections and methods with self-aligning connections for a two section mast. The methods include the steps of transporting the elongated bottom mast section to a guide frame adjacent to a well site, the bottom mast section having a pair of front legs and a pair of rear legs. An elongated top mast section is transported to the well site, the top mast section having a pair of front legs and a pair of rear legs. The legs of the bottom mast section are positioned slightly below a level of the legs of the top mast section. Thereafter, the bottom mast section is raised slightly to order to engage the top mast section while simultaneously aligning the mast sections together. The sections are thereafter pinned together. In one method of self-aligning connections for a two section mast, the method includes: transporting an elongated bottom mast section to a guide frame adjacent to a well site, the bottom mast section having a pair of front legs and a pair of rear legs so that the bottom mast section is in a substantially horizontal orientation; thereafter transporting an elongated top mast section to the well site so that the top mast section is in a substantially horizontal orientation and so that the mast sections are substantially aligned lengthwise, the top mast section having a pair of front legs and a pair of rear legs; positioning the legs of the bottom mast section slightly below a level of the legs of the top mast section; raising the bottom mast section; and simultaneously engaging and guiding the mast sections together in a final connecting orientation. [0012] U.S. Pat. No. 7,155,873 discloses structural connectors for a drilling rig substructure; and a method and apparatus for connecting sections of a drilling rig substructure, in one aspect a structural connector is provided so that sections of a drilling rig substructure can be connected together without the use of pins or pin-type connectors. The structural connector utilizes specially-shaped fixed members connected to, and extending through, support plates that are attached to sections of a drilling rig substructure that mate with specially-shaped mating lugs that are mounted on mating lug plates that are attached to separate sections of the drilling rig substructure. When the sections of the drilling rig substructure to be connected are positioned together, the specially-shaped mating lugs engage the specially-shaped fixed members and form a high strength structural connection between the sections of the drilling rig substructure. In one aspect a structural connector is provided that has: a plurality of support plates each having a plurality of fixed support members extending therethrough, the fixed support members extending outwardly from both sides of the support plates and having side walls and contoured tops; a mating lug assembly having a plurality of mating lug plates and a plurality of mating lugs attached to each mating lug plate, each mating lug having a support notch therein; wherein the support notch of each mating lug has tapered guide surfaces at the entry point of the support notch, side walls, and a contoured top. BRIEF SUMMARY OF THE INVENTION [0013] The present invention, in certain aspects, provides drilling rigs with erectable masts. In one aspect, a mast includes a bottom mast component and a second, upper or midsection component that are connected together. [0014] In certain aspects, the present invention discloses a bottom mast section connectible to a midsection by moving a vehicle, e.g. a truck/trailer combination to place the two sections adjacent each other; connecting the bottom section to a support, e.g. but not limited to, a rig's substructure; raising, if necessary, the support or rig's substructure to which the bottom mast section is connected; and moving the vehicle to engage connections and, in one aspect, to align connections, of the bottom mast section and midsection. Once the connections have been engaged, the truck can move away and pins are used as a further securement to lock the two sections together and the truck moves away. [0015] The present invention discloses, in certain aspects, a method for connection two parts of a mast of a drilling rig, the method including: connecting a bottom mast section to a support, the bottom mast section having bottom connection apparatus; moving a second mast section adjacent the bottom mast section, the second mast section releasably connected to a vehicle and said moving done by moving said vehicle, the second mast section having second connection apparatus; and moving the bottom mast section so that the bottom connection apparatus contacts the second connection apparatus and engages the second connection apparatus to secure the bottom mast section to the second mast section, and, in certain aspects to facilitate connection engagement and align the mast sections as one mast section is lifted. [0016] The present invention discloses, in certain aspects, a mast system for rig operations, the mast system including: a support, a bottom mast section connected to the support; the bottom mast section having bottom connection apparatus; a second mast section adjacent and connectible to the bottom mast section, the second mast section releasably connected to a vehicle for moving the second mast section; the second mast section having second connection apparatus; and the bottom mast section movable on the support so that the bottom connection apparatus can contact the second connection apparatus and engage the second connection apparatus to secure the bottom mast section to the second mast section. [0017] Accordingly, the present invention includes features and advantages which are believed to enable it to advance drilling rig technology and rig mast erection and assembly technology. Characteristics and advantages of the present invention described above and additional features and benefits will be readily apparent to those skilled in the art upon consideration of the following detailed description of preferred embodiments and referring to the accompanying drawings. [0018] Certain embodiments of this invention are not limited to any particular individual feature disclosed here, but include combinations of them distinguished from the prior art in their structures, functions, and/or results achieved. Features of the invention have been broadly described so that the detailed descriptions that follow may be better understood, and in order that the contributions of this invention to the arts may be better appreciated. There are, of course, additional aspects of the invention described below and which may be included in the subject matter of the claims to this invention. Those skilled in the art who have the benefit of this invention, its teachings, and suggestions will appreciate that the conceptions of this disclosure may be used as a creative basis for designing other structures, methods and systems for carrying out and practicing the present invention. The claims of this invention are to be read to include any legally equivalent devices or methods which do not depart from the spirit and scope of the present invention. [0019] What follows are some of, but not all, the objects of this invention. In addition to the specific objects stated below for at least certain preferred embodiments of the invention, there are other objects and purposes which will be readily apparent to one of skill in this art who has the benefit of this invention's teachings and disclosures. It is, therefore, an object of at least certain preferred embodiments of the present invention to provide the embodiments and aspects listed above and: [0020] New, useful, unique, efficient, non-obvious drilling rigs, with new, useful, unique, efficient, nonobvious rig masts, and methods of their assembly and erection; and [0021] Such systems in which connections on a first mast section engage and become held in corresponding connections on a second mast section to secure the two sections together. [0022] The present invention recognizes and addresses the problems and needs in this area and provides a solution to those problems and a satisfactory meeting of those needs in its various possible embodiments and equivalents thereof. To one of skill in this art who has the benefits of this invention's realizations, teachings, disclosures, and suggestions, various purposes and advantages will be appreciated from the following description of preferred embodiments, given for the purpose of disclosure, when taken in conjunction with the accompanying drawings. The detail in these descriptions is not intended to thwart this patent's object to claim this invention no matter how others may later attempt to disguise it by variations in form or additions of further improvements. [0023] The Abstract that is part hereof is to enable the U.S. Patent and Trademark Office and the public generally, and scientists, engineers, researchers, and practitioners in the art who are not familiar with patent terms or legal terms of phraseology to determine quickly from a cursory inspection or review the nature and general area of the disclosure of this invention. The Abstract is neither intended to define the invention, which is done by the claims, nor is it intended to be limiting of the scope of the invention or of the claims in any way. [0024] It will be understood that the various embodiments of the present invention may include one, some, or all of the disclosed, described, and/or enumerated improvements and/or technical advantages and/or elements in claims to this invention. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS [0025] A more particular description of embodiments of the invention briefly summarized above may be had by references to the embodiments which are shown in the drawings which form a part of this specification. These drawings illustrate certain preferred embodiments and are not to be used to improperly limit the scope of the invention which may have other equally effective or equivalent embodiments. [0026] FIG. 1A is a side view of part of a drilling rig. [0027] FIG. 1B is a top view of the rig parts of FIG. 1A . [0028] FIG. 1C is a side view which illustrates a step in a method according to the present invention for assembling and erecting a rig mast. [0029] FIG. 1D is a side view which illustrates a further step in the method of FIG. 1C . [0030] FIG. 1E is a top view of the step of FIG. 1D . [0031] FIG. 1F is a side view of a further step in the method of FIG. 1C . [0032] FIG. 1G is a side view of a further step in the method of FIG. 1C . [0033] FIG. 1H is a side view of a further step in the method of FIG. 1C . [0034] FIG. 1I is a top view of a bottom section of a mast as assembled in FIGS. 1C-1H . [0035] FIG. 1J is a side view of the bottom section of FIG. 1I . [0036] FIG. 1K is a bottom view of the bottom section of FIG. 1I . [0037] FIG. 1L is an end view along the bottom section of FIG. 1I . [0038] FIG. 1M is a side view of the bottom midsection of a mast as assembled in FIGS. 1F , et seq. [0039] FIG. 1N is a side view of the bottom midsection of FIG. 1M . [0040] FIG. 10 is a bottom view of the bottom midsection of FIG. 1M . [0041] FIG. 1P is an end view along the bottom section of FIG. 1N . [0042] FIG. 2 is a perspective view of a bottom section of a mast according to the present invention connected to rig substructure (shown partially). [0043] FIG. 3 is a perspective view of a midsection of a mast according to the present invention. [0044] FIG. 4A is a perspective view illustrating a bottom section as in FIG. 2 for connection to a midsection as in FIG. 3 . [0045] FIG. 4B shows the bottom section of FIG. 4A connected to the midsection of FIG. 4A . [0046] FIG. 4C is a perspective view illustrating a step in a method of connecting the sections shown in FIG. 4A . [0047] FIG. 4D is a side view illustrating a further step in the method of FIG. 4C . [0048] FIG. 4E is a perspective view of a further step in the method. [0049] FIG. 4F is a side view of the step of FIG. 4E . [0050] FIG. 4G is a perspective view illustrating a further step in the method. [0051] FIG. 4H is a side view of the step shown in FIG. 4G . [0052] Presently preferred embodiments of the invention are shown in the above-identified figures and described in detail below. Various aspects and features of embodiments of the invention are described below and some are set out in the dependent claims. Any combination of aspects and/or features described below or shown in the dependent claims can be used except where such aspects and/or features are mutually exclusive. It should be understood that the appended drawings and description herein are of preferred embodiments and are not intended to limit the invention or the appended claims. On the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims. In showing and describing the preferred embodiments, like or identical reference numerals are used to identify common or similar elements. The figures are not necessarily to scale and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.[i. As used herein and throughout all the various portions (and headings) of this patent, the terms “invention”, “present invention” and variations thereof mean one or more embodiment, and are not intended to mean the claimed invention of any particular appended claim(s) or all of the appended claims. Accordingly, the subject or topic of each such reference is not automatically or necessarily part of, or required by, any particular claim(s) merely because of such reference. So long as they are not mutually exclusive or contradictory any aspect or feature or combination of aspects or features of any embodiment disclosed herein may be used in any other embodiment disclosed herein. DETAILED DESCRIPTION OF THE INVENTION [0053] FIG. 1A shows a drilling rig's substructure 11 supporting a drill floor 12 with a drawworks 14 positioned on the drill floor 12 . The substructure 11 and drill floor 12 have an open area A into which equipment can be moved. [0054] As shown in FIG. 1C the substructure 11 is in a lower position and a truck T has moved a bottom section 20 of a mast according to the present invention toward the drill floor 12 . An A-frame 13 is connected to the bottom section 20 of the mast. Mast raising cylinders 22 are in position for connection to the bottom section 20 . [0055] As shown in FIG. 1D , the truck T is stopped moving the bottom section 20 into the area A. The bottom section 20 is then connected to the mast raising cylinders 22 . The positions substructure raising cylinders 18 are adjusted and the A-frame 13 is connected to the drill floor 12 . [0056] As shown in FIG. 1E , legs 21 of the mast 21 legs are swung open for bolting to mast shoes 23 of the drill floor 12 . The mast raising cylinders 22 are then extended and the truck T is moved away. The mast raising cylinders 22 are then retracted to lower the bottom section 20 . [0057] As shown in FIG. 1F , a truck R has moved a midsection 30 of a mast according to the present invention toward the bottom section 20 . FIG. 1G shows the truck R stopped after moving the midsection 30 adjacent a projecting end of the bottom section 20 . The sub cylinder 18 and the mast cylinder 22 are raised to raise jaw members according to the present invention of the bottom section 20 adjacent corresponding connection members 32 according to the present invention of the midsection 30 . [0058] FIGS. 1I-1L show the bottom section 20 and FIGS. 1M-1P show the midsection 30 . The bottom section 20 has two legs 20 a each with a jaw member 29 having a slot 23 in each of two spaced-apart plates 24 . A space 25 is formed between ends of the plates 24 . A throat 25 a is formed between flared out portions 25 b of the plates 24 (or separate pieces 25 b are used connected to the plates). Two legs 20 r each have a connection member 26 with two spaced-apart plates 27 and holes 28 . A throat 27 a is formed between flared out portions 27 b of the plates 27 . A throat 27 c is formed between flared out portions 27 d of the plates 27 . In certain aspects of the present invention, any one or two throats described above may be deleted, or they may all be deleted. [0059] As shown in FIGS. 1F-1L , the midsection 30 has two legs 31 each with a connection member 32 having a transverse bar 33 . Each leg has a connection member 35 with holes 38 corresponding, upon section connection, to the location of the holes 28 of the connection members 26 . [0060] Ends of the connection members 32 are sized for movement into the spaces 25 of the jaw members 29 and the bars 33 are sized for receipt in the slots 23 . The connection members 35 are sized for receipt between the plates 27 of the connection members 26 and pins are insertable through the holes 28 , 38 to lock the two mast sections together. If one jaw member connects to one connection member and the other jaw-member/connection/member connection has not been fully effected, raising of the bottom section will force the other connection member into contact with and engagement with the other jaw member, facilitating alignment of the two sections and their connection. [0061] The truck R moves the midsection 30 adjacent the bottom section 20 so that ends of the connection members 32 move into the spaces 25 of the jaw member 29 and the bars 33 then move into the slots 23 . The connection members 35 are moved through the throats 27 a between the plates 27 and pins are inserted through the holes 28 , 38 to lock the two sections together. [0062] It is within the scope of this invention to delete one of the jaw members 29 and to releasably connect the two sections of the mast together at the location of the deleted jaw member 29 in any suitable fashion (e.g., but not limited to) with bolt(s) bolting the two sections together. [0063] Upon interengagement of the connection members of the sections 20 , 30 , as shown in FIG. 1H , and insertion of locking pins through the holes 28 , 38 , the mast raising cylinders 22 are partially extended so the truck R can move away. The mast raising cylinders 22 are then further extended and a racking board B is opened. [0064] FIG. 2 shows a bottom section 120 of a mast according to the present invention (like the bottom section 20 ); and FIG. 3 shows a midsection 130 of a mast according to the present invention (like a midsection 30 ). [0065] As shown in FIG. 2 , the bottom section 120 has four legs 122 and a series of interconnecting beams 121 . A square tube 123 spans two of the legs 122 . Each of two of the legs 122 has a jaw member 126 like the jaw members 29 , FIG. 1F and the two opposite legs 122 have end connection members 127 (like the connection members 27 , FIG. 1F ). [0066] A jaw member 126 has a body 126 a which includes two spaced-apart plates 126 p secured to a leg 122 ; a slot 126 b; an upright projection 126 c; and a throat 126 d (like the throat 25 a, FIG. 1L ) between two flared out parts which decreases in width from an outer end to an inner end. [0067] An end connection member 127 has a body 127 a with two spaced-apart plates 127 p each with a flared end 127 e so that the plates 127 p together form an open throat 127 t which decreases in width from the outer end to the inner end. Each plate 127 p has a hole 127 h for receiving a removable locking pin. A throat 127 x is formed between parts 127 y. The throat 127 t is like the throat 27 c, FIG. 1L and the throat 127 x is like the throat 27 a, FIG. 1L . [0068] As shown in FIG. 3 , the midsection 30 has four legs 132 and a series of interconnecting beams 131 . Each of two of the legs 132 has a connection member 136 and the two opposite legs have a connection member 137 . [0069] Each connection member 136 has a body 136 a made of two plates 136 p. A bar 136 b is held by and projects slightly from the plates 136 p. [0070] Each connection member 137 has a body 137 a made of two plates 137 p. Each plate 137 p has a hole 137 h for receiving a removable locking pin. [0071] As shown in FIGS. 4A-4C the midsection 130 has been moved on a truck into position adjacent the bottom section 120 (e.g. as in FIG. 1F and prior to FIG. 1G ). The truck moves the midsection 130 directly above the bottom section 120 ( FIG. 4C ). A substructure (e.g. like the substructure 11 ) raises the bottom section. For mating of the upper mast section initially to the lower mast section, both sections are oriented so that they are sloping downwards towards each other to insure that the upper jaws 126 come to a mating position before the opposite connections. The jaws 126 are then brought into contact with the mating bars 136 b of the lower connection members by raising the lower mast section using the hydraulic cylinders. [0072] Continued raising then forces the mating ends of the mast sections upwards rotating them so that the gap between the lower connections is forced closed. The flared design on the lower connections forces them into alignment as they are forced closed. As shown in FIGS. 4F and 4G , the hydraulic cylinders (substructure raising cylinders and mast raising cylinders) have been raised to raise the bottom section 120 level with the midsection 130 , moving the connection member 137 fully into the connection member 127 . Pins 129 have not yet been inserted into and through the holes 127 h, 137 h. The bars 136 b are in the slots 126 s. The two sides of the mast can be misaligned when the connection method starts which can result in a jaw and bar on one side being tensioned while the opposite jaw and bar are floating-but this is self-corrected as the raising process continues and the total mast begins to be lifted. [0073] As shown in FIGS. 4G and 4H , the substructure raising cylinders and the mast raising cylinders have been adjusted to install the pins 129 have been inserted through the connection member 127 , 137 . Pins 139 have not yet been inserted into the slots 126 b. Each pin 139 has a body 139 a with a lower projection 139 c which is sized and configured to fit into a space 131 formed by surfaces of the connection member 126 and of the bars 136 b. [0074] Once the pins 139 have been inserted and the two mast sections 120 , 130 are connected, the mast is ready to be raised. [0075] The present invention, therefore, provides in some, but not in necessarily all, embodiments a method for connection two parts of a mast of a drilling rig, the method including: connecting a bottom mast section to a support, the bottom mast section having bottom connection apparatus; moving a second mast section adjacent the bottom mast section, the second mast section releasably connected to a vehicle and said moving done by moving said vehicle, the second mast section having second connection apparatus; and moving the bottom mast section so that the bottom connection apparatus contacts the second connection apparatus and engages the second connection apparatus to secure the bottom mast section to the second mast section. Such a method may one or some, in any possible combination, of the following: releasing the second mast section from the vehicle, and moving the vehicle away from the second mast section; raising with mast raising apparatus the mast comprising the bottom mast section secured to the second mast section; wherein the support is a substructure with raising apparatus, the method further including: raising the substructure with the raising apparatus to move the bottom mast section with respect to the second mast section to facilitate engagement of the bottom connection apparatus with the second connection apparatus; locking together the bottom connection apparatus and the second connection apparatus; the bottom mast section comprises a jaw member connected to the bottom mast section with a throat and a slot, the second connection apparatus comprises a an insertion member with a bar, the insertion member sized and located for receipt of an end thereof in the throat of the jaw member and the bar sized and located for receipt within the slot, the method further including moving the bottom mast section to move the end of the insertion member into the throat and to move the bar into the slot; the jaw member has two spaced-apart plates each with a flared portion and a throat defined between the flared portions, the method further including moving an end of the insertion member into the throat; the bottom mast section is two legs each with a jaw member connected thereto, each with a throat and a slot, the second connection apparatus comprises an insertion member with a bar, the insertion member sized and located for receipt of an end thereof in the throat of the jaw member and the bar sized and located for receipt within the slot, the method further including moving the bottom mast section to move the ends of the insertion members into the throats and to move the bars into the slots; the jaw member has two spaced-apart plates each with a flared portion and a throat defined between the flared portions, the method further including moving an end of the insertion member into the throat; wherein the bottom mast section has a primary connection member connected thereto and spaced-apart from the jaw member, the second mast section has a secondary connection member connected thereto, the method further including securing the secondary connection member to the primary connection member; the primary connection member has two spaced-apart plates each with an outwardly flared portion and includes a throat between the outwardly flared portions of the two spaced-apart plates for facilitating entry of part of the secondary connection apparatus between the two spaced-apart plates; the bottom mast section has two legs each with a primary connection member connected thereto and spaced-apart from a jaw member, the second mast section has two legs each with a secondary connection member connected thereto, the method further including securing the secondary connection members to the primary connection members; the primary connection members each have two spaced-apart plates each with an outwardly flared portion and include a throat between the outwardly flared portions of the two spaced-apart plates for facilitating entry of part of the secondary connection apparatuses between the two spaced-apart plates; and/or wherein the support is a substructure with raising apparatus, the method further including raising the substructure with the raising apparatus to move the bottom mast section with respect to the second mast section to engage the bottom connection apparatus with the secondary connection apparatus, and said raising aligning the bottom mast section with the second mast section as the substructure is raised. [0076] The present invention, therefore, provides in some, but not in necessarily all, embodiments a mast system for rig operations, the mast system including: a support, a bottom mast section connected to the support; the bottom mast section having bottom connection apparatus; a second mast section adjacent and connectible to the bottom mast section, the second mast section releasably connected to a vehicle for moving the second mast section; the second mast section having second connection apparatus; and the bottom mast section movable on the support so that the bottom connection apparatus can contact the second connection apparatus and engage the second connection apparatus to secure the bottom mast section to the second mast section. Such a mast system may one or some, in any possible combination, of the following: wherein the support is a substructure with raising apparatus, the substructure with the raising apparatus able to raise the bottom mast section with respect to the second mast section prior to facilitate engagement of the bottom connection apparatus with the second connection apparatus; locking apparatus for locking together the bottom connection apparatus and the second connection apparatus; the bottom mast section having a jaw member connected to the bottom mast section, the jaw member having a throat and a slot, the second connection apparatus comprising an insertion member with a bar, the insertion member sized and located for receipt of an end thereof in the throat of the jaw member and the bar sized and located for receipt within the slot, and the bottom mast section movable to move the end of the insertion member into the throat and to move the bar into the slot; the jaw member has two spaced-apart plates each with a flared portion and a throat defined between the flared portions, the throat for receipt therein of an end of the insertion member into the throat; the bottom mast section having two legs each with a jaw member connected to a leg and each with a throat and a slot, the second mast section having two legs each with a second connection apparatus comprising an insertion member with a bar, the insertion member sized and located for receipt of an end thereof in the throat of a jaw member and the bar sized and located for receipt within a slot of the jaw member, and the bottom mast section movable to move the ends of the insertion members into the throats and to move the bars into the slots; the bottom mast section having a primary connection member connected thereto and spaced-apart from the jaw member, the second mast section having a secondary connection member connected thereto, and the secondary connection member securable to the primary connection member; and/or the bottom mast section has two legs each with a primary connection member connected thereto and spaced-apart from a jaw member, the second mast section has two legs each with a secondary connection member connected thereto, and each secondary connection member securable to an adjacent primary connection member; the primary connection member has two spaced-apart plates each flared out and including a throat defined between the two spaced-apart plates for facilitating entry of part of the second connection apparatus between the two spaced-apart plates. [0077] The systems and methods of the inventions described in the following pending U.S. patent applications, co-owned with the present invention, filed on even date herewith, naming donnally et al as inventors, fully incorporated herein for all purposes, may be used with certain embodiments of the present invention, the applications entitled: “Drilling Rig Structure Installation And Methods”; “Drilling Rig Drawworks Installation”; and “Drilling Rigs And Erection Methods”. [0078] In conclusion, therefore, it is seen that the present invention and embodiments disclosed herein and those in the appended claims are well adapted to do the objectives and obtain the ends set forth. Certain changes can be made in the subject matter without departing from the spirit and the scope of this invention. Changes are possible within the scope of this invention and it is further intended that each element or step recited in any of the following claims is to be understood as referring to the step literally and/or to all equivalent elements or steps. The following claims are intended to cover the invention as broadly as legally possible in whatever form it may be utilized. The invention claimed herein is new and novel in accordance with 35 U.S.C. §102 and satisfies the conditions for patentability in §102. The invention claimed herein is not obvious in accordance with 35 U.S.C. §103 and satisfies the conditions for patentability in §103. This specification and the claims are in accordance with all of the requirements of 35 U.S.C. §112. The inventors may rely on the Doctrine of Equivalents to determine and assess the scope of their invention and of the claims that follow as they may pertain to apparatus not materially departing from, but outside of, the literal scope of the invention as set forth in the following claims. All patents and applications identified herein are incorporated fully herein for all purposes. It is the express intention of the applicant not to invoke 35 U.S.C. §112, paragraph 6 for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function. In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are including, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements.
Methods for connection parts of a mast of a drilling rig without using a crane or other lifting machine are disclosed. In certain aspects, these methods include moving parts of a mast to be assembled with trucks and positioning the parts with the trucks to facilitate their connection. This Abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims, 37 C.F.R. 1.72 (b).
4
FIELD OF THE INVENTION The present invention generally concerns solar energy collection. More specifically, the present invention concerns increasing the efficiency of a tubular solar collector apparatus. DESCRIPTION OF THE RELATED ART The application of solar energy to heating generally requires a collector that efficiently absorbs solar radiation. The collector transfers the radiated energy to a fluid, which transports the energy to a final application in the form of heat. This final application may include a domestic water or space heating apparatus. An effective collector must absorb a high percentage of incident solar radiation, while losing only a small amount of the absorbed energy to the ambient through either heat conduction or radiation. Solar collectors including two concentric glass tubes with an evacuated space there between have generally been recognized as an effective configuration for absorbing a high percentage of incident radiation and minimizing heat loss by conduction. A solar collector configured in such a manner is similar to the configuration of a Dewar flask, which may be used as an insulated storage vessel, and are sometimes appropriately referred to as Dewar-type evacuated-tube collectors. The need to minimize radiation heat loss has been addressed by coating the vacuum-side of the inner glass tube with a selective surface that has a high absorptivity for visible radiation and low emissivity for infrared radiation. The primary developmental effort relating to evacuated tube solar concerns removal of the thermal energy absorbed by the elongated glass tubes. One method of removing the thermal energy from the elongated inner glass tube of evacuated tube solar collectors is to circulate water or other working fluid into and out of the interior of the glass tube. The working fluid circulated through the glass tube absorbs the solar energy and carries that energy to a location where the energy can be stored or put to practical use. An alternative methodology circulates the water or working fluid through the elongated glass tube via pipes or circulation tubes positioned inside the glass tube so that the water or other working fluid does not actually come in contact with the glass tube. A further technique uses heat pipes to transfer the absorbed solar energy to a working fluid medium that functions as a heat sink. The heat sink “stores” the collected thermal energy and/or transfers the energy to a location where the stored energy can be put to practical use. In such an embodiment, the heat pipe may include an evaporator portion that absorbs the solar energy and causes a volatile thermal transfer fluid in the heat pipe—not the working fluid medium—to vaporize. The vapor pressure drives the vapor toward the cooler condenser section of the heat pipe, which is placed in contact with the working fluid medium or heat sink. The thermal energy absorbed from the sun in the evaporator portion is conducted from the vapor of the thermal transfer fluid inside the heat pipe to the working fluid or heat sink outside the heat pipe by way of the condenser. The lower temperature of the thermal transfer fluid vapor, which is due to conduction of the heat from the vapor to the working fluid, results in condensation of the thermal transfer fluid in the heat pipe. The condensed thermal transfer fluid then flows from the condenser portion back to the evaporator portion of the heat pipe where solar energy is absorbed to continue the cycle. An additional method for transferring heat out of a Dewar-type evacuated-tube solar collector involves absorbed solar energy boiling water within the collector. The steam generated from the boiling water transports heat out of the collector through a process called vapor-phase pumping. A solar collector utilizing vapor-phase-pumping involves a tubular absorber filled almost to the top with a heating liquid, such as water, to provide a relatively small vapor-phase zone at the upper end of the absorber; a boiler mounted at a higher elevation than the solar collector; a tube through which liquid flows from the boiler into the tubular absorber and that extends into the interior of the tubular absorber for substantially the full length of the absorber; and a tube that connects the upper vapor-phase zone in the boiler with the vapor-phase zone in the tubular absorber. Extracting heat from an evacuated-tube solar collection using vapor-phase-pumping is easier than with a heat pipe and also avoids the need for a mechanical pump. It has generally been viewed as disadvantageous not to fill the tubular absorbers such that the top half is in contact with the liquid. Vapor-phase pumping devices have intentionally avoided such a configuration by filling the inner absorber cylinder with liquid or converting the inner absorber cylinder into a heat pipe. Another option has involved inserting a separate heat pipe or U-tube into the inner absorber cylinder and using a metal, thermally conductive fin to thermally couple the evaporator of the heat pipe or the U-tube to the inner absorber cylinder. The vapor-phase-pumping arrangement described above, however, has several limitations. By operating with the tubular absorber filled almost to the top, the hot fluid within the tubular absorber stores a significant amount of thermal energy. Most of this thermal energy will be lost to the ambient during the night. Furthermore, if the fluid within the tubular absorber is water, the absorber is likely to be damaged by freezing in cold climates since water expands when it freezes. If the vapor that is produced within the absorber is to flow to the boiler without interfering with the in-flowing liquid, an inlet tube that extends into the absorber must be used. This tube, which is often metallic as to withstand possible stagnation conditions within the evacuated-tube collector, increases the cost for the solar collector, especially for more expensive metals such as copper. SUMMARY OF THE CLAIMED INVENTION A first claimed embodiment sets forth an apparatus for converting liquid to vapor. The apparatus includes a tubular solar collector having a transparent outer cylinder with one closed end and a concentric inner cylinder with one closed end. The inner cylinder includes a surface coating that absorbs solar radiation. The longitudinal axes of both cylinders are substantially horizontal and the inner cylinder is oriented within the outer cylinder so that the closed ends of the two cylinders are proximate to each other whereby an evacuated space is formed between the two cylinders. The apparatus also includes a manifold that maintains the level of a volatile liquid flowing into the tubular solar collector so that no more than 80% of the volume of the inner cylinder is filled with liquid. The manifold also collects the vapor produced when heat is transferred from the surface of the inner glass cylinder that absorbs solar radiation to the volatile liquid. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a perspective view of a multi-tube solar collector with tubes in the same horizontal plane. FIG. 2 illustrates a longitudinal sectional view through one horizontal tube of the multi-tube solar collector of FIG. 1 . FIG. 3 illustrates a side view of the multi-tube solar collector of FIG. 1 including a reflecting back plane. FIG. 4 illustrates a perspective view of a multi-tube solar collector composed of three separate manifold-tube sub-assemblies. FIG. 5 is a longitudinal sectional view through the end-caps and horizontal tubes of a multi-tube solar collector for which the horizontal tubes lie in a plane that is not horizontal. FIG. 6 is a perspective view of a multi-tube solar collector with horizontal tubes used to evaporate a volatile component of a multi-component liquid. FIG. 7 illustrates a cut-away perspective view of a multi-tube solar collector with horizontal tubes used to evaporate a volatile component of a multi-component liquid and including an internal artery to deliver the multi-component liquid to one of the tubes. FIG. 8 illustrates a longitudinal sectional view through the center plane of a manifold that uses a partition with an orifice to allow concentrated liquid to be withdrawn from the manifold through an end wall fitting. FIG. 9 illustrates performance data corresponding to a multi-tube solar collector that produces steam. FIG. 10 illustrates a water level control system for a solar collector according to an exemplary embodiment of the present invention. FIG. 11 illustrates a water level control system for a solar collector according to another exemplary embodiment of the present invention. DETAILED DESCRIPTION A solar collector apparatus with Dewar-type evacuated tubes is generally described. The tubes may be oriented essentially horizontally and partially filled with liquid unlike a prior art solar collection apparatus that operates with liquid filling the tube almost to the top. Instead, the tubes of embodiments of the present invention may be filled only partially with liquid so that the space for vapor above the liquid extends more than three-quarters the length of the tube. With the tubes oriented close to horizontal and partially filled with liquid, the vapor produced within the tube can leave the tube without interfering with the entering liquid. Such a configuration, specifically the relatively low amount of liquid within the tube, reduces the heat lost during the night and, in applications where the tubes are less than half filled with liquid, a liquid that expands during freezing can do so within the tube without creating high stresses that might damage the tube. An embodiment of the invention as described herein may heat a liquid within an absorber tube, the liquid having a volatile and a non-volatile component. As heat is transferred to the liquid, a fraction of the volatile component is converted to vapor, leaving the liquid more concentrated in the non-volatile component. Both the vapor and the more concentrated liquid leave the absorber tube through its open end. FIG. 1 illustrates a perspective view of a multi-tube solar collector 10 with tubes 20 in the same horizontal plane. Each of the tubes 20 of solar collector 10 may be of a Dewar-type evacuated tube configuration as is reflected in the context of FIG. 2 . FIG. 2 illustrates a longitudinal sectional view through one horizontal tube 20 of the multi-tube solar collector 10 of FIG. 1 . Each evacuated tube 20 has, as illustrated in FIG. 2 , an outer transparent cylinder 22 and an inner absorber cylinder 24 . As shown in FIG. 1 , the open end of each evacuated tube 20 is inserted into a grommet 36 (also illustrated in FIG. 2 ) that fits into a circular opening 32 in the sidewall 31 of a central manifold 30 . The central manifold 30 has a layer of insulation 50 ( FIG. 2 ) to reduce heat loss to the ambient. Insulation 50 is not shown in FIG. 1 so that the underlying features of the solar collector 10 may more easily be understood. In FIGS. 1 and 2 , the manifold 30 has a square cross section, but may be circular, rectangular, or of any other shape that corresponds to the particular requirements of the application or associated manufacturing costs. The grommet 36 is preferably made from an elastomer that is compatible with liquid 40 that is being heated within the collector 10 . The grommet 36 is designed to form a fluid seal between the evacuated tube 20 and the manifold 30 . Use of grommet 36 allows for damaged evacuated tubes 20 to be more easily replaced. Notwithstanding, grommet 36 may be interchangeable with other means to seal the evacuated tubes 20 in the manifold 30 . For example, the manifold 30 may be made from a material that creates a fluid seal when the evacuated tubes 20 are inserted into the circular openings 32 . Beads of sealant such as a silicone RTV can alternatively be laid around the joints between the evacuated tubes 20 and the manifold 30 to achieve the same sealing effect. Liquid 40 enters the manifold 30 through an inlet fitting 35 ( FIG. 1 ), which may be located in an end wall 33 of the manifold 30 . The flow of liquid 40 may be controlled such that liquid 40 only partially fills the tubes 20 . With the tubes 20 horizontally configured, the vapor space 44 above the liquid will extend the entire length of each tube 20 . Though shown in FIGS. 1 and 2 as being round, the tubes 20 could be designed in other shapes including oval, pear, or reverse pear shaped, as well as other shapes that may be used to maximize solar energy collection or optimize fluid flow in the collector 10 . While a preferred embodiment of collector 10 may implement the tubes 20 in a horizontal configuration, if the tubes 20 are arranged such that the open end is higher than the closed end, the length of the vapor space 44 might be less than the length of the tube 20 . The length of the vapor space 44 as a fraction of the length of the tube 20 may contribute to the efficient operation of solar collector 10 . For example, if liquid 40 is water, the collector 10 may be more vulnerable to damage by freezing as the amount of water (liquid 40 ) in the tubes 20 increases. Heat loss at night may likewise increase as the amount of liquid 40 in the tubes 20 increases. When tubes 20 are arranged such that the open end is lower than the closed end, the level of liquid 40 within the tube 20 may be such that liquid 40 does not extend the full length of the tube 20 . In such a configuration, the surface of the inner absorber cylinder 24 may be modified to act as a wick so that liquid is drawn by capillary forces either axially towards the closed end of the inner absorber cylinder 24 or circumferentially around the inner absorber cylinder. This wick can be of granulated glass particles that are bonded to the inner absorber cylinder like that illustrated in U.S. Pat. No. 4,474,170. Other refractory particles that can withstand high temperatures may be used such as sand or particles of aluminum oxide. The wick can also be a thin woven or non-woven layer of glass fibers that are inserted into the inner absorber cylinder 24 . Other wicks are possible so long as they can be wetted by liquid 40 and do not degrade when exposed to the highest temperatures that could be produced within an evacuated-tube solar collector 10 . In one embodiment, a wick might draw liquid onto the hotter upper portion of the inner absorber cylinder 24 thereby improving performance of the solar collector 10 . During the operation of solar collector 10 , solar radiation passes through the outer transparent glass cylinders 22 of the evacuated tubes 20 and impinges on the inner absorber cylinder 24 . The volume 23 between the outer glass cylinder 22 and the inner absorber cylinder 24 is evacuated to eliminate heat loss by conduction from the inner absorber cylinder to the surroundings. The surface of the absorber cylinder 24 that faces the vacuum may have high absorptivity for solar radiation and low emissivity for infrared (i.e., thermal) radiation. The absorptivity and emissivity of the absorber cylinder 24 may be controlled through a galvanically applied selective coating such as black chrome, black nickel, or aluminum oxide with nickel. A titanium-nitride-oxide layer may alternatively be applied via steam in a vacuum process. This titanium-nitride-oxide coating has low emission rates and can be produced by an emission-free, energy-efficient process. The solar radiation that impinges on the absorber cylinder 24 is converted to thermal energy and raises the temperature of the upper portion of the absorber cylinder 24 . A combination of radiation from the inner wall of the absorber cylinder 24 , heat conduction, and heat convection transfers thermal energy from the absorber cylinder 24 to liquid 40 within the absorber cylinder 24 . If the incident solar radiation is sufficiently intense, liquid 40 will be heated to a temperature at which its vapor pressure is above the ambient pressure. At this temperature, the evolving vapor will flow out of the absorber cylinder 40 and into the manifold 30 . Said flow pushes out any air that might be in the cylinder. The vapor leaves the manifold 30 through the vapor outlet fitting 37 . The vapor can be used as a heat source for desiccant regeneration, water heating, space heating or similar operations. During normal operation of the invention, steam is produced within the tubes during the day. As discussed, this steam flows to a point-of-use, which might include a desiccant regenerator, a water heater, a space heater or similar thermal device, where it condenses, providing thermal energy to the point-of-use. According to an exemplary embodiment of the present invention, the condensed steam is returned to the solar collector to maintain an approximately constant level of water in the collector. As previously noted, a solar collector apparatus with Dewar-type evacuated tubes becomes more efficient as the amount of water stored in the tubes decreases since the lower mass of water reduces heat loss that will occur at night. Since the critical parameter affecting efficiency is the amount of water within the solar collector at night, a more efficient mode of operation would not immediately return the condensed steam to the solar collector. In this more efficient mode of operation, the condensed steam may be stored in an insulated tank and returned to the solar collector shortly before the sun begins to illuminate the solar collector in the morning. Since the volume of water in the solar collector during the night is further reduced by storing the condensed steam, night-time heat loss is also reduced. A common Dewar-type evacuated tube has an inner tube with a diameter of 47 mm. Under clear sky conditions, this inner tube will absorb solar radiation in one day that at most could convert an amount of water into steam that was equivalent to between 25% and 30% of the total tube inner volume. Thus, a Dewar-type evacuated tube that was more than 30% full of water at the start of the day, would never convert all of the water into steam before the end of the day. Since most days do not exhibit perfect, clear sky conditions, the amount of water in the Dewar-type evacuated tube at the start of the daylight portion of the day can be less than 30% without the tube drying out before the end of the daylight portion of the day. A control algorithm that predicts the maximum amount of water that could be converted to steam during one day and adjusts the amount of water in the solar collector at the start of the daylight portion of the day to be greater than this amount would reduce night-time heat loss and improve the efficiency of the solar collector. In an exemplary embodiment, an object of the control algorithm may be to control the amount of water to be just slightly greater than the maximum amount that could be converted to steam. In any case, the amount of water delivered to the solar collector at the start of the daylight portion of the day may be controlled so that no additional water needs to be delivered until the next day, which improves the overall efficiency of the solar collector apparatus. The control algorithm could account for several factors including (1) time of year, (2) latitude of location (3) site-specific shading, (4) historical weather conditions, and (5) forecasted weather conditions. According to an exemplary embodiment, the preferred approach to reducing night-time heat loss may be to drain the water from the solar collector into an insulated tank at the end of the day. This approach may require at least one pump to transfer the hot water either from the collectors to the insulated tank or from the insulated tank to the collectors. When water is drained from the solar collector at the end of the daylight portion of the day and stored in an insulated tank during the night, then heat loss from the solar collector depends only slightly on the amount of water in the solar collector during the daylight portion of the day. While efficient operation of the solar collector still requires that it not be empty of water during the daylight portion of the day, the amount of water within the collector both at the start of and throughout the daylight portion of the day can be any amount that does not restrict the flow of vapor out of the inner tubes of the collector. Furthermore, vapor produced within the collector that condenses at the point-of-use may or may not be immediately returned to the collector. For installations with one or more manifolds that lie in a common horizontal plane and which are fluidly coupled together as shown in FIG. 4 , a common water level will exist within the coupled manifolds and the tubes connected to these manifolds. For installations where all water is transferred to an insulated tank at the end of the daylight portion of the day, the coupled manifolds and associated tubes can be filled to a desired level by delivering a predetermined quantity of water from the tank to the empty solar collectors. According to an exemplary embodiment, a method for determining the quantity of water that is delivered to the collectors involves monitoring the level of water in the storage tank and delivering a quantity of water that produces a change in level that corresponds to the desired quantity of water. Conventional methods for measuring the level of water in a tank could be used, including but not limited to ultrasonic sensors, radar sensors, laser sensors, pressure sensors and mechanical float-type gauges. FIG. 10 shows one possible configuration in which a pressure sensor 202 at the bottom of the storage tank 204 measures the level of water 206 within the storage tank. A controller 210 receives a signal from the pressure sensor and energizes a transfer pump 212 and opens a flow valve 216 b so that the desired quantity of water is delivered to the collectors 214 . The pressure sensor 202 may also be used to identify a condition in which insufficient water is in the storage tank following the transfer of water from the collectors to the tank. If a low level is detected, the controller 210 may open a flow valve 216 a that introduces additional water into the tank 204 . At the end of the daylight portion of the day, the control valve 216 b in the line that connects the collector 214 to the storage tank 204 is opened by the controller 210 so that water in the collector can drain by gravity through the idle transfer pump 212 into the storage tank. It should be appreciated that the control algorithms discussed herein may be implemented via one or more processors based on instructions received from one or more non-transitory, computer readable media. For installations where water is not drained from the manifolds and associated tubes at the end of the daylight portion of the day, it may be necessary to directly measure the level of water within the manifolds and associated tubes. In such an embodiment, the level sensor may be mounted in a convenient location where it can sense the level of water in one of the one or more coupled manifolds. FIG. 11 shows one possible configuration in which an ultrasonic level sensor 222 is mounted in a fitting on the top surface of the first of two coupled manifolds 224 . A controller 210 receives a signal from the ultrasonic level sensor 222 and energizes the tank outlet valve 226 a when water is to be gravity fed from the storage tank to the manifolds and associated tubes and, in the event that a low water level is detected by the ultrasonic level sensor, energizes the make-up water valve 226 b. FIG. 3 illustrates a side view of the multi-tube solar collector of FIG. 1 including a reflecting back plane. As shown in FIG. 3 , a reflecting surface 52 positioned below the tubes 20 can be used to increase the amount of solar radiation collected by each tube 20 . In FIG. 3 , the reflecting surface 52 is illustrated as flat and the incident solar radiation 53 that is not absorbed by the evacuated tube 20 reflects as diffuse radiation 55 upward towards the evacuated tubes 20 . Reflecting surface 52 can also specularly reflect the solar radiation; surface 52 may thus have a compound parabolic shape. Other shapes may be implemented in the context of reflecting surface 52 . Alternatively, mirror image pairs of manifolds 30 can be interspersed to maximize the amount of surface areas available for solar absorption. This interleaved or interspersed tube arrangement would result in two parallel manifolds and a smaller space requirement for implementation. Such an arrangement may sacrifice some reflected energy potential provided by a mirror placed behind the tubes of the collector 10 . In applications that require large amounts of thermal energy, it may not be practical to couple all the evacuated tubes 20 to a single manifold 30 . As shown in FIG. 4 , which illustrates a perspective view of a multi-tube solar collector composed of three separate manifold-tube sub-assemblies, coupling sleeves 38 can be used to join two or more manifolds 30 end-to-end so that they function as a single manifold. A toric joint 39 , sometimes referred to as a mechanical gasket or O-ring, may be utilized to properly seal manifolds 30 and coupling sleeves 38 . When multiple manifolds are joined together, end walls 33 may be applied only to the outer ends of the first and last manifold 30 in the series. Such end walls 33 may sealed with the manifold 30 using the aforementioned toric joint 39 . The evacuated tubes 20 of the solar collector 10 illustrated in FIGS. 1 and 2 all lie in essentially the same flat, horizontal plane. With the evacuated tubes 20 all in the same horizontal plane and no obstructions to the flow of liquid between the evacuated tubes 20 , the level of liquid 40 will generally be the same in all the evacuated tubes 20 . In some embodiments, however, the evacuated tubes may lie in a plane that is not horizontal. FIG. 5 is just such an embodiment and illustrates a longitudinal sectional view through the end-caps and horizontal tubes of a multi-tube solar collector for which the horizontal tubes lie in a plane that is not horizontal. The embodiment illustrated in FIG. 5 will allow the solar collector 10 to operate with each tube 20 substantially horizontal but the tubes no longer lying in the same horizontal plane. In FIG. 5 , a levelizing end cap 64 is added to the open end of each evacuated tube 20 . During the operation of the solar collector 10 of FIG. 5 , liquid 40 is pumped into the uppermost levelizing end cap 64 a through an inlet tube 66 . Upon reaching a predetermined level within the evacuated tube 20 , the liquid flows over weir 65 . The overflow liquid flows by gravity through transfer tube 67 and into the next lower levelizing end cap 64 b . This cascading of liquid 40 continues to the lowest levelizing end cap 64 c . From the lowest levelizing end cap 64 c , liquid 40 flows out of the solar collector 10 via the outlet tube 68 . Liquid 40 that flows from outlet tube 68 can be re-circulated to inlet tube 66 using a pump (not shown). Aside from the use of levelizing end caps 64 and the possible recirculation of liquid 40 , the operation of the solar collector 10 as shown in FIG. 5 is substantially similar to that of the solar collector 10 of FIGS. 1 and 2 . FIG. 6 is a perspective view of a multi-tube solar collector 70 with horizontal tubes used to evaporate a volatile component of a multi-component liquid. The solar collector 70 shown in FIG. 6 is used to partially separate a liquid mixture into a volatile component and a non-volatile component. Although not limited to this application, the solar collector 70 can be used to remove water (i.e., the volatile component) from an aqueous solution of an ionic salt such as calcium chloride (i.e., the non-volatile component). Other ionic salts that are soluble in water include lithium chloride, calcium bromide, lithium bromide, sodium chloride, potassium sulfate, sodium sulfate, as well as solutions in which the vapor produced when the solution is heated has only one component (i.e., water in the case of an aqueous salt solution). The liquid mixture with the higher fraction of the non-volatile component will be called the concentrated liquid, and the liquid mixture with the lower fraction, the dilute liquid. Thus, dilute liquid 72 is supplied to the solar collector 70 and concentrated liquid 74 and vapor 75 are returned from the solar collector. As the concentration of the non-volatile component increases and as its temperature decreases, the density of the liquid mixture may increase. In this context, consider an application where the dilute liquid 72 that is supplied to the solar collector 70 is heated to a sufficiently high temperature to ensure that its density is lower than that of the hot, concentrated liquid 74 that is returned from the solar collector. In this case, the inlet fitting 76 for the dilute liquid 72 may be located on the front end wall 82 of the central manifold 84 at an elevation that is close to the level of the liquid within the evacuated-tubes 20 . Such a configuration is illustrated in FIG. 6 . The concentrated liquid 74 is withdrawn from the central manifold 84 through an outlet fitting 78 that may be located on the rear-end wall 83 at an elevation near the bottom of the central manifold 84 as is also illustrated in FIG. 6 . With this arrangement of inlet fitting 76 and outlet fitting 78 , the dilute liquid 72 will tend to spread out over the surface of the liquid within the solar collector 70 and be delivered to each evacuated tube 20 in a relatively uniform manner. As the dilute liquid 72 is heated by the solar radiation that is absorbed by the evacuated tube 20 , some of the volatile component of dilute liquid 72 is converted to vapor. As this happens, the dilute liquid 72 becomes more concentrated and the density of dilute liquid 72 increases thereby causing dilute liquid 72 to sink to a lower level within the evacuated tube 20 . During the operation of the solar collector 70 , there may be a continuous flow of dilute liquid to the tubes and return of concentrated liquid from the tubes, the dilute liquid flowing above the concentrated liquid. The vapor 75 flows out of manifold 84 through vapor outlet fitting 77 that is located above the liquid level within the manifold as illustrated in FIG. 6 . In some applications, it may be convenient to locate the inlet fitting 76 for the dilute liquid and the outlet fitting 78 for the concentrated liquid on the same end wall of the manifold 84 . In these applications, the inlet fitting 76 can be extended within the manifold so that the dilute liquid is delivered to a location within the manifold that is away from location where the concentrated liquid flows out of the manifold. This design would prevent “short-circuiting” of the weak liquid directly to the outlet fitting. In some applications it may not be practical to preheat the dilute liquid 72 to a sufficiently high temperature to ensure that its density is lower than the concentrated liquid 74 . In these applications, an internal artery 86 can be added to the solar collector 70 as shown in FIG. 7 . FIG. 7 illustrates a cut-away perspective view of a multi-tube solar collector with horizontal tubes used to evaporate a volatile component of a multi-component liquid and including an internal artery to deliver the multi-component liquid to one of the tubes. Internal artery 86 delivers the dilute liquid 72 to the closed end of one evacuated tube 20 a of the many tubes 20 that are a party of solar collector 70 . The dilute liquid will be heated within this evacuated tube 20 a to a temperature at which its density is less than that of the concentrated liquid 74 . The heated dilute liquid that leaves the evacuated tube 20 a will then flow to the other evacuated tubes 20 along the surface of the liquid that fills these tubes 20 . Once the dilute liquid 72 has flowed to the other evacuated tubes 20 , the process of creating vapor and concentrated liquid within these tubes 20 will be the same as that described for the operation of the solar collector 70 in FIG. 6 . Depending on the temperature of the dilute liquid 72 that is supplied to the solar collector 70 , it may be necessary to use more than one internal artery 86 and more than one evacuated tube 20 a for preheating. The number of internal arteries 86 will nevertheless be less than the number of evacuated tubes 20 ; this configuration remains a simplification over those prior designs that require one internal artery for each evacuated tube. In the solar collector 70 illustrated in FIGS. 6 and 7 , if the diameter of the outlet fitting 78 is large and the concentrated liquid 74 freely flows out of the central manifold 84 , then the elevation of this fitting may set the level of the liquid within the manifold 84 and the evacuated tubes 20 . The denser concentrated liquid that is produced within the solar collector 70 will, however, flow below the less dense dilute liquid. As such, it may be preferable for the outlet fitting 78 to be located near the bottom of the central manifold 84 so that only the concentrated liquid is withdrawn from the manifold. FIG. 8 illustrates a longitudinal sectional view through the center plane of a manifold that uses a partition with an orifice to allow concentrated liquid to be withdrawn from the manifold through an end wall fitting. As shown in FIG. 8 , a partition 89 with an orifice 91 near the bottom of the partition 89 can be used to form a pool 93 of liquid at the end of the central manifold 84 . The liquid that flows into this pool 93 through the orifice 91 will be concentrated liquid. The level of the liquid in the pool 93 will be nearly the same as the level of liquid within the remainder of the central manifold 84 and the evacuated tubes 20 . If the concentrated liquid freely flows out of the outlet fitting 78 , then the elevation of this fitting can be used to establish the level of liquid within the pool 93 , the remainder of the central manifold 84 , and the evacuated tubes 20 . In the embodiments illustrated in FIGS. 1 through 8 , only the lower portion of the inner absorber cylinder 24 is wetted by liquid. A significant fraction of the solar radiation that impinges on the solar collector is absorbed by the upper portion of the inner absorber cylinder 24 , which faces the sky. This portion of the inner absorber cylinder is not wetted by liquid. Nor if there is a thermally conductive element within the evacuated tubes that would facilitate the transfer of heat from the hot, upper portion of the inner absorber cylinder 24 and the liquid 40 that is within the tube. FIG. 9 illustrates performance data corresponding to a multi-tube solar collector that produces steam. The performance data of FIG. 9 corresponds, specifically, to a 24-tube solar collector implemented in the context of the embodiment illustrated in FIG. 3 . The diameter of the transparent outer cylinder of the evacuated tubes resulting in the data of FIG. 9 was 58 mm and the diameter of the inner absorber cylinder was 47 mm; the length of each tube was 1.8 m. The tubes were spaced apart along the central manifold so that the distance between their axial centerlines was equal to 94 mm. The backplane was a white, diffusely reflecting surface located 94 mm below the axial centerlines of the evacuated tubes. The 24-tube solar collector operated with water entering the collector at close to ambient temperature and pressure, and steam leaving the collector slightly superheated to approximately 105.degree. C. The curve labeled A in FIG. 9 shows the solar energy that was productively used to produce steam in the 24-tube solar collector expressed as a percentage of the non-reflected solar energy that was incident on the inner absorber cylinders of the collector when the tubes were approximately one-half full of water. The curve labeled B in FIG. 9 shows the performance of the collector when the tubes were approximately one-third full of water. As shown in FIG. 9 , following an initial three-hour period of heating for the collector that was one-half full (i.e., Curve A) and a two and one-half hour period of heating for a collector that was one-third full (i.e., Curve B), both collectors produced steam at a rate that corresponds to approximately 80% to 100% of the non-reflected solar radiation incident on the inner absorber cylinders of the related tube. It should be noted that the tubes also receive reflected radiation from the backplane, so the 100% conversion rate does not imply that all the incident radiation is converted to steam. Otherwise, once at operating temperature, both collectors—regardless of fill levels—produce steam at about the same efficiency. While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. The descriptions are not intended to limit the scope of the invention to the particular forms set forth herein. To the contrary, the present descriptions are intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims and otherwise appreciated by one of ordinary skill in the art. Thus, the breadth and scope of a preferred embodiment should not be limited by any of the above-described exemplary embodiments. For example, the solar absorber of the present invention can also be used to heat a multi-component liquid like glycol and water, thereby producing vapor that has a much higher fraction of water than the initial liquid. In such case the present invention could be used as the thermal source for a distillation column.
A method of converting a liquid into a vapor includes directing liquid into one or more solar collectors through a manifold that supports the one or more solar collectors. Each of the one or more solar collectors includes a transparent outer cylinder having a closed end and an open end, an inner cylinder having a closed end and an open end, the inner cylinder being concentric with and disposed within the transparent outer cylinder so that the closed end of the inner cylinder is located proximate to the closed end of the transparent outer cylinder, an outer surface of the inner cylinder being made of a material that absorbs solar radiation to generate heat, the longitudinal axes of the transparent outer cylinder and the inner cylinder being substantially horizontal, and an enclosed and evacuated space formed between the transparent outer cylinder and the inner cylinder. A maximum value is determined for the amount of liquid to be converted to vapor during a daylight portion of a day as a result of the heat generated in the inner cylinders of the one or more solar collectors. An amount of the liquid is directed into the one or more solar collectors, where the amount is a value that is at least the maximum amount value.
8
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation-in-part of U.S. Ser. No. 10/194,540, filed Jul. 15, 2002, which is a division of U.S. Ser. No. 09/706,391, filed Nov. 6, 2000, issued Sep. 3, 2002 as U.S. Pat. No. 6,444,165, which is a continuation-in-part of U.S. Ser. No. 09/228,741, filed Jan. 12, 1999 (abandoned). BACKGROUND OF THE INVENTION [0002] This invention relates to troughing for molten metals and more particularly it relates to heated troughing for flowing molten metal such as molten aluminum from one station to another. [0003] Conventional troughing used for conveying molten aluminum from a molten aluminum source such as a holding furnace to a work station such as a degasser or caster is either not heated or if heated, utilizes radian heaters such as glow bars which radiate heat from above the surface of the molten metal. If no heaters are used in the troughing, then the distance the metal can be conveyed is limited or the molten metal must be superheated to compensate for the loss in temperature, with its attendant problems such as skim generation. However, radiant heaters have the problem of short service life because they are exposed to aluminum vapors, splashing of molten aluminum and mechanical abuse. Also, radiant heat has the problem that it results in local heating of the surface of the molten metal in the roughing and deposition of a metal skim on the sidewalls of the troughing which contributes to oxide formation. Thus, it can be seen that there is a great need for an improved troughing for conveying molten metal such as molten aluminum which overcomes these problems. This invention provides such an improved troughing. SUMMARY OF THE INVENTION [0004] It is an object of this invention to provide an improved refractory troughing. [0005] It is another object of this invention to provide an improved heated trough member for conveying molten metal such as molten aluminum. [0006] It is a further object of this invention to provide a heated refractory trough for flowing molten aluminum from a molten aluminum source to a work station such as a degasser. [0007] These and other objects will become apparent from a reading of the specification and claims appended hereto. [0008] In accordance with these objects, there is provided a method of heating molten aluminum flowing in a heated trough member comprising the steps of providing a source of molten aluminum and providing a rough member comprised of a first side and a second side, the first and the second sides having outside surfaces, the sides formed from a ceramic material resistant to attack by molten aluminum. The first side and second side have heating element receptacles provided therein with protection tubes provided in the receptacles. The protection tubes are comprised of a refractory selected from the group consisting of mullite, boron nitride, silicon nitride, silicon carbide, graphite, silicon aluminum oxynitride or a metal selected from Kovar® and titanium. Electric heating elements are positioned in the tubes. Molten aluminum is flowed along the trough member from the source and electric power is passed to the heating elements to heat the molten aluminum as it flows along the trough member. BRIEF DESCRIPTION OF THE DRAWINGS [0009] [0009]FIG. 1 is a schematic of a molten aluminum source (holding furnace) connected to a processing station, e.g., degasser, by troughing. [0010] [0010]FIG. 2 is a schematic of a section of the trough in FIG. 1. [0011] [0011]FIG. 3 is a cross section of a trough member along the line A-A of FIG. 2 in accordance with the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0012] The refractory materials useful in the present invention for troughing can include alumina, silica, silicon carbide, base material or mixtures thereof. The refractory material can utilize mullite, kyanite, bauxite and kaolin, for example. Any refractory material may be used, depending on the end use. If the use is high temperature application, then the alumina, silica, or silica carbide are particularly useful. These materials are usually ground to provide a particle size preferably not greater than about 40 mesh with smaller particle size being preferred, e.g., less than about 30 mesh, to facilitate mixing with metal fiber reinforcing or heat conduction material. That is, the use of large particles resist mixing or intrusion into the metal fiber matrix, resulting in voids which adversely affect the integrity of the refractory body. Further, smaller particle size improves the fluidity of the refractory when mixed with a refractory cement prior to infiltrating the metal fiber matrix, when such is used for reinforcing or heat conduction. [0013] For purposes of preparing a mix for infiltrating the metal fiber matrix, the refractory material is mixed with a refractory cement such as calcium aluminate cement, gypsum, sodium silicate or the like to provide a mix. However, any refractory cement may be used, depending on the end use. The cement typically is used in equal parts with the refractory material; however, adjustments can be made to add more or less cement as desired. [0014] It will be appreciated that water is added to the mix in the range of about 10 to 35 wt. % or more to provide a slurry suitable for intruding or pressure infiltrating the metal fiber matrix. Plasticizers may be added to the mix to aid in infiltrating the metal fiber matrix. [0015] Refractory bodies of the present invention have many uses in high temperature applications such as in molten metal, for example, molten aluminum. Thus, it is important that the refractory have high durability and furthermore it is important that the metal component when used for reinforcing has a low coefficient of thermal expansion and preferably high oxidation resistance at elevated temperatures. The low coefficient of thermal expansion is important to avoid cracking of the refractory body at high temperatures. The high oxidation resistance is important to minimize high temperature oxidation in environments where fibers are exposed above the metal line. [0016] In the present invention, the metal component, e.g., metal fibers, are carefully selected to provide the low coefficient of thermal expansion. Thus, the metal component can be comprised of nickel based alloys, iron-nickel based alloys, iron-nickel-cobalt based alloys and titanium based alloys. Preferably, the metal component is comprised of an alloy having a coefficient of thermal expansion of less than 10×10 −6 in/in/° F. and preferably less than 7×10 −6 in/in/° F. Typically, such coefficients of thermal expansion are applicable over a temperature range of about 400° to 2000° F. Further, it is preferred that such alloys have an oxidation resistance (as measured by weight gain) of less than about 15 mg/cm 2 , typically less than 5 mg/cm 2 . [0017] The nickel based alloys include Incoloy alloys 903, 907, 908 and 909; Inconel alloys 783 and 718; Thermo-Span; Haynes alloy 242; and Nilo alloys 36 and 42. These alloys have the following compositions: Nominal Chemical Compositions (wt. %) Ni Fe Co Cr Nb Al Ti Si Other Incoloy alloy 903 38.0 42.0 15.0 — 3.0 0.9 1.4 — — Incoloy alloy 907 38.0 42.0 13.0 — 4.7 0.03 1.5 0.15 — Incoloy alloy 909 38.0 42.0 13.0 — 4.7 0.03 1.5 0.4 — Incoloy alloy 783 28.5 26.0 34.0 3.0 3.0 5.4 0.1 — — Incoloy alloy 718 52.5 18.5 — 19.0 5.13 0.50 0.90 .18 3.05 Mo Thermo-Span 25 34 29 5.5 4.8 0.5 0.8 0.3 — Haynes alloy 242 64 1.0 1.25 8.0 — 0.25 — 0.4 25.0 Mo Nilo alloy 36 36.0 64.0 — — — — — — — Nilo alloy 42 42.0 58.0 — — — — — — — Incoloy alloy 908 49 41 — 4 3 1 1.5 — — [0018] Other controlled expansion alloys include: Ni—Fe—Co Incoloy alloy 904, and Inconel alloy 625. [0019] Titanium alloys having controlled or low coefficient of thermal expansion include CP (commercial purity) grade titanium, or alpha and beta titanium alloys or near alpha titanium alloys, or alpha-beta titanium alloys. The alpha or near-alpha alloys can comprise, by wt. %, 2 to 9 Al, 0 to 12 Sn, 0 to 4 Mo, 0 to 6 Zr, 0 to 2 V and 0 to 2 Ta, and 2.5 max. each of Ni, Nb and Si, the remainder titanium and incidental elements and impurities. [0020] Specific alpha and near-alpha titanium alloys contain, by wt. %, about: [0021] (a) 5 Al, 2.5 Sn, the remainder Ti and impurities. [0022] (b) 8 Al, 1 Mo, 1 V, the remainder Ti and impurities. [0023] (c) 6 Al, 2 Sn, 4 Zr, 2 Mo, the remainder Ti and impurities. [0024] (d) 6 Al, 2 Nb, 1 Ta, 0.8 Mo, the remainder Ti and impurities. [0025] (e) 2.25 Al, 11 Sn, 5 Zr, 1 Mo, the remainder Ti and impurities. [0026] (f) 5 Al, 5 Sn, 2 Zr, 2 Mo, the remainder Ti and impurities. [0027] The alpha-beta titanium alloys comprise, by wt. %, 2 to 10 Al, 0 to 5 Mo, 0 to 5 Sn, 0 to 5 Zr, 0 to 11 V, 0 to 5 Cr, 0 to 3 Fe, with 1 Cu max., 9 Mn max., 1 Si max., the remainder titanium, incidental elements and impurities. [0028] Specific alpha-beta alloys contain, by wt. %, about: [0029] (a) 6 Al, 4 V, the remainder Ti and impurities. [0030] (b) 6 Al, 6 V, 2 Sn, the remainder Ti and impurities. [0031] (c) 8 Mn, the remainder Ti and impurities. [0032] (d) 7 Al, 4 Mo, the remainder Ti and impurities. [0033] (e) 6 Al, 2 Sn, 4 Zr, 6 Mo, the remainder Ti and impurities. [0034] (f) 5 Al, 2 Sn, 2 Zr, 4 Mo, 4 Cr, the remainder Ti and impurities. [0035] (g) 6 Al, 2 Sn, 2 Zn, 2 Mo, 2 Cr, the remainder Ti and impurities. [0036] (h) 10 V, 2 Fe, 3 Al, the remainder Ti and impurities. [0037] (i) 3 Al, 2.5 V, the remainder Ti and impurities. [0038] The beta titanium alloys comprise, by wt. %, 0 to 14 V, 0 to 12 Cr, 0 to 4 Al, 0 to 12 Mo, 0 to 6 Zr and 0 to 3 Fe, the remainder titanium and impurities. [0039] Specific beta titanium alloys contain, by wt. %, about: [0040] (a) 13 V, 11 Cr, 3 Al, the remainder Ti and impurities. [0041] (b) 8 Mo, 8 V, 2 Fe, 3 Al, the remainder Ti and impurities. [0042] (c) 3 Al, 8 V, 6 Cr, 4 Mo, 4 Zr, the remainder Ti and impurities. [0043] (d) 11.5 Mo, 6 Zr, 4.5 Sn, the remainder Ti and impurities. [0044] These alloys are illustrative of the invention and other alloys may be used having low coefficient of thermal expansion and preferably with high oxidation resistance. [0045] As well as having a low coefficient of thermal expansion, the metal fibers should high strength at elevated temperatures for high temperature applications, such as for use with molten aluminum. For example, stainless steels have high oxidation resistance and good strength at room temperature, but at elevated temperatures, strength drops off as temperature rises. For example, when stainless steels are compared to nickel based alloys at 1200° F. the yield strength properties (0.2% offset) are inferior, as will be seen in the following Table. Material YS KSI at 1200° F. 302 SS 12 321 SS 19 309 SS 26 410 SS 27 Hastealloy X 40 Hastealloy S 47 Waspalloy 100 Inconel X-750 103 Inconel IN-718 148 [0046] In the present invention, it is preferred that such alloys be used in fibrous form and may be used in mat form where chopped fibers are formed into mats before using in the mold. Preferably, the fibers are less than about 5 inches long with a diameter of less than 50 mils. [0047] It will be appreciated that plasticizing agents may be used to facilitate intrusion of the fibers with the slurry. Further, infiltration of the fibers can be further facilitated by applying vibrating and/or vacuum means to the mold to improve impregnation of the fibers with slurry. After the slurry has been added, typically the refractory body has a green strength in about 4 to 5 hours. For most compositions, good green strength is obtained overnight. Thereafter, the refractory body can be treated at an elevated temperature to remove water, typically in the range of 150° to 750° C. [0048] Refractory bodies formed using the low coefficient of thermal expansion of the present invention have high levels of strength and are resistant to cracking at elevated temperatures because of the controlled coefficient of thermal expansion. Prior material using steel reinforcing undergoes selective oxidation of the steel. Oxidation continues progressively until overall strength is compromised due to loss of reinforcement and eventually the material fails. [0049] The refractory bodies of the present invention are useful in molten metal treatment processes. For example, the refractory bodies can be formed to accept electric heaters and used for baffle heaters to treat molten metal, such as aluminum as well as other metals. [0050] Further, the refractory bodies can be used as liners and blocks for molten metal furnaces and find great use in high temperature applications where thermal stress is a concern. [0051] In another aspect of the invention, the refractory may be used to form a trough member for conveying molten metal from a molten metal source, e.g., holding furnace, to a work station such as a processing station, e.g., degasser or casting station (FIG. 1). [0052] The trough member can be any shape but preferably has a U-shaped configuration such as shown, for example, in FIG. 2. The trough member illustrated in FIG. 2 has sides 2 and 4 connected to bottom 6 for containing and flowing molten metal 8 . In FIG. 2, leads 10 are shown connected to electric heaters positioned in walls or sides 2 of trough member 1 for the purpose of adding heat to the molten metal as it passes along the trough. Although not shown in FIG. 2, trough member 1 can be provided with a lid to minimize heat loss. [0053] Referring now to FIG. 3, there is shown a cross section along the line A-A of FIG. 2 of the trough member in accordance with the invention. The trough member comprises a metal shell 12 which is generally U-shaped and extends down side 14 , along bottom 16 and up side 18 . A layer of insulation 20 is provided inside metal shell 12 and extends down side 14 , along bottom 16 and up side 18 . On sides 14 and 18 , a reflective sheet 22 of metal may be provided to reflect heat inwardly towards the molten metal in the trough. The reflective sheet may be comprised of any metal having a reflective surface such as, for example, stainless steel or nickel steel. [0054] An inner liner 24 of refractory is provided against the reflective sheet. Refractory liner 24 may be provided as a monolith or it may be comprised of side panels 26 and 28 maintained or anchored in position by bottom panel 30 . Refractory liner 24 extends down side 14 along bottom 16 and up side 18 . If it is provided in sections then sides 26 and 28 are closely fitted with bottom 30 and preferably sealed using a refractory cement to contain the molten aluminum. Electric heating elements 32 are shown located in refractory sides 26 and 28 for connecting to a source of electric power. If desired, heating elements may be placed in bottom 30 . Further, in some applications, it may be sufficient to provide heating elements in just one side. The electrical heating elements may be electrically connected in a series circuit and the heaters can be controlled as part of a closed loop control system. In another aspect of the invention, the electrical power input to the heaters can be modulated or controlled by a controller to avoid overheating the element. [0055] Liner 24 may be fabricated from any material which is resistant to attack by molten metal such as molten aluminum. Thus, liner 24 should be comprised of a material having high thermal conductivity, high strength, good impact resistance, low thermal expansion and oxidation resistance. Liner 24 may be fabricated from silicon carbide, silicon nitride, magnesium oxide, spinel, carbon, graphite or a combination thereof. Liner 24 may be reinforced with metal fibers as disclosed earlier for strength. Metal fibers having a high heat conduction may be used for purposes of facilitating transfer heat from the heater to the molten metal in the trough member. Thus, metal fibers such as copper fibers may be used with or without reinforcing fibers. The liner material is available from Wahl Refractories under the tradename “Sifca®”, or from Carborundum Corporation under the tradename “Refrax® 20” or “Refrax® 60”. [0056] In forming refractory liner 24 , preferably holes 34 having smooth walls are formed therein during casting for insertion of heaters 32 thereinto and further it is preferred that heaters 32 have a snug fit with holes or receptacles 34 for purposes of transferring heat to refractory liner 24 . Thus, it is preferred to minimize the air gaps between the heater and the refractory liner. However, sufficient clearance should be provided to permit extraction of the heating element, if necessary. Tubes or sleeves 36 may be cast in place in refractory liner 24 to provide for the smooth surface. Preferably, tubes 36 have a strength which permits their collapse to avoid cracking the liner material upon heating. If the tubes are metal, preferred materials are titanium or Kovar® or other metals having a low coefficient of expansion, e.g., less than 7.5×10 −6 in/in/° F. Preferably, tubes 36 are comprised of a refractory material substantially inert to molten aluminum. Thus, if after extended use, refractory liner 24 becomes damaged and cracks permitting molten aluminum to intrude to heater 32 , it is desirable to protect against attack by the molten aluminum. That is, it is preferred to use a refractory tube 36 to contain heater 32 and protect it from molten metal. Refractory tube 36 may be comprised of a material such as mullite, boron nitride, silicon nitride, silicon aluminum oxynitride, graphite, silicon carbide, zirconia, stabilized zirconium and hexalloy (a pressed silicon carbide material) and mixtures thereof Such materials have a high thermal conductivity and low coefficient of expansion. The refractory tubes may be formed by slip casting or pressure casting and fired to provide the refractory or ceramic material with suitable properties resistant to molten aluminum. Metal composite material such as described in U.S. Pat. No. 5,474,282, incorporated herein by reference, may be used. [0057] For purposes of providing extended life of the heated liner, particularly when it is in contact with molten aluminum, it is preferred to use a non-wetting agent applied to the surface of the liner or incorporated in the body of the liner during fabrication. It is important that such non-wetting agents be carefully selected, particularly when the heating element is comprised of an outer metal tube. That is, when heaters 32 are used in the receptacles or holes in the liner which employ a nickel-based metal sheath, the non-wetting agent should be selected from a material non-corrosive to the nickel-base metal sheath. It has been discovered that, for example, sulfur containing non-wetting agents, e.g., barium sulfate, are detrimental. The sulfur from the non-wetting agent reacts with the nickel-based material of the metal sheath or sleeve. The sulfur reacts with the nickel forming nickel sulfide which is a low melting compound. This reaction destroys the protective, coherent oxide of the nickel-based sheath and continues until perforations or holes result in the sheath and destruction of the heater. It will be appreciated that the reaction is accelerated at temperatures of operation e.g., 1400° F. Other materials that are corrosive to the nickel-based sheath include halide and alkali containing non-wetting agents. Non-wetting agents which have been found to be satisfactory include boron nitride and barium carbonate and the like because such agents do not contain reactive material or components detrimental to the protective oxide on the metal sleeve of the heater. [0058] In another aspect of the invention, a thermocouple (not shown) may be placed in the holes in the liner along with the heating element. This has the advantage that the thermocouple provides for control of the heating element to ensure against overheating of element 32 . That is, if the thermocouple senses an increase in temperature beyond a specified set point, then the heater can be shut down or power to the heater reduced to avoid destroying the heating element. [0059] For better heat conduction from the heater to the liner material, a contact medium such as a low melting point, low vapor pressure metal alloy may be placed in the heating element receptacle in the liner. [0060] Alternatively, a powdered material may be placed in the heating element receptacle. When the contact medium is a powdered material, it can be selected from silica carbide, magnesium oxide, carbon or graphite. When a powdered material is used, the particle size should have a median particle size in the range from about 0.03 mm to about 0.3 mm or equivalent U.S. Standard sieve series. This range of particle size greatly improves the packing density of the powder and hence the heat transfer from the element to the liner material. For example, if mono-size material is used, this results in a one-third void fraction. The range of particle size reduces the void fraction below one-third significantly and improves heat transfer. Also, packing the particle size tightly improves heat transfer. [0061] Heating elements that are suitable for use in the present invention are available from Watlow AOU, Anaheim, Calif. or International Heat Exchanger, Inc., Yorba Linda, Calif., and may operate at 120 volts or less. [0062] The low melting metal alloy can comprise lead-bismuth eutectic having the characteristic low melting point, low vapor pressure and low oxidation and good heat transfer characteristics. Magnesium or bismuth may also be used. The heater can be protected, if necessary, with a sheath of stainless steel; or a chromium plated surface can be used. After a molten metal contact medium is used, powdered carbon may be applied to the annular gap to minimize oxidation. [0063] Any type of heating element 32 may be used. Because the liner extends above the metal line, the heaters are protection from the molten aluminum. Further, because the liner supplies the heat to the metal, small diameter heating elements can be used. [0064] Using the liner heater of the invention has the advantage that no additional space is needed for heaters because they are placed in the liner. [0065] In the present invention, it is important to use a heater control. That is, for efficiency purposes, it is important to operate heaters at highest watt density while not exceeding the maximum allowable element temperature. As noted earlier, a thermocouple placed in holes in the liner senses the temperature of the heater element. The thermocouple can be connected to a controller such as a cascade logic controller to integrate the heater element temperature into the control loop. Such cascade logic controllers are available from Watlow Controls, Winona, Minn., designated Series 988. [0066] For purposes of the present invention, watt density is an expression of heat flux; that is, the quantity of heat passing through a surface of unit surface area per unit time. Power per unit area is one such expression. The driving force for heat flux is temperature gradient. As the temperature gradient increases, the heat flux also increases. [0067] Heaters are designed with a watt density that allows the heater to safely operate within the prevailing heat flux conditions. If the heat extraction rate from a heater is not commensurate with the design watt density, the heater element temperature increases. The consequential increase in temperature gradient results in an increase in heat flux. In situations where heat flux is limited by thermal conductivity or other heat transfer considerations, the heater element temperature may reach unacceptably high levels. [0068] Conversely, if the design watt density of an electric heater is intentionally limited to restrict the maximum attainable heating element temperature to a safe value, heating rate can be compromised. During a heat-up from cold start situation, for example, the temperature gradient is high, and therefore the heat transfer rate is high. A high watt density heater can be safely used. As heat-up progresses, however, the temperature relaxes and heat transfer is reduced. Since energy (heat) transfer from the electric heater is reduced, the heater element temperature will increase. Over-temperature will result. [0069] Cascade logic control allows for the use of high watt density heaters, however, the power input to the heater is modulated in accordance with temperature gradient conditions. In cascade logic control, two thermocouple positions are used. The first, or primary position is the process or metal temperature itself. An operator establishes the set point for process temperature. The second input is the heater element or sheath temperature. In some systems, the primary input establishes heater power input by an on/off, proportional, or proportional integrating derivative (PID) control circuit. The secondary input, or sheath temperature, usually functions as a high temperature safety limit. If this limit is reached, the system either shuts down, or cycles on/off. Cascade logic uses the secondary input in a second PID control loop. In combination with the primary input, the secondary loop provides proportional power input to the heater element. Watt density is therefore maximized for any given temperature gradient condition. The principle of cascade logic control is important to heater life and maximizing heat flux input to the metal. [0070] When refractory tubes are used to contain the heaters, it is preferred to coat the inside of the tube with a black colored material such as black paint resistant to high temperature to improve heat conductivity. [0071] When the heaters are used in the liner, typically each heater has watt density of about 12 to 50 watt/in 2 . [0072] While heaters have been shown located in the liner, it will be appreciated that heaters may be inserted directly (not shown) into molten metal through lid or side 28 . Such heaters require protective sleeves or tubes to prevent corrosive attack by the molten aluminum. Heaters disposed directly in the melt have the advantage of higher watt densities. [0073] While it has been noted that for better heat conduction from the heater to the refractory, a low melting metal alloy or a powdered material may be used, it has been found that a glass amalgam molten or softened (having a softening point, SP) at molten aluminum temperatures can be used to improve heat transfer or conduction to the refractory liner. The amalgam may be added in powdered or molten form to the receptacle containing the heater. [0074] Any amalgam that is molten or softened at about 1400° F. or the temperature of molten aluminum conveyed by the trough member may be used. Examples of such amalgams, by weight, are as follows: SiO 2 PbO B 2 O 2 Na 2 O K 2 O ZnO Bi 2 O 3 SP° C. (%) (%) (%) (%) (%) (%) (%) 1 475 44 42 10.5 3.5 — — — 2 550 51 43 2.5 — 3.5 — — 3 335 45 47 8 — — — — 4 338 — 85 15 — — — — 5 553 32 60 3 — 5 — — 6 476 20 60 15 5 — — — 7 — — 15 2 — — 5 75 [0075] For purposes of the invention, an amalgam is a material involving a low melting point solvent and at least one solute component. In the case of an amalgam, a nominal composition is selected with a liquidus temperature above the maximum anticipated service temperature. A mechanical mixture of the components is made, and when heated, results in melting of the solvent and subsequent dissolution of the solute elements. The liquidus temperature follows the value predicted by the multi-component phase diagram and typically first decreases in the case of a eutectic system. As the amount of dissolved solute passes through the eutectic composition, however, the liquidus begins to increase and progressively increases until the service temperature is reached. The amalgam then solidifies. The liquidus temperature may continue to increase as a result of solid state diffusion of solute, this mechanism being known as diffusion solidification. [0076] To improve heat conduction in liner 24 , copper metal powder or pellets and preferably fibers may be added to the refractory in the same way as described herein with respect to the strengthening metal fibers. It has been discovered that the use of copper fibers significantly improves heat conduction through the refractory liner to the molten aluminum. Typical fiber lengths are about 1.3 inch long and about 0.0025 inch in diameter and the copper fibers can comprise 3-35 vol. % of the refractory liner. [0077] The copper fibers can result in up to at least 30% improvement in heat conduction through said refractory. [0078] While the trough member has been illustrated without a lid or cover, it will be understood that a suitable lid or cover comprised of suitable material such as refractory or metal may be provided to contain heat. [0079] While the invention has been particularly illustrated for molten aluminum, its application can be applied to other molten materials or molten metals, including without limitation, copper, lead, iron, magnesium and zinc, for example. [0080] While the invention has been described in terms of preferred embodiments, the claims appended hereto are intended to encompass other embodiments which fall within the spirit of the invention.
A method of heating molten aluminum flowing in a heated trough member comprising the steps of providing a source of molten aluminum and providing a rough member comprised of a first side and a second side, the first and the second sides having outside surfaces, the sides formed from a ceramic material resistant to attack by molten aluminum. The first side and second side have heating element receptacles provided therein with protection tubes provided in the receptacles. The protection tubes are comprised of a refractory selected from the group consisting of mullite, boron nitride, silicon nitride, silicon carbide, graphite, silicon aluminum oxynitride or a metal selected from Kovar® and titanium. Electric heating elements are positioned in the tubes. Molten aluminum is flowed along the trough member from the source and electric power is passed to the heating elements to heat the molten aluminum as it flows along the trough member.
5
TECHNICAL FIELD The present invention pertains generally to a method for learning the flow rate of hydraulic fluid in an automatic transmission. BACKGROUND OF THE INVENTION Generally, a motor vehicle automatic transmission includes a number of gear elements coupling its input and output shafts, and a related number of torque establishing devices such as clutches and brakes that are selectively engageable to activate certain gear elements for establishing a desired speed ratio between the input and output shafts. As used herein, the term “torque transmitting device” will be used to refer to brakes as well as clutches. The transmission input shaft is connected to the vehicle engine through a fluid coupling such as a torque converter, and the output shaft is connected directly to the vehicle wheels. Shifting from one speed ratio to another is performed in response to engine throttle and vehicle speed, and generally involves releasing one or more clutches (off-going) associated with the current or attained speed ratio and applying one or more clutches (on-coming) associated with the desired or commanded speed ratio. The speed ratio is defined as the transmission input speed or turbine speed divided by the output speed. Thus, a low gear range has a high speed ratio and a higher gear range has a lower speed ratio. Shifts from one speed ratio to another require precise timing in order to achieve high quality shifting. The quality of shift depends on the cooperative operation of several functions, such as pressure changes within the clutch apply chambers and the timing of control events. Moreover, manufacturing tolerances in each transmission, changes due to wear, variations in oil quality and temperature, etc., lead to shift quality degradation. SUMMARY OF THE INVENTION The method of the present invention includes estimating a flow rate value for each of a plurality of temperatures. Thereafter, the current transmission temperature is measured. The flow rate corresponding to the current transmission temperature is then learned in the following manner. The process of learning the flow rate initially includes identifying the presence of a predefined shift aberration. If the predefined shift aberration was not identified, the flow rate estimation corresponding to the current transmission temperature is iteratively adjusted. If the predefined shift aberration was identified, the flow rate estimation corresponding to the current transmission temperature is reversed by one iterative step thereby providing the learned flow rate value for the current transmission temperature. The process of learning the flow rate may be performed only after the completion of a shift from which the flow rate is to be learned. The process of learning the flow rate may be performed only if the measured transmission temperature is outside a predefined normal operating temperature range. The process of learning the flow rate may be performed only if the completed shift occurred at the normal shift point. The process of learning the flow rate may be performed only if the maximum engine speed during the shift from which the flow rate is to be learned was less than a predefined engine speed value. The process of learning the flow rate may be performed only if a transmission pump speed is adequate to regulate pressure. The method for approximating the flow rate of hydraulic fluid in an automatic transmission may also include storing the learned flow rate value into a non-volatile memory device. The method for approximating the flow rate of hydraulic fluid in an automatic transmission may also include decreasing the iterative step after the flow rate value has been learned. The above features and advantages and other features and advantages of the present invention are readily apparent from the following detailed description of the best modes for carrying out the invention when taken in connection with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of a vehicle power train in accordance with the present invention; FIG. 2 is an exemplary table on which estimated flow rate values corresponding to a plurality of temperatures are stored; FIG. 3 is a flow chart illustrating a method of estimating flow rate based on a preceding upshift; and FIG. 4 is a flow chart illustrating a method of estimating flow rate based on a preceding regulated closed throttle downshift or a regulated garage shift. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings wherein like characters represent the same or corresponding parts through the several views, there is shown in FIG. 1 a schematic illustration of an exemplary vehicle power train 10 . It should be appreciated that the power train 10 is shown for illustrative purposes, and that the present invention is also applicable to alternate power train configurations. The vehicle power train 10 preferably includes an engine 12 , a transmission 14 , and a torque converter 16 providing a fluid coupling between the engine 12 and a transmission input shaft 18 . A torque converter clutch or TCC 19 is selectively engaged under certain conditions to provide a mechanical coupling between engine 12 and transmission input shaft 18 . The transmission output shaft 20 is coupled to the driving wheels of the vehicle in one of several conventional ways. The illustrated embodiment depicts a four-wheel-drive (4WD) application in which the output shaft 20 is connected to a transfer case 21 that is also coupled to a rear drive shaft R and a front drive shaft F. Typically, the transfer case 21 is manually shiftable to selectively establish one of several drive conditions, including various combinations of two-wheel-drive and four-wheel drive, and high or low speed range, with a neutral condition occurring intermediate the two and four wheel drive conditions. The transmission 14 has three inter-connected planetary gear sets, designated generally by the reference numerals 23 , 24 and 25 . The planetary gear set 23 includes a sun gear member 28 , a ring gear member 29 , and a planet carrier assembly 30 . The planet carrier assembly 30 includes a plurality of pinion gears rotatably mounted on a carrier member and disposed in meshing relationship with both the sun gear member 28 and the ring gear member 29 . The planetary gear set 24 includes a sun gear member 31 , a ring gear member 32 , and a planet carrier assembly 33 . The planet carrier assembly 33 includes a plurality of pinion gears rotatably mounted on a carrier member and disposed in meshing relationship with both the sun gear member 31 and the ring gear member 32 . The planetary gear set 25 includes a sun gear member 34 , a ring gear member 35 , and a planet carrier assembly 36 . The planet carrier assembly 36 includes a plurality of pinion gears rotatably mounted on a carrier member and disposed in meshing relationship with both the sun gear member 34 and the ring gear member 35 . The input shaft 18 continuously drives the sun gear 28 of gear set 23 , selectively drives the sun gears 31 , 34 of gear sets 24 , 25 via clutch C 1 , and selectively drives the carrier 33 of gear set 24 via clutch C 2 . The ring gears 29 , 32 , 35 of gear sets 23 , 24 , 25 are selectively connected to ground 42 via clutches (i.e., brakes) C 3 , C 4 and C 5 , respectively. The state of the clutches C 1 -C 5 (i.e., engaged or disengaged) can be controlled to provide six forward speed ratios (1, 2, 3, 4, 5, 6), a reverse speed ratio (R) or a neutral condition (N). For example, the first forward speed ratio is achieved by engaging clutches C 1 and C 5 . Shifting from one forward speed ratio to another is generally achieved by disengaging one clutch (referred to as the off-going clutch) while engaging another clutch (referred to as the on-coming clutch). For example, the transmission 14 is downshifted from second to first by disengaging clutch C 4 while engaging clutch C 5 . The torque converter clutch 19 and the transmission clutches C 1 -C 5 are controlled by an electro-hydraulic control system, generally designated by reference numeral 44 . The hydraulic portions of the control system 44 include a pump 46 which draws hydraulic fluid from a reservoir 48 , a pressure regulator 50 which returns a portion of the pump output to reservoir 48 to develop a regulated pressure in line 52 , a secondary pressure regulator valve 54 , a manual valve 56 manipulated by the driver of the vehicle, and a number of solenoid-operated fluid control valves 58 , 60 , 62 and 64 . The electronic portion of the electro-hydraulic control system 44 is primarily embodied in the transmission control unit 66 , or controller, which is microprocessor-based and conventional in architecture. The transmission control unit 66 controls the solenoid-operated fluid control valves 58 - 64 based on a number of inputs 68 to achieve a desired transmission speed ratio. Such inputs include, for example, signals representing the transmission input speed TIS, a driver torque command TQ, the transmission output speed TOS, and the hydraulic fluid temperature Tsump. Sensors for developing such signals may be conventional in nature, and have been omitted for simplicity. The control lever 82 of manual valve 56 is coupled to a sensor and display module 84 that produces a diagnostic signal on line 86 based on the control lever position; such signal is conventionally referred to as a PRNDL signal, since it indicates which of the transmission ranges (P, R, N, D or L) has been selected by the vehicle driver. Finally, fluid control valves 60 are provided with pressure switches 74 , 76 , 78 for supplying diagnostic signals to control unit 66 on lines 80 based on the respective relay valve positions. The control unit 66 , in turn, monitors the various diagnostic signals for the purpose of electrically verifying proper operation of the controlled elements. The solenoid-operated fluid control valves 58 - 64 are generally characterized as being either of the on/off or modulated type. To reduce cost, the electro-hydraulic control system 44 is configured to minimize the number of modulated fluid control valves, as modulated valves are generally more expensive to implement. To this end, fluid control valves 60 are a set of three on/off relay valves, shown in FIG. 1 as a consolidated block, and are utilized in concert with manual valve 56 to enable controlled engagement and disengagement of each of the clutches C 1 -C 5 . Valves 62 , 64 are of the modulated type. For any selected ratio, the control unit 66 activates a particular combination of relay valves 60 for coupling one of the modulated valves 62 , 64 to the on-coming clutch, and the other one of the modulated valves 62 , 64 to the off-going clutch. The modulated valves 62 , 64 each comprise a conventional pressure regulator valve biased by a variable pilot pressure that is developed by current controlled force motors (not shown). Fluid control valve 58 is also a modulated valve, and controls the fluid supply path to converter clutch 19 in lines 70 , 72 for selectively engaging and disengaging the converter clutch 19 . The transmission control unit 66 determines pressure commands for smoothly engaging the on-coming clutch while smoothly disengaging the off-going clutch to shift from one speed ratio to another, develops corresponding force motor current commands, and then supplies current to the respective force motors in accordance with the current commands. Thus, the clutches C 1 -C 5 are responsive to the pressure commands via the valves 58 - 64 and their respective actuating elements (e.g., solenoids, current-controlled force motors). As indicated above, each shift from one speed ratio to another includes a fill or preparation phase during which an apply chamber 91 of the on-coming clutch is filled in preparation for torque transmission. Fluid supplied to the apply chamber compresses an internal return spring (not shown), thereby stroking a piston (not shown). Once the apply chamber is filled, the piston applies a force to the clutch plates, developing torque capacity beyond the initial return spring pressure. Thereafter, the clutch transmits torque in relation to the clutch pressure, and the shift can be completed using various control strategies. A typical control strategy involves commanding a maximum on-coming clutch pressure for an empirically determined clutch fill time. The clutch fill time can be calculated based on the clutch volume and the flow rate according to the equation: clutch fill time=“clutch volume”/“flow rate”. The “clutch volume” is the volume of fluid required to fill a clutch apply chamber and thereby cause the clutch to gain torque capacity. The “flow rate” is the rate at which hydraulic fluid is transferred to the clutch apply chamber. According to the preferred embodiment, the on-coming clutch volume is calculated or “learned” in the manner disclosed in commonly assigned U.S. Pat. No. 6,915,890 issued to Whitton et al., and which is hereby incorporated by reference in its entirety. Advantageously, the “learned” on-coming clutch volume can account for build variations and tolerances, and can also account for variation over time due to wear. For purposes of the present invention, a “learned value” is value that is estimated using an adaptive process. The adaptive process is so named because the process is adaptable or variable to reflect new information and thereby account for changes over time. It has been observed that the flow rate of the hydraulic fluid being transferred to a clutch apply chamber is temperature dependent. Conventionally, the flow rate was measured at a wide variety of temperatures to generate a flow rate curve. Generating flow rate curves requires extensive hot and cold testing such that the flow rate curves are expensive and time consuming to produce. It is therefore an object of the present invention learn the flow rate without reliance on extensive testing. According to the preferred embodiment of the present invention, the flow rate is first roughly estimated in a conventional manner (e.g., based on a nominal flow rate or on previously compiled test data) at a plurality of temperatures, and is thereafter learned at such temperatures to provide a more accurate estimation. The learned flow rate values and their corresponding temperatures are preferably stored as a table in a non-volatile memory device such as the non-volatile random access memory (NOVRAM) 96 . Advantageously, the NOVRAM 96 retains information after losing power such that the flow rate data saved therein is not lost when the vehicle is shut off. Referring to FIG. 2 , an exemplary flow rate table 98 as stored in the NOVRAM 96 (shown in FIG. 1 ) is shown. The flow rate data of FIG. 2 is representative of the initial rough estimates for flow rate at the plurality of different temperatures (i.e., −40, 0, 40, 80 and 120 degrees Celsius). It should be appreciated that table 98 of FIG. 2 is merely illustrative, and that the estimated flow rate values and/or the listed temperatures may be varied as required to meet the needs of a particular application. Each time the flow rate is learned at one of the temperatures included in table 98 , the learned flow rate value is saved to the table thereby replacing any previously estimated value. The learned flow rate data is retrievable from the table 98 to calculate the clutch fill time of the on-coming clutch for subsequent ratio changes. If a measured temperature falls between two temperatures included in table 98 , the corresponding flow rate can be obtained by interpolation. Referring to FIG. 3 , a method 100 (also referred to herein as algorithm 100 ) for learning a flow rate during an upshift is shown. More precisely, FIG. 3 shows a block diagram representing steps performed by a control device such as the control unit 66 (shown in FIG. 1 ). At step 102 , the algorithm 100 determines whether an upshift from which the flow rate is to be learned is completely finished. This step is implemented to ensure the upshift has been completed before the process of learning from the upshift is initiated. If, at step 102 , the upshift has not yet been completed, the algorithm 100 repeats step 102 . If, at step 102 , the upshift has been completed, the algorithm 100 proceeds to step 104 . At step 104 , the algorithm 100 determines whether the current transmission temperature is outside a predefined normal operating range (e.g., between 70 and 100 degrees Celsius). The current transmission temperature is obtainable using temperature sensors (not shown) configured to measure and transmit temperature data to the control unit 66 (shown in FIG. 1 ). The flow rate within the normal operating range is preferably estimated based on a nominal hydraulic fluid flow rate value and the method of the present invention is applied to learn the flow rate only when the current transmission temperature is outside this range. Therefore, if the current transmission temperature is within the predefined normal operating range, the algorithm 100 proceeds to step 106 at which the algorithm 100 waits for the next upshift, and thereafter the algorithm 100 returns to step 102 . If the current transmission temperature is outside the predefined normal operating range, the algorithm 100 proceeds to step 108 . At step 108 , the algorithm 100 determines whether the minimum throttle input to the engine 12 (shown in FIG. 1 ) during the upshift was greater than a predetermined amount. This step is implemented because the method of the present invention learns the flow rate during an upshift in response to an engine flare condition, which is described in detail hereinafter, and such engine flare may not be detectable unless the minimum engine throttle is greater than a predetermined amount. Therefore, if the minimum engine throttle is below the predetermined amount, the algorithm 100 proceeds to step 106 at which the algorithm 100 waits for the next upshift, and thereafter the algorithm 100 returns to step 102 . If the minimum engine throttle is equal to or greater than the predetermined amount, the algorithm 100 proceeds to step 110 . At step 110 , the algorithm 100 determines whether the previous upshift occurred at the normal shift point. This step is implemented because the method of the present invention preferably does not learn from an upshift unless it occurs at the normal shift point. As an example, if the vehicle operator overrides the normally scheduled shift point by manually moving the shift selector (not shown), timing information pertaining to the manual shift is not implemented to learn the flow rate. Therefore, if the previous upshift did not occur at the normal shift point, the algorithm 100 proceeds to step 106 at which the algorithm 100 waits for the next upshift, and thereafter the algorithm 100 returns to step 102 . If the previous upshift did occur at the normal shift point, the algorithm 100 proceeds to step 112 . At step 112 , the algorithm 100 determines whether the maximum engine speed during the upshift was less than a predetermined speed. This step is implemented because the method of the present invention learns flow rate in response to an engine flare condition, which is described in detail hereinafter, and such engine flare may not be detectable if the engine speed is high enough to induce engine output limits such as with a governor (not shown). Therefore, the maximum engine speed during the upshift was equal to or greater than the predetermined speed, the algorithm 100 proceeds to step 106 at which the algorithm 100 waits for the next upshift, and thereafter the algorithm 100 returns to step 102 . If the maximum engine speed during the upshift was less than the predetermined speed, the algorithm 100 proceeds to step 114 . At step 114 , the algorithm 100 determines if engine flare has been identified. Engine flare is a shift aberration wherein the on-coming clutch gains capacity late resulting in a condition similar to the neutral gear speed ratio. Engine flare is preferably identified when the turbine speed or the transmission input speed, which can be measured with a speed sensor, rises more than a predetermined amount (e.g., 50 rpm) above the commanded gear speed. If engine flare has not been identified at step 114 , the algorithm 100 proceeds to step 116 . If engine flare has been identified at step 114 , the algorithm 100 proceeds to step 118 . At step 116 , the algorithm 100 iteratively increases the estimated flow rate value in the table 98 (shown in FIG. 2 ) corresponding to the current transmission temperature. The “iterative step” is the amount by which the flow rate value is increased, and is configurable to meet the needs of a particular application. According to the preferred embodiment, the iterative step is larger before a flow rate value is learned for the first time, and after a particular flow rate value has been learned the iterative step is reduced. As an example, the iterative step before a flow rate value is learned may be 10 cc/second, and thereafter be reduced to 2 cc/second. If the current transmission temperature falls between two of the temperatures listed in table 98 , a flow rate estimation is obtainable by interpolating or scaling between the flow rate values in table 98 that correspond to the two closest temperatures. At step 118 , the algorithm 100 reduces the estimated flow rate value in the table 98 (shown in FIG. 2 ) corresponding to the current transmission temperature by one iterative step. As engine flare was identified at step 114 , the estimated flow rate value used to calculate clutch fill time during the previous ratio change is likely to be too high. Therefore, the estimated flow rate is reduced at step 118 by one iterative step to provide a closer approximation of the actual flow rate. The iteratively reduced flow rate is the “learned” flow rate value for the current transmission temperature and is saved into the table 98 . If the current transmission temperature falls between two of the temperatures listed in table 98 , a flow rate estimation is obtainable by interpolating or scaling between the flow rate values in table 98 that correspond to the two closest temperatures. Also at step 118 , after the flow rate value has been learned as described hereinabove, the iterative step for this value is preferably reduced to a minimal value (e.g., 2 cc/second) so that the process of learning can continue throughout the life of the vehicle and thereby account for changes to the system over time. The reduction of the iterative step is optional and is predicated on the assumption that the previously learned flow rate value is close to the actual and therefore any changes to the learned flow rate should be relatively small. Although the present invention has been described only as being applicable to upshifts, other shift types may be envisioned. Referring to FIG. 4 , a method 130 (also referred to herein as algorithm 130 ) for learning a flow rate during a “regulated closed-throttle downshifts” or a “regulated garage shift” is shown. More precisely, FIG. 4 shows a block diagram representing steps performed by a control device such as the control unit 66 (shown in FIG. 1 ). For purposes of the present invention, the term “regulated” refers a shift which takes place while the transmission pump 46 (shown in FIG. 1 ) is capable of meeting the pressure requirements of the hydraulic system. A non-regulated shift may take place, for instance, when the pump 46 is being driven by the engine 12 (shown in FIG. 1 ) and the engine 12 is operating at low speeds. A “closed throttle downshift” is a downshift taking place with zero throttle input to the engine 12 . A “garage shift” is a shift from neutral to drive or from neutral to reverse. At step 132 , the algorithm 130 determines whether the “regulated closed-throttle downshift” or the “regulated garage shift” from which the flow rate is to be learned is completely finished. This step is implemented to ensure the shift has been completed before the process of learning from the shift is initiated. If, at step 132 , the shift has not yet been completed, the algorithm 130 repeats step 132 . If, at step 132 , the shift has been completed, the algorithm 130 proceeds to step 134 . At step 134 , the algorithm 130 determines whether the current transmission temperature is outside a predefined normal operating range (e.g., between 70 and 100 degrees Celsius). The current transmission temperature is obtainable using temperature sensors (not shown) configured to measure and transmit temperature data to the control unit 66 (shown in FIG. 1 ). The flow rate within the normal operating range is preferably estimated based on a nominal hydraulic fluid flow rate value and the method of the present invention is applied to learn the flow rate only when the current transmission temperature is outside this range. Therefore, if the current transmission temperature is within the predefined normal operating range, the algorithm 130 proceeds to step 136 at which the algorithm 130 waits for the next “regulated closed-throttle downshift” or the next “regulated garage shift”, and thereafter the algorithm 130 returns to step 132 . If the current transmission temperature is outside the predefined normal operating range, the algorithm 130 proceeds to step 138 . At step 138 , the algorithm 130 determines whether the maximum throttle input to the engine 12 is less than a predetermined amount. This step is implemented because the method of the present invention learns the flow rate during a “regulated closed-throttle downshift” or a “regulated garage shift” in response to an overfill condition, which is described in detail hereinafter, and such overfill may be falsely detected unless the maximum engine throttle is less than a predetermined amount. If throttle is applied during a “regulated closed-throttle downshift”, the increase in turbine speed could be caused by either an overfilled condition or the off-going clutch releasing prematurely and letting the input speed be increased by the increase in engine torque. However, if throttle is near zero, torque is neutral or negative and an increase in input speed would only be caused by an overfilled condition. Therefore, if the maximum engine throttle is greater than or equal to the predetermined amount, the algorithm 130 proceeds to step 136 at which the algorithm 130 waits for the next “regulated closed-throttle downshift” or the next “regulated garage shift”, and thereafter the algorithm 130 returns to step 132 . If the maximum engine throttle is less than the predetermined amount, the algorithm 130 proceeds to step 140 . At step 140 , the algorithm 130 determines whether the previous “regulated closed-throttle downshift” or “regulated garage shift” occurred at the normal shift point. This step is implemented because the method of the present invention preferably does not learn from a shift unless it occurs at the normal shift point. As an example, if the vehicle operator overrides the normally scheduled shift point by manually moving the shift selector (not shown), timing information pertaining to the manual shift is not implemented to learn the flow rate. Therefore, if the previous “regulated closed-throttle downshift” or “regulated garage shift” did not occur at the normal shift point, the algorithm 130 proceeds to step 136 at which the algorithm 130 waits for the next “regulated closed-throttle downshift” or the next “regulated garage shift”, and thereafter the algorithm 130 returns to step 132 . If the previous “regulated closed-throttle downshift” or “regulated garage shift” did occur at the normal shift point, the algorithm 130 proceeds to step 142 . At step 142 , the algorithm 130 determines whether speed at which the transmission pump 46 (shown in FIG. 1 ) is being driven is sufficient to meet the needs of the hydraulic system. This step is implemented to ensure the previous shift was regulated because, as previously indicated, the method 130 is preferably only applied to regulated shifts. The determination made at step 142 may be based on a conventional speed sensor attached to the engine 12 and/or the pump 46 . If the transmission pump speed is not sufficient to meet the needs of the hydraulic system, the algorithm 130 proceeds to step 136 at which the algorithm 130 waits for the next “regulated closed-throttle downshift” or the next “regulated garage shift”, and thereafter the algorithm 130 returns to step 132 . If the transmission pump speed is sufficient to meet the needs of the hydraulic system, the algorithm 130 proceeds to step 144 . At step 144 , the algorithm 100 determines if an overfill condition has been identified. Overfill is a shift aberration wherein the on-coming clutch gains capacity too soon. Overfill during a “regulated closed-throttle downshift” is preferably identified when the turbine speed or the transmission input speed, which can be measured with a speed sensor, increases before it is scheduled to do so. Overfill during a “regulated garage shift” is preferably identified when the turbine speed or the transmission input speed, which can be measured with a speed sensor, decreases before it is scheduled to do so. If overfill has not been identified at step 144 , the algorithm 130 proceeds to step 146 . If overfill has been identified at step 144 , the algorithm 130 proceeds to step 148 . At step 146 , the algorithm 130 iteratively decreases the estimated flow rate value in the table 98 (shown in FIG. 2 ) corresponding to the current transmission temperature. According to the preferred embodiment, the iterative step is larger before a flow rate value is learned for the first time, and after a particular flow rate value has been learned the iterative step is reduced. If the current transmission temperature falls between two of the temperatures listed in table 98 , a flow rate estimation is obtainable by interpolating or scaling between the flow rate values in table 98 that correspond to the two closest temperatures. At step 148 , the algorithm 130 increases the estimated flow rate value in the table 98 (shown in FIG. 2 ) corresponding to the current transmission temperature by one iterative step. As overfill was identified at step 144 , the estimated flow rate value used to calculate clutch fill time during the previous ratio change is likely to be too low. Therefore, the estimated flow rate is increased at step 148 by one iterative step to provide a closer approximation of the actual flow rate. The iteratively increased flow rate is the “learned” flow rate value for the current transmission temperature and is saved into the table 98 . If the current transmission temperature falls between two of the temperatures listed in table 98 , a flow rate estimation is obtainable by interpolating or scaling between the flow rate values in table 98 that correspond to the two closest temperatures. Also at step 148 , after the flow rate value has been learned as described hereinabove, the iterative step for this value is preferably reduced to a minimal value (e.g., 2 cc/second) so that the process of learning can continue throughout the life of the vehicle and thereby account for changes to the system over time. The reduction of the iterative step is optional and is predicated on the assumption that the previously learned flow rate value is close to the actual and therefore any changes to the learned flow rate should be relatively small. While the best modes for carrying out the invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention within the scope of the appended claims.
The present invention provides a method for approximating the flow rate of hydraulic fluid in an automatic transmission. The method includes estimating a flow rate value for each of a plurality of temperatures. Thereafter, the current transmission temperature is measured. The flow rate corresponding to the current transmission temperature is then learned in the following manner. The process of learning the flow rate initially includes identifying the presence of a predefined shift aberration. If the predefined shift aberration was not identified, the flow rate estimation corresponding to the current transmission temperature is iteratively adjusted. If the predefined shift aberration was identified, the flow rate estimation corresponding to the current transmission temperature is reversed by one iterative step thereby providing the learned flow rate value for the current transmission temperature.
8
BACKGROUND OF THE INVENTION I. Field of the Invention This invention relates to compositions and processes for thermoplastic processing of PET, more particularly extrusion/melt shaping of PET. II. Description of the Prior Art Until now, linear thermoplastic polyesters such as PET have found no utility in extrusion/melt shaping and related thermoplastic fabrication techniques that require dimensional stability in the melt because such techniques require high melt viscosity and a high degree of melt strength and elasticity. PET generally has an intrinsic viscosity of about 0.5 to 1.1 dl. per gm. and insufficient melt strength and elasticity for such applications. Furthermore, PET exhibits a fast rate of crystallization at temperatures above 140° C. which makes the achievement of clear amorphous articles by such thermoplastic fabrication techniques difficult. Therefore, until now, articles produced from PET had to be made by injection blow-molding techniques in which a parison or perform is injection molded, cooled rapidly and then reheated to a temperature above the T g but below the crystalline melting point and then blown to the desired shape. See U.S. Pat. Nos. 3,733,309; 3,745,150; and 3,803,275. While amorphous articles would be preferred because of their clarity and toughness as compared to crystalline articles, until now such processing required very specialized equipment such as is shown in U.S. Pat. No. 3,803,275 wherein a hollow slug was extruded directly into a mold maintained at less than 0° C. It has been previously suggested by Dijkstra et al, U.S. Pat. No. 3,553,157, to prepare thick-walled shaped articles of improved impact strength from PET and a compound capable of reacting with hydroxyl or carboxyl end groups, for example polyanhydrides. "Thick-walled" is defined by Dijkstra et al as "shape and/or dimensions are such that they are not readily conducive to orientation of the polymer by drawing." Dijkstra et al prefer crystalline articles reinforced by glass fibers, and teach nothing with regard to methods of producing blow-molded articles, blown film or foam from PET, nor anything regarding enhancement of melt characteristics of PET. Extrusion/melt shaping of poly(butylene terephthalate) (PBT) at intrinsic viscosities at least 1.05 dl./gm. has been accomplished by a variety of techniques. See U.S. Pat. Nos. 3,814,786 and 3,931,114. Borman et al, Ser. No. 382,512 of July 25, 1973 (Netherlands 74,07268) attempt to solve this melt strength problem by the use of branched polyesters. The branching necessarily must be conducted in the polyester kettle and thus there is an upper limit as to how much viscosity Borman et al can achieve while still being able to handle the branched polyester. The object of the present invention is to provide a method of thermoplastic processing of PET to form amorphous articles. It is a further object to provide amorphous extrusion/melt shaped PET articles. A still further object is to provide clear PET bottles by extrusion blow-molding. SUMMARY OF THE INVENTION These and other objects as will become apparent from the following disclosure are achieved by the present invention which comprises in one aspect a composition for improving the thermoplastic processing characteristics of PET comprising (A) a polyanhydride selected from the group consisting of pyromellitic dianhydride, mellitic trianhydride, tetrahydrofuran dianhydride, and polyanhydrides containing at least two unsubstituted or substituted phthalic anhydride radicals; and (B) a fatty acid or N-substituted fatty acid amide having at least 10 carbon atoms in the acid portion of the molecule. In another aspect the invention comprises a composition for thermoplastic processing to form amorphous articles comprising PET, the polyanhydride, and the fatty acid or N-substituted fatty acid amide. In another aspect, the invention comprises a process for preparing noncrystalline shaped articles comprising adding about 0.1 to 5% by weight of a polyanhydride, selected from a defined group, to PET before processing. A still further aspect of the invention comprises films, pipes, foams, containers, profiles, or other articles prepared in accordance with the above-mentioned process. DETAILED DESCRIPTION OF THE INVENTION The PET used with this invention contains terminal hydroxyl groups and possesses relatively low melt strength and elasticity before modification. The PET generally has an intrinsic viscosity of about 0.5 to about 1.1 dl/g, preferably about 0.6 to 0.8 dl/g. The polyanhydride used is selected from the group consisting of pyromellitic dianhydride, mellitic trianhydride, tetrahydrofuran dianhydride, and polyanhydrides containing at least two unsubstituted or substituted phthalic anhydride radicals such as the reaction product from two moles of pyromellitic dianhydride or trimellitic anhydride with one mole of a glycol or other active hydrogen-containing compound. It has been found that certain types of polyanhydrides do not function in this invention. These include maleic anhydride copolymers, cyclopentane tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and bicyclo (2:2:2) oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride. Optimum results are achieved by use of 0.1 to 5% by weight of the polyanhydride, preferably 0.2 to 1.5 percent and most preferably about 0.3 to 1.0 percent by weight based on PET. The most preferred polyanhydride is pyromellitic dianhydride. The maximum melt viscosity is achieved with stoichiometric equivalence of anhydride groups and terminal hydroxyl groups in the polyester after making allowances for possible side reactions. The higher the processing temperature, the higher the concentration of the modifier composition required for high melt strength at that processing temperature up to the stochiometric equivalence of anhydride and terminal hydroxyl groups. The optional fatty acid or N-substituted fatty acid amide has at least 10 carbon atoms in the acid portion of the molecule. By the term "fatty acid" is meant to include fatty acids and other materials which generate fatty acids under the processing conditions used. Preferred compounds are palmitic acid, lauric or stearic acid, N-alkyl stearamide, N,N-dialkyl stearamide or alkylene bis(stearamide). Surprisingly other types of lubricants which would be expected to function equivalently in this process have been found to be unsuitable. The lubricants found to be unsuitable were metal stearates, unsubstituted fatty acid amides, paraffin waxes, ester waxes, polyethylene, and oxidized polyethylenes. From about 0.1 to 5% by weight of fatty acid or N-substituted fatty acid is suitable, with a preferred amount being about 0.25 to 1.5 percent by weight. The polyanhydride and the optional fatty acid or N-substituted fatty acid amide are suitably incorporated in the composition by mixing at some time prior to melt blending in the extruder. The melt blending step may be separate and distinct or identical with the processing step to produce the finished article. It is important that no crystallization promoter is present in the composition since this invention is directed to compositions suitable for producing amorphous, non-crystalline articles. If substantial crystallization occurs in the process the resultant articles become opaque and brittle. In some cases, such as with pipe, foam and profile extrusion, a small degree of crystallinity may be acceptable and can be achieved by control of the cooling cycle. However, in most cases it is preferred to prepare amorphous articles on standard extrusion equipment with no special cooling device. The type of article to be produced, whether it be bottles, films, foams, pipes or profile, will govern the auxiliary equipment to be employed. For instance, to produce bottles, blow-molding equipment is necessary. To produce film, blown film equipment is necessary. The PET, polyanhydride, and optional fatty acid or N-substituted fatty acid amide are extruded to a molten self-supporting preform which is subsequently shaped into a final form and then allowed to cool to a shaped article. The shaping step can be accomplished by either injecting a fluid into the molten composition, or by means of a die. In the case where a fluid is used, air or inert gas are the preferred fluids, and bottles, foams, films, and containers can be made. By "blow-molding" is meant shaping by inserting the molten self supporting preform (or "parison") in a mold and injecting a gas such as air into the parison to form the shaped article. In the case of films, shaping is accomplished by extruding a hollow tube and expanding to a larger diameter while still molten by gas pressure within the tube. The film "bubble" is cooled and subsequently collapsed to a film. Clear film can be made by the latter process. Shaping is also accomplished by extrusion blow-molding, wherein a hollow tube or parison of molten resin is extruded vertically downward until a prespecified length has been achieved. The length of the parison depends upon the size of the bottle to be produced. The tube of molten resin is cut and carried to the blow-molding equipment where it is clamped into a mold having a shape of the bottle to be produced. It is then blown with fluid, usually air, to conform to the mold shape, and then is cooled and ejected. The mold walls are usually cooled with tap water. Unmodified PET is unsuitable for these types of operations because it does not have sufficient melt strength to prevent sagging. Although melt strength varies with viscosity of PET, it is not solely a function of viscosity or of molecular weight. The shaping operation is meant to also include drawing or stretching below the melting point of the polymer to achieve orientation. Thin-walled articles are produced by the present invention. By "thin-walled" is meant articles of shape and/or dimensions such that they are readily conducive to orientation of the polymer by drawing. Drawing, and the resultant orientation, is entirely optional, however. Blow-molded bottles are usually only about 20 to 30 mils thick, and blown film is generally only about 0.5 to 10 mils thick. Conventional additives such as antioxidants, thermal stabilizers, fillers, pigments and flame retardant additives can be used in the composition of this invention provided they do not exert any adverse effect on the melt strength. It is preferred not to have glass fiber reinforcement. It is highly preferred that clear articles are produced. The following examples are presented to illustrate but a few embodiments of the invention. Comparative examples are also presented. All parts and percentages are by weight unless otherwise indicated. EXAMPLE 1 Poly(ethylene terephthalate), 1000 gms, having an intrinsic viscosity of 0.67 dl/g and moisture content below 0.02%. and pyromellitic dianhydride, 3.0 gms. were mixed and melt blended in a 1-inch extruder at 260°-275° C. The extrudate was in the form of a clear, molten, hollow tube that was blow-molded into a clear 4 oz. bottle. There was no evidence of parison sag. The intrinsic viscosity of the walls of the bottles was 0.86 dl/g and was found to be completely amorphous by DSC measurements. The bottle mold temperature was 10° C. and the time in the mold was 30 to 40 seconds. The parison or molten, hollow tube, exhibiting only moderate die swell and some die lip sticking, was produced at a smooth, steady rate allowing continuous production of bottles. No additional cooling was needed to achieve clear bottles other than the tap water cooled mold. The air pressure for blow molding was about 90 psig. The bottle had properties characteristic of amorphous unoriented poly(ethylene terephthalate); tensile strength (yield/break) = 6489/4536 psi; tensile modulus = 254,918 psi; elongation (yield/break) = 3.1/281%, water vapor transmission = 6.9 gm-mil/100 in 2 /24 hrs. at 38° C. and 90% R.H., wall thickness = 20-25 mils. EXAMPLE 2 Example 1 was repeated except that the pyromellitic dianhydride was replaced with 7.6 g of the ethylene glycol bis(4-trimellitate anhydride) which is the ester adduct of trimellitic anhydride and ethylene glycol. Clear self-supporting parisons were formed which could be blow-molded into clear bottles. EXAMPLE 3 Example 1 was repeated except that pyromellitic dianhydride was replaced by 9.0 gms. of 3,3',4'-benzophenonetetracarboxylic dianhydride. Clear, self-supporting parisons were formed which could be blown into clear bottles. EXAMPLE 4 Poly(ethylene terephthalate), 100 gms. having an intrinsic viscosity of 0.67 dl/g and a moisture content below 0.02%, pyromellitic dianhydride, 5.0 gms., and ethylene bis(stearamide), 10.0 grams, were mixed and melt blended in a 1-inch extruder at 260°-275° C. The extrudate was in the form of a clear, molten, hollow tube that was blow-molded into a clear 4 oz. bottle. There was no evidence of parison sag or opacity even when the molten tube was 12 to 16 inches in length. The walls of the bottles had an intrinsic viscosity of 0.84 dl/g and were found to be completely amorphous by DSC measurements. The bottle mold temperature was about 10° C. and the dwell time in the mold was 30 to 40 seconds. The parison or molten, hollow tube, exhibiting only moderate die swell and no die lip sticking, was produced at a smooth, steady rate, allowing continuous production of the bottles. No additional cooling was required to achieve clear bottles other than the tap-water cooled mold. The air pressure for the blow-molding operation was about 90 psig. The bottles had properties characteristic of amorphous, unoriented poly(ethylene terephthalate); tensile strength (yield/break) = 6263/4929 psi, tensile modulus = 243,149 psi, % elongation (yield/break) = 2.9/237%, water vapor transmission = 6.5 gm-mil/100 in 2 /24 hours at 39° C. and 90% R.H., bottle weight = 15 gms, wall thickness = 25-30 mils. EXAMPLE 5 Example 4 was repeated except the ethylene bis(stearamide) was replaced with 5.0 gms of stearic acid. Stable molten parisons that were readily blow-molded into clear bottles, were produced at a smooth steady rate. The intrinsic viscosity of the bottle walls was about 1.1 dl/g, and there was no evidence of crystallization in the body walls by appearance or DSC measurements. EXAMPLE 6 Example 4 was repeated except the ethylene bis(stearamide) was replaced with 10.0 gms of N,N-dibutyl stearamide. No evidence of parison sag was encountered and clear bottles were readily produced. EXAMPLE 7 Example 4 was repeated except the pyromellitic dianhydride was replaced with the reaction product from two moles of pyromellitic dianhydride and one mole of 1,5-pentanediol. Stable, clear, molten parisons were produced that could be blow-molded into clear bottles. EXAMPLE 8 -- Comparative For comparative purposes, unmodified poly(ethylene terephthalate) having an intrinsic viscosity of 0.67 dl/g and a moisture content of less than 0.02% was extruded under conditions similar to Example 1. The extrudate exhibited excessive sagging and formed a very thin rod rather than a hollow tube. A stable, molten parison or hollow tube could not be formed under any conditions and the intrinsic viscosity of the extrudate was 0.65 dl/g. The melt strength was not great enough to allow bottles to be blow-molded. EXAMPLE 9 -- Comparative Example 8 was repeated except poly(ethylene terephthalate) with an intrinsic viscosity of 1.04 dl/g was employed. Excessive parison sag occurred and it was impossible to maintain a stable, molten parison long enough to allow bottles to be blow-molded. EXAMPLE 10 This Example illustrates the manufacture of blown film in accordance with the invention. Poly(ethylene terephthalate), 1000 gms. having an intrinsic viscosity of 0.67 deciliters/gm. and a moisture content below 0.02%, pyromellitic dianhydride, 4.0 grams, and ethylene bis(stearamide), 10.0 grams, were melt blended in a 1 inch extruder at 260°-275° C. through a vertical film blowing die with a 2 inch diameter and a 30 mil die land into a 5 ft. bubble tower. A stable film bubble was made by introducing air into the interior of the extruded tube. The melt was cooled with a circular jet of air as it emerged from the die. The extrudate had sufficient melt strength that a stable film bubble could be maintained without difficulty. The thickness of the film could be varied from 0.5 to 6.0 mils. It was completely clear and had tensile properties characteristic of unoriented, amorphous PET; tensile strength (break) = 7500 psi, tensile modulus = 350,000 psi, % elongation (break) = 2.5%. EXAMPLE 11 -- Comparative Example 10 was repeated except the pyromellitic dianhydride and ethylene bis(stearamide) were deleted. A stable bubble could not be maintained due to low melt strength. The extrudate continually collapsed on the die or holes developed in the tube.
Composition and method for improving the thermoplastic processing characteristics of poly(ethylene terephthalate) (PET) in amphorous form are disclosed, as well as PET with improved melt strength.
2
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a continuation of application Ser. No. 13/225,131, filed on Sep. 2, 2011, which is a divisional of application Ser. No. 11/027,860, filed on Dec. 30, 2004, issued on Sep. 27, 2011 as U.S. Pat. No. 8,024,898, the contents of which are fully incorporated herein by reference. FIELD OF THE INVENTION [0002] The present invention relates to a system and method for finishing fenestration openings. BACKGROUND OF THE INVENTION [0003] General contractors engaged in the construction of a commercial or residential building are responsible for scheduling various subcontractors to complete their assigned tasks in a timely manner. When a certain subcontractor's work is delayed for some reason, further delays may be caused for other subcontractors whose tasks are dependent on the first subcontractor. For instance, plumbing and electrical work must be completed before interior drywall can be hung; likewise painting and finishing cannot proceed until the drywall is hung. To the extent that a job can be planned so that as few subcontractors are dependent on the completion of each other's work as possible, a smoother job with fewer delays is likely to result. [0004] While better scheduling and planning on the part of the general contractor can reduce these bottlenecks, some are unavoidable due to requirements imposed by current building materials. For example, fenestration openings are unfinished openings in the side of a building which will ultimately receive a window or door assembly. Currently, windows are delivered by the manufacturer having a frame which is attached to the framing members of the fenestration opening. Until this frame is installed, the finishing crews, which apply the exterior finish such as plastering to the building as well as the interior drywall crews, cannot complete their work. Accordingly, delays in shipment and installation of the windows and frames lead to significant problems in work scheduling for the building as a whole, which can potentially cause an entire job to fall behind schedule. [0005] A need exists for a system and method which reduces the need for a high degree of coordination between subcontractors. With such a system and method, the burden on the window and door manufacturers to deliver on a tight schedule is reduced, and the general contractor regains a degree of control over his schedule without worrying about being held up by his custom window and door suppliers not delivering on time. SUMMARY OF THE INVENTION [0006] Accordingly, a fenestration cap system is provided as a separate piece from the frame of the window. The fenestration cap can be installed prior to the delivery of the widows and accompanying frames, and allows interior and exterior finishing to be completed without having to install the window and door systems. This allows more time for custom window and door orders to be filled by the supplier without holding up progress in other areas of the job. The waiting for the actual windows to arrive and be installed is no longer one of the critical paths of the job schedule, and may be completed at the convenience of the contractor. [0007] This system is compatible with the frames of major door and window suppliers, and gives consumers the flexibility to choose the windows and doors that best fit their specific needs without being forced to make a selection due to manufacturer lead times. Furthermore, the present system is easy to install, and can be done by tradesmen with minimal training. The inclusion in certain embodiments of the present invention of flanges and stops reduces the need for careful measuring and placement of finishing materials such as drywall sheeting. [0008] The fenestration cap system allows window and door openings to be made ready to receive their corresponding accessories, while at the same time being easily made weatherproof in the absence of these accessories with the addition of a simple piece of panel or sheeting. [0009] Additional benefits are provided if accessories such as windows and doors are installed after finishing crews complete their work, which may include the application of plaster to the outside of the storefront, or the installation of drywall along the inside. In this case, The window and door systems installed within the fenestration cap do not need to be masked off by the finishing crews, and they are not in danger of being damaged by the finishing crews. [0010] In one embodiment of the present fenestration cap system, future window replacement can be achieved by simply removing the window fasteners holding the window and possibly the frame within the fenestration cap, cutting out the perimeter window sealant, and sliding the window out leaving the integrity of the structural and building substrates in a finished undisturbed state. [0011] In an exemplary embodiment, a window sill comprises a structural base having a first side and a second side, a fenestration cap attached to the structural base, a window frame mounted on the fenestration cap, and finish elements applied to the structural base and adjacent to the fenestration cap. The window frame may be removed from the fenestration cap without disturbing the finish elements. [0012] In an alternative embodiment, a fenestration cap comprises a first surface for receiving a window and a second surface attached to the first surface for attachment to a fenestration opening. The window is separably detachable from the first surface and the fenestration opening is detachable from the second surface. Furthermore, detachability of the window from the first surface is independent of detachability of the fenestration opening from the second surface. [0013] A method of installing a window in a window opening comprises providing a window opening and preparing the window opening for receiving a fenestration cap, installing a fenestration cap by placement within and attachment to the window opening in a primary step, and installing a window within the window opening by placement within and attachment to the fenestration cap in a secondary step. BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIG. 1 shows a side view of a prior art commercial window assembly; [0015] FIG. 2 shows an isometric view of a prior art window assembly; [0016] FIG. 3 shows a fenestration cap according to one embodiment of the present invention; [0017] FIG. 4 shows a fenestration cap having a built in plaster key and a channel in the interior side according to another embodiment of the present invention; [0018] FIG. 5 shows a recessed fenestration cap having a built in plaster key and a flush interior side according to one embodiment of the present invention; [0019] FIG. 6 shows a recessed fenestration cap having a channel in the interior side according to one embodiment of the present invention; [0020] FIG. 7 shows a recessed fenestration cap having a flush interior side according to one embodiment of the present invention; [0021] FIG. 8 shows a fenestration cap having a built in plaster key which is attached to a window pane using a caulked butt joint; [0022] FIG. 9 shows a recessed fenestration cap having a built in plaster key which is attached a window pane using a caulked butt joint; [0023] FIG. 10 shows a sill detail of a fenestration cap anchored to a concrete slab; [0024] FIG. 11 shows a fenestration cap according to an alternative embodiment of the present invention; and [0025] FIG. 12 shows a head detail of a fenestration cap anchored to a concrete slab. [0026] Before any embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and arrangements of components set forth in the following description, or illustrated in the drawings. The invention is capable of alternative embodiments and of being practiced or being carried out in various ways. Also, it is to be understood that the terminology used herein is for the purpose of illustrative description and should not be regarded as limiting. DETAILED DESCRIPTION OF THE INVENTION [0027] The present fenestration cap was designed to systematically coordinate and weatherproof fenestration openings before the installation of commercial or residential windows or doors. In one embodiment, the fenestration cap is a permanent fixtures in the building in which it is installed. The present cap allows for plastering and installation of interior drywall to be completed after installation of the fenestration cap itself, all of which may be completed at the leisure of a general contractor before delivery of the windows and associated frames is even taken. As such, a delay in such delivery will not unnecessarily inconvenience the contractor and delay the job; plasterers and finishing crews no longer need to wait for the delivery of windows to a job site to complete their portions of the build. [0028] Once the windows and frames do arrive, they can be installed separately by attachment to the fenestration cap with sheet metal screws or other appropriate fastening means. Furthermore, if the window panes themselves ever need to be replaced, the frames in which they are mounted can be easily detached from the fenestration cap without the need to remove the cap itself. Formerly, the unitary frame in which windows were mounted and which was attached directly to the window opening necessitated a complete tear-out of the window opening to replace the window itself. As such, windows and doors are made independent and easily replaceable building components rather than permanent parts of the building structure. [0029] FIG. 1 is a side view of a prior art commercial window assembly showing a nail on concrete slab detail. A sill can 150 is attached directly to a concrete slab 101 using a fastener 102 . A pair of caulk beads 152 are also shown at the periphery of the interface between the sill can 150 and the concrete slab 101 . A sealant 106 is used to waterproof the intersection of the fastener 102 and the sill can 150 . A shim 107 may be used to position the sill can 150 on the concrete slab 101 . Also, backer rods 108 may be used to provide a stop for the application of the caulk bead 152 . [0030] Such an arrangement is known by those skilled in the art to be prone to leakage. The sill can 150 , together with a sill can filler 155 and a sill can stop 160 forms a frame assembly which secures a window 170 . One or more top load gaskets 171 as well as a setting block 172 may also be used with this assembly to further secure, cushion and waterproof the window 170 . [0031] With the embodiment shown, finish work on the window opening may only be completed once the window 170 and frame arrives. As such, the scheduling problems discussed above are common with this prior art embodiment. Furthermore, if the window 170 and frame needed to be changed, any plastering and drywall used to finish the window opening would have to be removed at that time. [0032] FIG. 2 shows an isometric view of a prior art window assembly of a similar type to that shown in profile in FIG. 1 . Here, a vertical sill can 250 forms an assembly together with a sill can filler 255 and a sill can stop 260 to receive a window. The vertical sill can 250 is sealed to a jamb 201 using a caulk bead 25 . The vertical sill can 250 is shown at right angles to a horizontal sill can 250 which is secured to its mounting platform using a fastener 202 . [0033] FIG. 3 shows a fenestration cap 300 according to a simplified embodiment of the present invention. Alternative fenestration caps are discussed in greater detail with reference to the following figures. Here, a fenestration cap 300 is shown having a vertical flashing 312 , a drywall channel 345 and a plaster key 346 , in addition to one or more screw races 305 . The dry wall channel is defined between a mounting flange 305 and a top side 305 b. The fenestration cap 300 is an independent piece separate from any sill can or window frame assembly which may be independently installed from the window to act as a terminal point for plaster and drywall installation as well as other finish work. [0034] FIG. 4 shows one embodiment of a fenestration cap 400 according to the present invention. The cap shown in FIG. 4 is being used in a window opening framed by wood framing members 435 and faced on the exterior side by plywood sheeting 437 . FIG. 4 shows a sill can 450 supporting a window 470 . As is known to one skilled in the art, a head can of a like, though not necessarily identical design, may be used to support the top edge of the window 470 in a storefront. Similarly, the fenestration cap 400 may be used to finish the top of the window opening rather than the bottom as is shown in FIG. 4 so as to provide a platform for attachment of the head can. [0035] As discussed above, finishing crews are responsible for the installation of the plaster 436 and drywall sheeting 438 , but these elements cannot be installed until a terminal point is provided for them to be finished against. In the prior art, this terminal point was provided by the sill can or frame of the window itself. However, this caused the previously mentioned problems of delays in construction while the finishing crews waited for the window and associated sill can and frame to be delivered. [0036] In the embodiment shown in FIG. 4 , a fenestration cap 400 is provided as a single piece separate from any sill can or window frame; as such it may be independently installed and acts as a terminal point for plaster and drywall installation. To this end, the fenestration cap 400 includes a plaster key 446 on its exterior side. The front edge of the plaster key 446 is designed to act as a guide for the tradesperson applying the plaster 436 ; a trowel may easily be drawn along this edge of the plaster key 446 to quickly and neatly apply an even layer of plaster to the assembly. In one embodiment, the plaster 436 is applied to a depth of ⅞″. As mentioned above, because the fenestration cap 400 is provided as a single separate piece, plaster may be applied to the plaster key 446 prior to the installation of the window or frame, avoiding the risk of damage to these elements. [0037] Similarly, in the shown exemplary embodiment, the fenestration cap 400 includes a base 415 , a top side 417 generally parallel to the base, as well as a first support 419 and a second support 421 between the base and the top side. The key 446 has at least a portion that extends perpendicularly from a side 411 defining a flashing 412 , and along the same plane as the top side 471 . The exemplary embodiment fenestration cap also includes a drywall channel 445 provided as a guide to receive a piece of drywall sheeting 438 such as standard ⅝″ sheetrock. This channel aids an unskilled laborer in the installation of interior drywall, plaster or paneling. The built in receiving and self-aligning channel creates a level fit for the installation of interior finish materials. Accordingly, the sheeting running from a corner bead 439 to the fenestration cap 400 can be quickly and accurately installed in a level position without the time consuming process of shimming or manual adjustment of the sheeting necessary with prior art systems. [0038] In the embodiment of the present invention shown in FIG. 4 , inserting the drywall sheeting 438 into the drywall channel 445 is all that is necessary to present a finished appearance for the inside of the window assembly. It is not necessary to tape or spackle the exposed joint between the drywall sheeting 438 and the fenestration cap 400 which lies below the water dam 411 . Thus, further time and expense is saved in the installation process. The drywall channel 445 may include one or more vertical fins 417 therein, which aid in gripping the portion of drywall sheeting 438 inserted into the drywall channel 445 . These fins also provide a cushioning effect for the drywall sheeting 438 during seismic activity. [0039] In one embodiment of the present invention, the fenestration cap 400 is installed in the window opening using one or more wood screws 430 through the vertical flashing 412 and a mounting flange 415 to secure the fenestration cap 400 to the underlying structure of the window opening, namely the wood framing members 435 and/or the plywood sheeting 437 . A vertical flashing 412 may be provided allowing the fenestration cap 400 to be attached to the plywood sheeting 437 . A self healing membrane 434 may be placed between the vertical flashing 412 and the plywood sheeting 437 to provide further waterproofing for the underlying structure of the window opening. The self healing membrane 434 may be in one embodiment a continuous waterproof self healing rubberized membrane is manufactured from polypropylene. The vertical flashing 412 also provides additional waterproofing to the finished window assembly by providing a water barrier to any water which infiltrates behind the plaster 436 . The fenestration cap 400 may be attached by its interior side with one or more additional wood screws 430 to the wood framing members 435 . [0040] An expansion cavity 433 may be provided between the fenestration cap 400 and the wood framing members 435 which may contain a foam strip, 3/16″ thick in one exemplary embodiment to act as a shock absorber in the event of thermal or other expansion of the underlying members or seismic movement. [0041] It will be understood by one skilled in the art that the inventive concepts of the invention described herein are not limited to a fenestration cap for use only with the specific materials discussed above, such as plaster and drywall for instance. In lieu of plaster for example, a variety of siding materials can be used to finished the exterior of the storefront assembly shown in FIG. 4 . Likewise, plaster or paneling or a variety of other interior finishing materials may be used instead of the drywall sheeting 438 discussed above. [0042] The fenestration cap 400 shown in FIG. 4 can be made from aluminum, vinyl, steel, plastic and other appropriate materials known to those skilled in the art. In one exemplary embodiment, the fenestration cap may be manufactured as an extruded aluminum piece in twenty-four foot lengths. This exceeds the length of typical extruded pieces used in window openings such as j-molds, for which the industry standard length is ten feet. Accordingly, with this embodiment of the present invention, the need for making time consuming splices between the lengths is reduced. [0043] Furthermore, the width of the fenestration cap may be designed in various widths to fit various windows and window openings. The present invention is designed to work with window systems from multiple companies. As is known to one skilled in the art, the width of a commercial window is customarily measured with reference to its mullion width. These widths come in standard sizes including 2, 3, 4, 4.5 and 6 inches in width, among others. It is envisioned that a fenestration cap may be designed to match each of these standard window widths, although one skilled in the art will understand that a fenestration cap according to the present invention can be made to match any width window. FIG. 4 shows a window 4.5 inches in width, and the fenestration cap 400 shown therein has been designed to match a window of this width. [0044] The fenestration cap 400 may be assembled in the contractor's shop or on the job site itself into a custom system for any size window opening by cutting stock lengths of the fenestration cap 400 at forty-five degree angles (or any other set of complementary angles). These lengths can then be attached to each other using fasteners passing through the integral screw races 405 of adjacent lengths of fenestration cap 400 . For an aluminum fenestration cap, stainless steel sheet metal screws can be used as fasteners. [0045] If the fenestration cap 400 is assembled in the contractor's shop and transported to the job site, a blank made of styrofoam or other material may be inserted into the center of the fenestration cap assembly to stiffen it for transport. This blank may be secured within the assembly using double-sided tape. Furthermore, after the fenestration cap is installed in the window opening, a blank secured within the fenestration cap 400 assembly using double sided tape may be also used to weatherproof the capped window opening in lieu of the window itself. Taped plastic sheeting may also be used for this purpose. In any event, fenestration cap assembly provides and easy base from which to tape or otherwise weatherproof a window opening prior to the installation of the window assembly. [0046] The sill can 450 shown in FIG. 4 is an industry standard sill can having a number of interlocking parts. A sill can filler 455 and a sill can stop 460 snap into place within the sill can 450 to lock a window 470 in position. The window 470 is firmly held by a pair of top load gaskets 471 , which may be neoprene gaskets. The sill can 450 is shown engaging window 470 through the pair of top load gaskets 471 and a setting block 472 . These top load gaskets 471 are held partially snapped into receiving tracks in the sill can filler 455 and the sill can stop 460 . These gaskets are also known to those skilled in the art as self-locking gaskets, given that the weight of the window 470 bears on these gaskets to create a seal between the gaskets 471 and the window 470 . [0047] In one embodiment of the present invention, at some point after the fenestration cap 400 itself has been installed in the window opening, the sill can 450 , having a window 470 therein, may be lifted onto the length of fenestration cap 400 shown in FIG. 4 . The sill can 450 can then be attached to the fenestration cap 400 using one or more sheet metal screws 451 . In an exemplary embodiment, the window 470 may be surrounded on multiple sides by either a sill can or frame which abuts a length of fenestration cap to which the sill can or frame may be attached. [0048] If the fenestration cap 400 is used with a frame such as the sill can 450 and related components shown in FIG. 4 , the point of attachment of the sill can 450 to the fenestration cap 400 must be made waterproof. Accordingly, before the sill can 450 is attached to the fenestration cap 400 using the sheet metal screws 451 , a caulk bead 452 is laid down therebetween to waterproof the joint. In one embodiment, the caulk used for the caulk bead 452 is structural grade silicone. At the portion of the joint nearest the exterior side of the storefront, a gap of set height 453 is provided which is designed to match the warranty requirements of the standard window sealants used in the industry. In the embodiment shown in FIG. 4 , this gap has a height of ⅜ inches. [0049] A water dam 411 may be provided at the interior side of the caulk bead 452 as a further moisture barrier in the event that water is able to infiltrate through to the interior side of the caulk bead 452 . The water dam 411 also provides a stop allowing for easy installation of the window and sill can 450 . Once the fenestration cap 400 is in place in a window opening, an unskilled laborer would easily be able to install the sill can 450 and related components to provide a finished storefront by lifting the window assembly up and into the opening within the fenestration cap assembly, placing the interior edge of the sill can 450 firmly against the water dam 411 . As such, no measuring is required for the installation of the window assembly itself when the fenestration cap 400 has been used to frame the window opening ahead of time. [0050] Furthermore, even if despite all the precautions built into the design of the fenestration cap 400 , water is able fully infiltrate the joint in the area of the caulk bead 452 and pass over the water dam 411 , the fenestration cap 400 fully spans the width of the window opening in which it is placed so that any water which does manage to flow over the fenestration cap 400 is directed over, rather than into, the wall on which the fenestration cap 400 rests. [0051] The fenestration cap 400 may be provided with a thermal break 410 to reduce the transfer of heat through the fenestration cap 400 to help meet energy efficiency building requirements such as California's Title 24 requirements. Accordingly, an insulation material is formed in a cavity of the fenestration cap 400 . This insulation material has sufficient strength such that after it is formed in the cavity, a portion of the fenestration cap 400 can be removed in the vicinity of the insulation such that the fenestration cap 400 becomes two thermally separate pieces joined only by the insulation. This helps to substantially thermally isolate the interior from the exterior of the finished storefront by preventing heat transmission through the fenestration cap 800 . [0052] The fenestration cap 400 has the additional advantage that over prior art systems in that it can span doorway openings in a storefront and need not be trimmed to the jamb of a doorway. With the addition of a separate threshold unit, the section fenestration cap 400 , spanning the bottom of a doorway, presents a finished appearance. Accordingly, a single length or series of lengths of the fenestration cap 400 can be made to span the base of an entire storefront serving as both a sill of a window and a door threshold. [0053] FIG. 5 shows a fenestration cap 500 for use with a frameless window system. While the fenestration cap 500 shares many of the same elements as the cap shown in FIG. 4 , the cap 500 is shown engaging the window 570 through a top load gasket 571 and a setting block 572 , rather than incorporating a separate sill can, as is the case in the cap of FIG. 4 . In one embodiment, the top load gasket 571 may be provided by a silicone glazed bead. [0054] As in the previous embodiment, the fenestration cap 500 is attached to the wood framing members 535 and plywood sheeting 537 using a series of wood screws 530 . The fenestration cap 500 is provided with a drywall channel 545 and plaster key 546 designed to receive drywall sheeting 538 and plaster 536 . A spacer 509 may be provided to support the drywall sheeting 538 in the area of a corner bead 539 . [0055] FIG. 6 shows a recessed fenestration cap having a channel in the interior side according to one embodiment of the present invention. In FIG. 6 , the top and front edges of the plaster key 647 and the top edge of the lip 649 are designed to act as guides to the tradesperson applying the plaster 436 to the assembly; a trowel may easily be drawn along these edges to quickly and neatly apply an even layer of plaster in the space between the plaster key 647 and the lip 649 . The surface created by plastering between the plaster key 647 and the lip 649 will not be completely horizontal however; the fenestration cap 600 is designed so that when level, the top edge of the plaster key 647 lies on a 2% decline from the horizontal with respect to the top edge of the lip 649 . This encourages water to shed off of the architectural reveal created by this plastered surface toward the exterior of the storefront. Furthermore, the fenestration cap 600 is provided with a serrated texture 648 to better anchor the plaster to the fenestration cap 600 . Also, the plaster key 647 is provided with holes drilled therein (not shown) so that the plaster applied below the plaster key 647 and the plaster applied to the side of the plaster key 647 is able to form one contiguous and stable mass, leading to increased durability. FIG. 6 also depicts one of two sheet metal screws 651 entering a cavity. In some embodiments of the present invention, one or more sheet metal screws is used to affix the sill can 650 to the fenestration cap. If water leaks under the sill can and above the fenestration cap, it could leak down through the sheet metal screw 651 hole. However, if the screw hole goes through a portion of the fenestration cap into the cavity, the cavity will serve as a reservoir to hold the water, preventing water from entering into the interior, and trapping water in the cavity until it evaporates. [0056] FIG. 7 shows a recessed fenestration cap 700 having a flush interior side according to one embodiment of the present invention. The fenestration cap 700 is attached to the wood framing members 735 and plywood sheeting 737 using a series of wood screws 730 . The fenestration cap 700 is attached to an assembly comprising a sill can 750 , sill can filler and 755 sill can stop 760 using sheet metal screws 751 and a caulk bead 752 . This assembly is shown engaging the window 770 through a top load gasket 771 and a setting block 772 . In contrast to FIGS. 4 , 5 and 6 however, the fenestration cap 700 is not provided with a drywall channel designed to receive drywall sheeting. Instead, the fenestration cap 700 is designed as a relatively flush assembly which may be placed over a corner bead 739 applied to finish the joint between the drywall sheeting 738 and the wood framing members 735 . [0057] FIG. 8 shows a fenestration cap 800 attached to a window 870 using a butt joint 895 . The arrangement shown in FIG. 8 is a counterpart to the fenestration cap 500 of FIG. 5 for use with a frameless window system. While the fenestration cap 500 supports the sill of a window in a frameless window system, the fenestration cap 800 may be applied to the jamb of such a window opening to support the sides of the window 870 . [0058] As in the previous figures, the fenestration cap 800 is provided with a plaster key 846 to facilitate the easy application of the plaster 836 , and a drywall channel 845 to facilitate the installation of the drywall sheeting 838 . The fenestration cap 800 is secured to the wood framing members 835 and the plywood sheeting 837 using one or more wood screws 830 . Furthermore, the fenestration cap 800 is provided with a thermal break 810 , which may be supplemented with the creation of a saw cut 896 in the fenestration cap 800 to substantially thermally isolate the interior from the exterior of the finished storefront, preventing heat transmission through the fenestration cap 800 . [0059] FIG. 9 shows a recessed fenestration cap 900 having a built in plaster key 947 which is attached a window pane using a caulked butt joint. The fenestration cap 900 is similar to the fenestration cap 800 of FIG. 8 in that it may be applied to the jamb of a window opening in a frameless window system to support the window therein. However, it differs in that it features a set back similar to that used in the fenestration cap 600 of FIG. 6 , wherein the top and front edges of the plaster key 947 and the top edge of the lip 949 are designed to act as guides to the tradesperson applying the plaster 936 to the assembly. [0060] As in FIG. 6 , the surface created by plastering between the plaster key 947 and the lip 949 will not be completely horizontal. The fenestration cap 900 is designed so that when level, the top edge of the plaster key 947 lies on a slight decline from the horizontal with respect to the top edge of the lip 949 . This encourages water to shed off of this architectural reveal toward the exterior of the storefront. The fenestration cap 900 is also provided with a serrated texture 948 to better anchor the plaster 936 to the fenestration cap 900 . [0061] FIG. 10 is an alternative embodiment of the present invention wherein a sill detail a fenestration cap 1000 shown is anchored to a concrete slab 1001 using a fastener 1002 . The concrete slab 1001 may be part of an overhanging eve. In place on the fenestration cap 1000 are a sill can 1050 , a sill can filler 1055 , and a sill can stop 1060 which, though the top load gaskets 1071 secure the window 1070 . [0062] The gap between the sill can 1050 and the fenestration cap 1000 is sealed with a caulk bead 1052 . As in other embodiments, a gap of set height 1053 is provided as part of the caulk bead 1052 to match industry standard warranty requirements. A water dam 1011 is provided at the interior side of the caulk bead 1052 as a moisture barrier in the event that water is able to infiltrate through to the interior side of the caulk bead 1052 , and to provide a stop for easy installation of the sill can 1050 . [0063] The embodiment of FIG. 10 additionally shows that the fenestration cap 1000 is slightly wedge shaped; having a narrower edge on the exterior side. As such, water will be more inclined to run to the outside of the window 1070 both if it infiltrates between the fenestration cap 1000 and the sill can 1050 , and if it gets into the sill can 1050 itself. In prior art models, if water infiltrated the sill can 1050 for example by flowing between it and the sill can filler 1055 , it would pool within the sill can. Weep holes were sometimes added in the sill can 1050 to aid in drainage, but cannot prevent pooling in the event of an unfavorable alignment of the sill can 1050 itself. [0064] FIG. 11 shows a fenestration cap 1100 according to an alternative frameless embodiment of the present invention wherein the window 1170 is mounted directly on the fenestration cap 1100 using a caulk joint 1195 . As is the previous figures, the fenestration cap 1100 is provided with a plaster key 1146 to facilitate the easy application of the plaster 1136 , and a drywall channel 1145 to facilitate the installation of the drywall sheeting 1138 . The fenestration cap 1100 is secured to the wood framing members 1135 and the plywood sheeting 1137 using one or more wood screws 1130 . [0065] FIG. 12 shows a head detail of a fenestration cap 1200 anchored to an overhang 1201 . The fenestration cap 1200 is of a type which can be attached on a continuous eve or overhang 1201 without need of a flange. In the embodiment shown, the fenestration cap 1200 is attached using the fastener 1202 . On the fenestration cap 1200 is mounted an assembly comprising a sill can 1250 , sill can filler 1255 and sill can stop 1260 . This assembly may be mounted using sheet metal screws 1251 , and seamed using a caulk bead 1252 . A window 1270 may be mounted in this assembly using top load gaskets 1271 . The fenestration cap 1200 may be installed before the sill can 1250 to allow for the completion of work involving the plaster 1236 and drywall sheeting 1238 , the latter of which fits easily into the drywall channel 1245 . [0066] The preceding description has been presented with reference to some embodiments of the invention. Workers skilled in the art and technology to which this invention pertains will appreciate that alterations and changes in the described structure may be practiced without meaningful departing from the principal, spirit and scope of this invention. Accordingly, the foregoing description should not be read as pertaining only to the precise structures and methods described and illustrated in the accompanying drawings, but rather should be read consistent with and as support to the following claims which are to have their fullest and fair scope. For instance, FIG. 10 depicts a fenestration cap that is slightly wedge shaped, and thus parts of the fenestration cap may not be perfectly parallel or perfectly perpendicular in reference to one another. Therefore, as used herein, parallel and perpendicular could mean substantially parallel and substantially perpendicular.
In an exemplary embodiment, a window sill comprises a structural base having a first side and a second side, a fenestration cap attached to the structural base, a window frame mounted on the fenestration cap and finish elements applied to the structural base and adjacent to the fenestration cap. The window frame may be removed from the fenestration cap without disturbing the finish elements. Alternatively, a method of installing a window in a window opening comprises providing a window opening and preparing the window opening for receiving a fenestration cap, installing a fenestration cap by placement within and attachment to the window opening in a primary step, and installing a window within the window opening by placement within and attachment to the fenestration cap in a secondary step.
4
BACKGROUND OF THE INVENTION This invention provides an earth anchor that has been developed primarily in conjunction with the stabilizing and re-positioning of basement walls that are in danger of being displaced by outside earth pressure. In freezing conditions, soil moisture solidifies, and expands with tremendous force. In warmer weather, the thawing ground relaxes the pressure, and sometimes withdraws as it contracts. The resulting gap can easily become at least partially filled, causing a renewed pressure layer against the already displaced basement wall when the ground freezes again. Resulting cracks in the wall invite the invasion of ground water into the basement, which is another factor that has focused attention on the problem of wall instability. Attempts have been made to stabilize basement walls against further displacement, and even return them to a vertical plane. One expedient (shown in the Johnson, et al, U.S. Pat. No. 4,189,891) involves digging an excavation at some distance out from the wall, and drilling a hole through the wall opposite the excavation. A rod is then driven through the earth from this hole, which is secured to some object deposited in the excavation. The excavation is then filled in, and the rod can function as a long bolt terminating inside the wall at a nut and a bearing plate. A much simpler system is described in the Harmon U.S. Pat. No. 4,970,835, issued on Nov. 20, 1990. This system requires no excavation, and replaces the buried terminal with an expandable earth anchor inserted in the hole in the basement wall, and driven out into the earth with the bolt rod. Pulling on the rod by tightening the nut against a bearing plate inside the basement wall opens the anchor device ultimately to a fully expanded position. In both of these systems, the bearing nuts can be periodically tightened to re-position the wall. An anchor device of this type can be expected to be inserted in a variety of different types of soil, ranging from solid clay, to pure sand. As the anchor is forced through the soil on installation, it will tend to produce a well-defined hole in a solid clay-type soil. With sand, however, the hole is less well-defined. It tends to fall back around the bolt rod as the anchor device is forced into position. The return pull on the rod by tightening the nut inside the basement wall causes the anchor device to readily dig into the loose soil, but can conceivably pull it right back through the hole that it has formed in a more solid soil. A need has been found for assuming an initial expansion of the anchor device sufficient to dig it into the walls defining the hole, regardless of whether or not the earth has tended to fill in behind the anchor as it was driven into position. The structure of these anchors centers in a threaded central portion to which arms are pivotally connected, and which trail from the pivot connection back along the bolt rod as the anchor is driven. On opposite movement of the bolt rod, however, they are opened by earth pressure into a position approaching 90° from the axis of the rod, where a stop limits further rotation. The problem here is to provide a system for initiating the expansion of the anchor that can be controlled by the bolt rod from the inside of the basement wall. In the looser types of soil, it also may be necessary to increase the anchoring effect by the use of multiple anchor devices on the same bolt rod. This simply means increasing the number of the pivoted arms that become subject to earth pressure. These arms are analogous to the "flukes" common in marine anchors. SUMMARY OF THE INVENTION An expandable earth anchor is driven laterally into the ground on the end of a bolt rod. Rotation of the rod initiates expansion of the anchor, which then is fully expanded by pulling back on the bolt rod. The initial expansion is obtained by the engagement of a cam member carried by the bolt rod, acting against arms pivoted to a member in threaded engagement with the bolt rod. A plurality of the anchor devices, or sets of these arms, can be mounted on a single bolt rod, with the initiation of expansion being provided in one modification by the rotation of the rod to independently open the sets of arms; and in another modification of the invention, the initial expansion of one set of arms itself operates to initiate the expansion of another set of arms pivoted at a position axially spaced along the bolt rod from the first set. DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional elevation showing a typical installation of an anchor device on a long bolt rod for the purpose of restoring a basement wall to a vertical plane. FIG. 2 is a side elevation on a scale enlarged over that of FIG. 1, showing the anchor device in the initial fully closed position. FIG. 3 illustrates the anchor device of FIG. 2 in the partially expanded condition. FIG. 4 illustrates the same device as shown in FIGS. 2 and 3, and in the fully expanded condition. FIG. 5 is a top view of the anchor device shown in FIGS. 2 and 3. FIG. 6 is a sectional elevation on a plane taken through the pivot bolt securing the expandable arms. FIG. 6 is taken on the plane VI--VI of FIG. 5. FIG. 7 is a view of a modified form of the invention involving a succession of independent anchor devices installed on a common bolt rod. FIG. 8 is a plan view of an anchor device of the type shown FIG. 7, in the partially expanded condition, and on an enlarged scale over that of FIG. 7. FIG. 9 is a fragmentary sectional view at the basement wall, showing the installation of the bearing plate and the associated nut used for applying the force to the wall, and showing a seal at the hole drilled through the wall for the installation of the anchor. FIG. 10 is a perspective view of a further modification of the invention, showing overlapped sets of pivoted arms, shown in the fully closed position. FIG. 11 is a perspective view of the partially opened anchor illustrated in FIG. 10. FIG. 12 is a perspective view showing the fully opened condition of the anchor device of FIGS. 10 and 11. FIG. 13 is a section on the plane XIII--XIII of FIG. 10. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIG. 1, the cement block basement wall 20 is shown bowed inward to a precarious degree, as a result of the previous freezing and expansion of the earth 21, followed by the thawing shrinkage producing a gap 22 between the earth and the outside of the wall. This gap has become partially filled, and presumably will eventually accumulate more loose soil to the point where the gap will be substantially closed. A successive period of freezing will thus produce the expansion of the soil 21, and apply renewed pressure on the already deflected wall 20. The house structure indicated generally at 23 is thus under considerable risk, as the deflected wall is no longer capable of carrying the weight of the house down to the footing 24. The bowed condition of the wall 20 also invites an assortment of cracks through which moisture can pass from the exterior of the wall into the basement to accumulate on the basement floor 25, where it may well cause considerable damage and inconvenience. The wall condition shown in FIG. 1 can be corrected by a system which includes the threaded bolt rod 26 and the earth anchor 27. A hole shown at 28 of approximately 4 inches in diameter is first drilled through the wall 20. The bolt rod 26, or a section of it carrying the anchor device 27, is then inserted from the interior of the basement through the hole 28. A coupling 29 then is connected to an air hammer, and the assembly shown in FIG. 1 driven from left to right out into the illustrated position in the earth. During this movement, the anchor device 27 remains in the un-expanded condition. Since the device may have to find its way through the root growth of trees as shown at 30, the anchor device is provided with a chisel point 31 to facilitate this movement. Referring to FIGS. 2-5, the anchor device 27 includes a pair of opposite arms 32 and 33 pivotally connected by the bolt 34 to the threaded tubular member 35. The trailing ends of the arms 32 and 33 are flared as shown at 36 and 37 to receive the washers 38 entrapped between the nuts 39 and 40. After the assembly shown in FIG. 1 has been driven into the illustrated position, the bolt rod 26 is rotated. The threaded interengagement between the rod 26 and the internally threaded tubular member 35 causes the nuts 39 and 40 to carry the washers 38 from the FIG. 2 to the FIG. 3 position. The nuts 39 and 40 had initially been set against each other sufficiently tight so that rotation of the rod will rotate these components along with it. It is preferable that the nuts should be set against each other to at least 100 foot pounds of torque. The movement from the FIG. 2 to the FIG. 3 position causes the washers 38 to function as cams acting against the central concave underside of the arms 32 and 33, inducing the degree of expansion illustrated in FIG. 3, where further movement of the rod into the tubular member 35 is halted by the engagement of the nut 39 with the outer end of the tubular member. Initially, the threaded rod 26 is engaged with only an inch or so of the outer extremity of the tubular member 35. The central concave portion (from the inside) shown at 41 of the arms is preferably of approximately the same curvature is that of the periphery of the washers 38. This tends to provide the best bearing surface, and also increases the tendency for the pivoted arms to remain in alignment as the assembly is driven into position. Referring to particularly to FIGS. 5 and 6, the arms 32 and 33 are reinforced by the channel-shaped pivot members 42 and 43, in which the side flanges are extended as shown at 44-47 to receive the pivot bolt 34. These side flanges are welded to the arms 32 and 33, and the bolt 34 is also preferably welded in position at its opposite ends, together with the retainer washer 48. Once the expansion of the anchor has been initiated to the point shown in FIG. 3, a pull on the rod 26 exerted by tightening the nut 49 against the surface plate 50, possibly through the intervening washer 51, will cause the entire anchor assembly to move toward the basement wall to ultimately achieve the fully expanded condition shown in FIG. 4. At this point, the edges 52 will engage the outer surface of the threaded tubular member 35 to form stops limiting any further rotation of the arms. The pressure of the nut 49 against the plate 50 becomes a resilient force, due to the inwardly concave configuration of this member. It is preferable that the plate 50 be of a material similar in nature to spring steel, and it has been found very effective to use agricultural cultivator discs (without the sharpened edges) for this purpose. If desired, the initial hole 28 in the block wall 20 may be filled with mortar or sealant, to inhibit the outflow of water through this opening. To permit the nut 49 to be tightened, accompanied by further movement of the threaded rod to the left, it is necessary that there be no effective bond between the rod and any surrounding mortar. To prevent this, a cardboard (or other inexpensive material) tube 52 may be inserted around the rod prior to packing in the sealant material, or mortar, shown at 53. During the installation of this assembly, it may be convenient to break the rod 26 into sections, as shown at 26a and 26b in FIG. 9, interconnected by a standard coupling 54. The proportions of the anchor components can vary over a considerable range, depending on the requirements of particular installations. For general use, a bolt rod 3/4" in diameter with standard coarse threading is adequate. The pivot pins should be about 3/8" to 1/2" in diameter, and the pivot reinforcements for the arms of material slightly thicker than the outer extremities of the arms, which can be about 1/8". All of these components are of steel. The length of the arms should be in the neighborhood of one foot as a maximum for good holding capability. FIGS. 7 and 8 show a modified form of the invention, in which a single threaded rod 55 is capable of independently actuating the initial expansion of separate pairs of pivoted arms, as shown at 56-57 and 58-59. The plates 58 and 59 are pivotally connected to the internally threaded block 60 on pins 61 and 62 which are laterally displaced from the axis of the rod 55 sufficiently that they do not intersect the rod. The rod is thus left free to continue on through the outer anchor, and actuate the inner anchor (including the arms 56 and 57) as previously described. The limitation of the threaded engagement of the rod 55 with respect to the anchors can be provided either by engagement of the nut-washer assemblies 63 or 64 with the end of the block 60 or that of the threaded tubular member 65. In either case, this engagement will prevent further threaded entrance of the rod 55 into the anchor system. The extent of this axial movement will have been sufficient to open both anchors. Referring to FIGS. 10-13, a modified form of the invention is illustrated in which overlapping pairs of pivoted arms 66-67 and 68-69 are used. The outer arms are mounted on pivot pins 70 and 71 traversing the chisel block 72 secured to the end of the internally threaded member 73. The inner pair of arms 66-67 are carried by a pivot pin traversing the tubular member 73 as shown in FIG. 3. The outer set of arms closes down over the inner set of arms 68 and 69. The initial expansion of these arms is initiated as before, by rotation of the rod 74 with respect to the threaded tubular member 73, and the corresponding advance of the nut-washer assembly 75 between the arms 68 and 69. The expansion of those arms induces the expansion of the arms 66 and 67.
An expandable earth anchor is provided with pivoted arms that remain contracted about a bolt rod as the rod, together with the anchor, is driven into the earth. Rotation of the rod with respect to the anchor induces an initial degree of expansion by rotation of the anchor arms about their pivot connection, followed by full expansion of the arms induced by movement of the bolt rod as a result of rotation of a bearing nut against a plate. Arrangements are provided for the expansion of a plurality of anchor devices on a single bolt rod, rendering the system suitable for various types of soils.
4
FIELD OF THE INVENTION The invention relates to mailing machines and more particularly to an improvement in a mailing machine for combination with an automatic mailpiece feeding device. BACKGROUND OF THE INVENTION Mailing machines generally comprise a postage meter for printing an indicia on a piece of mail or on a tape and a feed base for transporting mailpieces or tapes for printing by the postage meter. In many cases for reasons of cost and typically because of lighter volume of mail, automatic mailpiece feeders have not been used in connection with small mailing machines. One type of mailing machine produced by Pitney Bowes, which is described, for example, in Ser. No. 180,163 now U.S. Pat. No. 5,392,704, for Mailing Machine, Ser. No. 180,161, now U.S. Pat. No. 5,392,703, and Ser. No. 180,168 now U.S. Pat. No. 5,390,594, for Tape Feeding, Cutting and Ejecting Apparatus for a Mailing Machine all filed Jan. 11, 1994, and assigned to the assignee of the instant application, was originally designed for the hand feeding of mail by an operator. If it is desired that an automatic mail-feeding apparatus be used in combination with this mailing machine, it was found necessary to be able to convert such mailing machines for automatic mail feeding. The length of the deck and the lack of positive feeding make the interface of these mailing machines to the feeder less than straightforward. SUMMARY OF THE INVENTION It is therefore an object of the invention to provide an improved mailing machine having a modifiable deck for accommodating a mailpiece feeder. It has been found that the mailing machine can be modified by providing a plate which may be incorporated into the deck, the plate carrying a positive drive mechanism for the feeding of mailpieces at the desired speed. For best results, it was found that the drive mechanism comprises a positive drive roller and pulley which are aligned to use the drive mechanism of the mailing machine for belt driven power. Thus the above and other objects are attained in a novel mailing machine of the type having a deck and a feeding roller for transporting mailpieces along the deck, the improvement comprising the deck having a hole therein and a plate for filling said hole, said plate having a driven wheel mounted thereon, the wheel extending upwardly through the plate for engaging and transporting a mailpiece prior to the engagement by the feeding roller, and belt drive means connecting the feeding roller and the driven wheel for providing driving power to the driven wheel for transport of the mailpieces. In a further aspect there is provided a method for interfacing a mailing machine to an automatic feeder, the mailing machine having a deck and drive means for a feeding roller mounted thereon for transport of mailpieces, the method comprising the steps of providing a hole in the deck of the mailing machine, providing a plate having dimensions for fitting in the hole, mounting on said plate a driven wheel, a portion of said driven wheel extending upwardly through a slot in the plate for engaging with a mailpiece and being aligned so as to receive driving power from the drive for the feeding roller, placing and retaining the plate in the hole in the deck, and connecting the driven wheel to the feeding roller drive means by belt drive means for transporting the mailpieces. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a general perspective view of a mailing machine embodying the present invention. FIG. 2 is a frontal perspective view of the mailing machine shown in FIG. 1 with some covers removed for ease of viewing. FIG. 3 is a frontal perspective view of the base of the mailing machine shown in FIG. 1 having a plate in accordance with the invention. FIG. 4 is a bottom perspective view of the plate in accordance with the invention shown installed in the base. DESCRIPTION OF THE PREFERRED EMBODIMENT In FIGS. 1 and 2, there is shown generally at 10 a mailing machine as described generally in applications Ser. No. 180,163 for Mailing Machine, Ser. No. 180,161 and Ser. No. 180,168 for Tape Feeding, Cutting and Ejecting Apparatus for a Mailing Machine all filed Jan. 11, 1994, each assigned to the assignee of the present invention and specifically incorporated herein by reference. The mailing machine includes a base shown generally at 12, a postage meter generally designated at 14, and a tape feeding, cutting, and ejection apparatus shown generally at 16 (FIG. 2). The mailing machine preferably includes a housing having a pivoted cover 15 connected by hinges 17 which can be raised to provide access. The base 12 comprises a feed deck 18 which extends through the mailing machine 10 for support of mailpieces. Feeding rollers 20 project upward through the deck for engaging the underside of the mailpieces while belt 22 which extends around drive pulley 26 and idler pulley 28 serves to engage the upper surface for transporting the mailpiece for feeding to the postage meter. The outer surface of belt 22 passing around idler pulley 28 is mounted on elongate housing 30 which is pivoted about shaft 32 which drives the pulley 26. Housing 30 is spring loaded downwardly by spring 34 on bracket 36 formed on ink cartridge housing 38 which holds a removable ink cartridge 40. Belt 22 engages an roller 42 mounted beneath the feed deck 18 which acts as a pressure backup to ensure proper feeding of mailpieces between the belt 22 and roller 42. Postage meter 14 has a plurality of setting levers 44 for setting postage in accordance with numerals on scales 48. The postage meter includes a print drum which carries a printing die for printing the indicia on a mailpiece. As seen in FIG. 2, the base further includes a plurality of eject rollers 66 and cooperating spring loaded pressure rollers 67 in the postage meter for conveying the mailpiece to the end of the feed deck. The drive mechanism is implemented suitably with a DC reversing motor (not seen in these figures) as described in connection with applications Ser. No. 180,161 and Ser. No. 180,168 for Tape Feeding, Cutting and Ejecting Apparatus for a Mailing Machine, previously incorporated by reference herein. The complete operation is described in these referenced applications and will not be further described herein except as required for the discussion of the present invention. It has been found that in some applications, an automatic mailpiece feeder is required so as to be able to automatically feed mailpieces to the mailing machine, but the machine illustrated in the prior art does not provide a way to easily accommodate the mail feeder. In FIG. 3, a modified deck in accordance with the invention is shown generally at 200. In order to modify the mailing machine to accommodate an automatic feeder, the end 70 of the prior art mailing machine (FIG. 1) is trimmed and an L-shaped cap (not shown) is placed to cover the trimmed end. Further in accordance with the invention, a substantially square or rectangular hole is provided in the deck and a molded plate 202 of substantially the same dimensions is received into the hole. As best seen in FIG. 4, a tab 204 or the like is suitably molded as a part of the plate and when the plate is inserted into the hole, the tab 204 will deform and then spring back to hold the plate 202 in place. As shown in FIGS. 3 and 4, an additional roller or wheel 206 is mounted on shaft 208 which is in turn journalled on the plate 202, suitably as shown at molded projections 210 and 212, so that a portion of the circumference of wheel 206 extends through the plate at slot 214. On the other end of shaft 208 is mounted a pulley 216 connected by belt 218 to pulley 220 suitably mounted on the shaft of roller 42 of FIG. 2, which is driven by a motor not seen in the Figs. The wheel 206 thus is driven by the power provided to the existing feeding roller 42 of the mailing machine. For best results, a spring-loaded straddler (not shown) has arms projecting from above the deck on each side of the wheel 206 in order to provide a positive contact on the wheel 206 by pushing on the top of the mailpiece as it passes over the wheel 206. In operation, with the mailing machine juxtaposed to an automatic feeder, a mailpiece which is received on the deck is positively engaged by the wheel 206 and transported to the nip of the feeder wheel using the power from the same drive means as drives the feeder wheel 42. When the deck is trimmed as shown in FIG. 3, the length of path is reduced to allow mailpieces of the required minimum length to be fed.
An improved mailing machine has a modifiable deck for accommodating a mailpiece feeder. The mailing machine is modified by providing a plate which may be incorporated into the deck. The plate carries a positive drive mechanism for the feeding of mailpieces at the desired speed which comprises a positive drive roller and pulley which are aligned to use the drive mechanism of the mailing machine for belt driven power.
1
BACKGROUND [0001] The present invention relates to a gas permeable cloth covering an opening in the housing of electronic equipment. The cloth covering the opening is stabilized by a supporting structure. [0002] Cloths of the above kind are at present used in many different contexts. In this application the main use of the cloth is to keep out harmful substances and hinder the harmful substances from harming electronic or mechanical devices placed in connection to an opening of a housing of electronic equipment. The harmful substances may be different fluids, such as water, moisture, dust, dirt, particles, etc. Thus, the cloth should be impermeable to fluids, moisture, dust, dirt, particles, etc. At the same time the cloth should be permeable to gases, especially air. The devices to be protected by the cloth may be microphones and loudspeakers and, thus, the cloth should not hinder sound from going through. Furthermore, the cloth may be used to protect battery air inlets or inlets for other electronic units such as transmitters and receivers. One aim is to be able to use electronic equipment in harsh environments, such as at sea, outdoors, at building sites, in heavy industry, etc. [0003] The term electronic equipment includes portable radio communication equipment, such as mobile telephones, pagers, communicators, i.e., electronic organizers, smartphones or the like. [0004] It is not possible to use the cloths of the prior art to cover large openings. The large openings may be for large loudspeakers, ventilation means, computers and/or other electronic devices. When the cloth is stretched over a large opening the stress on the cloth is substantial. The cloth normally used is much too yielding, which means that it will not stand even small pressures or any kind of mechanical influence without being damaged. If the cloth is damaged it will not be able to fulfil its purpose. Furthermore, large cloths will be harder to fasten at the housing or frame. A larger cloth is heavier and the pressure or mechanical influence on the periphery, where the cloth is attached to the frame, will threaten to damage the periphery of the cloth, tearing it apart and making it lose its grip with the opening. The only possible solution according to the prior art is to have very thick and thus heavy cloths. In addition to the problems mentioned above such cloths are expensive. The cloths of the prior art used to cover small openings are also difficult to fasten at the edge of the opening. SUMMARY [0005] One object of the present invention is to provide good support for cloths covering an opening of electronic equipment. [0006] A further object is to simplify the mounting of the cloth in the opening of the housing or frame of the electronic equipment. [0007] According to the invention, a stabilizing structure is formed, allowing the cloth to cover large openings without being harmed or being too yielding. The stabilizing structure may have many different designs such as a net, longitudinal or transversal bars, which may he crossed and/or overlapping, forming plates, rings, triangles, rectangles or any other form. The formations may be flat or may form a framework having one or more points of support bearing against the frame. The stabilizing structure may be formed by thickened parts of the cloth. [0008] Furthermore, the cloth may be given a support by stretching the cloth and by fixing it in a stretched condition at the edges of the opening and/or at the points of support. If the cloth is made of an elastic material the stretched area will remain for a longer period of time compared to if the cloth is of a non-elastic material. Furthermore it will be easier to stretch an elastic cloth when mounting it over the opening. The support to the cloth may be provided by a combination of one or more of the above stated supports or stabilizing structures. [0009] The stabilizing structure may be placed on either side of the cloth or may be integrated in the cloth. The stabilizing structure may be made of plastics, metal, wood or any other suitable material. Furthermore the cloth is furnished with means of attachment at least in one location on the surface or at the edge of the cloth. Thus, according to the invention, large cloths may be mounted over large openings, whereby the cloth is used to atop fluids such as water, moisture, dirt, dust and other particles but to let air and thus sound through. Furthermore, the cloth will withstand pressures and mechanical influences. All in harsh environments. [0010] According to the invention, the cloth may be rather thin and have the same thickness throughout the part covering the opening. The cloth according to the invention is easy to mount as the stabilizing structure may be furnished with means of attachment, fixing the cloth in a proper way over the opening. The means of attachment may comprise snaps, barbs, screw joints, threads, seams, clamps, etc. [0011] The openings may have many different forms, such as circular, oval, rectangular, polygonal, etc. [0012] It should be emphasized that the term “comprises/comprising” when used in this description is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. BRIEF DESCRIPTION OF THE DRAWINGS [0013] The invention will be described in greater detail below with reference to the accompanying figures. In the figures, [0014] [0014]FIG. 1 is a schematic perspective view illustrating a stabilizing structure placed under a cloth; [0015] [0015]FIG. 2 illustrates a section of a part of the cloth and a part of a point of support; [0016] [0016]FIG. 3 illustrates a section through a part of the cloth having a means of attachment fixed to a housing of electronic equipment; [0017] [0017]FIG. 4 illustrates a section through a part of a cloth having an alternative means of attachment fixed to a housing of electronic equipment; and [0018] [0018]FIG. 5 illustrates a section through a part of a cloth having an integrated stabilizing structure. DETAILED DESCRIPTION [0019] In FIG. 1 one embodiment of the present invention is shown. A housing or frame 1 of electronic equipment such as a mobile telephone is shown. The housing 1 has an opening 2 for communication with either a microphone or a loudspeaker (not shown). The opening 2 is covered by a cloth 6 , which is supported by a stabilizing structure 4 . Stabilizing structure 4 has at least one means of attachment 3 . The means of attachment 3 fix the stabilizing structure 4 to the housing 1 at the edge 5 of the opening 2 . A person skilled in the art realizes that any number of means of attachment may be used in the shown embodiment the stabilizing structure 4 has crossed bars 7 forming a net. [0020] The stabilizing structure 4 may be placed on either side of the cloth 6 . When the stabilizing structure 4 is placed on top of the cloth 6 , the cloth 6 is normally fixed to the stabilizing structure 4 by means of glue, welding, etc. A stabilizing structure 4 on top of the cloth 6 will function as an impact protection. [0021] A structure forming a point of support 9 is shown in FIG. 2. On top of the point of support 9 a plate 10 receives the cloth 6 . The plate 10 of the point of support 9 may also receive a bar 7 of the stabilizing structure 4 . Thus, the point of support 9 will take up a part of the load of the cloth 6 and/or stabilizing structure 4 . Normally a number of points of support 9 are arranged. The plate 10 will help to distribute the load on a large part of the cloth 6 , reducing the risk of mechanical influence on the cloth 6 . The point of support 9 is integrated with or supported in the housing 1 . [0022] The cloth 6 is held at the edge 5 of the opening 2 by a means of attachment 3 . In the embodiment of FIG. 3 the means of attachment 3 comprise a male part 11 and a female part 12 . The male part 11 is fixed to the cloth 6 , by clamping the edge 14 of the cloth 6 . The male part 11 clamping the cloth 6 is received in the female part 12 . The male part 11 is assembled in a mainly horizontal direction in the female part 12 . The male part 11 may be elastic to snap into the female part 12 . A gasket 15 is arranged between the male and female parts 11 , 12 . The function of the gasket 15 is to hinder fluids and moisture to come into the electronic equipment at the means of attachment 3 . [0023] Depending on the size of the opening 2 , the only stabilizing structure may be the way the cloth 6 is attached to the edge 5 of the opening 2 . The cloth 6 is normally stretched at the assembly. However, for larger openings further stabilizing structures 4 , including one or more points of support, are arranged. [0024] In the embodiment of FIG. 4 the edge 14 of the cloth 6 is folded into a slit of the male part 11 . The cloth 6 may he held at the male part 11 by means of glue, welding, friction and/or that the male part 11 is pretensioned to give a clamping force on the cloth 6 . In this embodiment the female part 12 is actually a part of the housing 1 and has two perpendicular surfaces, one of which has a recess for receiving a gasket 15 . The gasket 15 seals between the male and female parts 11 , 12 . [0025] The male part 11 is held at the female part 12 in that barbs, cuts, grooves or the like 20 of respective part lock into each other. In other embodiments, the male and female parts 11 , 12 are attached to each other by means of an adhesive, by welding or the like. The male part 11 has an outer contour corresponding to the inner contour of the female part 12 . In a further embodiment, the outer dimension of the male part 11 is slightly larger than the inner dimension of the female part 12 , which allows a force fit to provide a stronger connection. [0026] In the embodiment of FIG. 5 the stabilizing structure 4 is received inside the cloth 6 . This is done by means of bars 7 interwoven into the cloth 6 , or by having channels in the cloth, which channels will receive bars 7 . The edge 14 of the cloth 6 is attached to the edge 5 of the opening 2 in any of the above ways. A person skilled in the art realizes that even if a cloth 6 having enclosed bars 7 is used the other stabilizing structures 4 may be used, including one or more points of support 9 . [0027] It should be emphasized that the terms “comprises” and “comprising”, when used in this specification as well as the claims, are taken to specify the presence of stated features, steps or components; but the use of these terms does not preclude the presence or addition of one or more other features, steps, components or groups thereof. [0028] Various embodiments of Applicants' invention have been described, but it will be appreciated by those of ordinary skill in this art that these embodiments are merely illustrative and that many other embodiments are possible. The intended scope of the invention is set forth by the following claims, rather than the preceding description, and all variations that fall within the scope of the claims are intended to be embraced therein.
A cloth for covering an opening in the housing of electronic equipment includes a stabilizing support structure. The cloth is permeable to gases, especially air, but is impermeable to fluids, moisture, dirt, dust, particles and the like. The stabilizing support structure may have one or more bars or may be adjacent to or integrated in the cloth. The support may also be provided by a fixed edge of the opening that the cloth is stretched over.
8
TECHNICAL FIELD [0001] The present invention relates to automatic gain control circuits. More specifically, the present invention relates to an automatic gain control circuit that maximizes front-end signal attenuation. BACKGROUND OF THE INVENTION [0002] A majority of receiver designs employ some form of front-end automatic gain control (AGC) to limit the amount of signal power present at the mixer input. This limits the signal being presented to the mixer and maintains a higher dynamic range. Three often-used terms in receiver front-end AGC circuits are “wideband AGC” (WBAGC), “narrowband AGC” (NBAGC), and “keyed AGC” (KAGC). WBAGC refers to the wide bandwidth signal strength indication of the total FM band. NBAGC refers to the on-channel bandwidth signal strength indication of a desired signal as defined by the bandwidth of the intermediate frequency (IF) strip. KAGC refers to a design that utilizes a control algorithm that limits the front-end attenuation based on the level of the desired signal. [0003] Referring to the block diagram in FIG. 4, the conventional implementation of AGC has been to use a WBAGC circuit 40 as a control mechanism for front-end signal attenuation. Modification to the WBAGC circuit 40 has been to use the NBAGC to limit the amount of WBAGC that can be applied to the front-end for signal attenuation. Referring to the block diagram in FIG. 5, this modification is most commonly called the KAGC circuit 50 . [0004] In such AGC circuits 40 , 50 , a situation is often present where there is a desired signal 60 that is weak and an undesired signal 62 (i.e. an undesired interferer) that is strong (FIGS. 6, 7). In the conventional WBAGC circuit 40 , the amount of the front-end attenuation (i.e. attenuation magnitude A, B) is dictated entirely by the RF strength of the undesired signal 62 . The attenuation magnitude, A, of the desired signal 60 is typically approximately equivalent to the attenuation magnitude, B, of the undesired signal 62 . Referring to FIG. 6, the WBAGC circuit 40 can essentially attenuate the desired signal 60 below any listenable level (i.e. a noise floor) by the attenuation magnitude, A, after the AGC is applied. When the attenuation of the desired signal 60 is below any listenable level, the situation is commonly referred to as desensitization or “flushing.” Thus, without KAGC, the desired signal 60 is flushed. [0005] The KAGC circuit 50 works satisfactorily for conditions in which the undesired signals do not produce intermodulation (IM) products that fall on the desired signal. Referring to FIG. 7, the KAGC circuit 50 prevents the desired signal 70 from being flushed for such conditions and is above the noise floor. Hence, the KAGC circuit 50 reduces the amount of desensitization of the desired signal 70 . Similar to the WBAGC circuit 40 for FIG. 6, the attenuation magnitude, A, of the desired signal 70 is typically approximately equivalent to the attenuation magnitude, B, of the undesired signal 72 in the KAGC circuit 50 . [0006] The amount of attenuation magnitude A, B in the KAGC circuit 50 is limited by the strength of the weak signal station. The limit to which this attenuation is applied is set with an internal reference in the front end IC (i.e. RFIC). This reference is compared with the narrowband level voltage or received signal strength indicator (RSSI). Once this narrowband level voltage reaches the threshold value of the comparator, no further attenuation is applied. The amount of the front-end AGC is limited with the help of the narrowband IF signal. [0007] Three different signal condition situations, which occur without producing any intermodulation (IM) products at the desired signal frequency, are covered with the present conventional systems that employ a combination of both the conventional WBAGC circuit 40 and the KAGC circuit 50 . In a first situation (not shown), when the desired and undesired signals are both weak, no attenuation is applied in an AGC action for the WBAGC circuit 40 . In a second situation for the WBAGC circuit 40 as seen in FIG. 8, when the desired signal 80 and the undesired signal 82 are strong, the desired AGC action is to apply attenuation until the undesired signal 82 reaches the threshold level. Thus, the desired signal 80 is attenuated down in magnitude that is approximately equivalent to A, and the undesired signal is attenuated down in magnitude that is approximately equivalent to B, where A is equal to B. In a third situation for the KAGC circuit 50 as seen in FIG. 9, when the desired signal 90 is weak and more than one strong undesired signal 92 produces an out-of-band IM product 94 , the desired AGC action is to apply AGC until the desired signal 90 is desensitized to the KAGC level. [0008] However, the deficiency as seen in FIG. 10, when two strong undesired signals 102 produce an inband IM product 104 , the deficiency of the third situation is the KAGC's inability to decipher between the desired signal 100 and the IM product 104 that occupies the same bandwidth as the desired signal 100 . These types of IM products 104 are one subset of generalized FM undesired spurious responses. These responses are generated by non-linear mixing operations that include harmonics of an IF signal, the local oscillator signal, and signals at the receiver input. [0009] It is contemplated by the applicants that conventional AGC circuits 40 , 50 may be enhanced to detect a spurious response at the desired frequency. Therefore, it is an objective of the applicants to overcome the fallbacks of conventional AGC circuits 40 , 50 to allow the front-end to exert full attenuation of the incoming signals without being limited by conventional AGC circuits 40 , 50 . SUMMARY OF THE INVENTION [0010] Accordingly one embodiment of the present invention is directed to an automatic gain control circuit that maximizes front-end signal attenuation. The automatic gain control circuit comprises an intermodulation detector and a keyed automatic gain control circuit. The intermodulation detector detects front-end signal interference and generates an intermodulation detection flag. The keyed automatic gain control circuit uses the intermodulation detection flag to control the front-end signal attenuation. [0011] Another embodiment of the invention comprises means for detecting signal interference, means for generating an intermodulation detection flag, and means for controlling the keyed automatic gain control circuit. [0012] Another embodiment of the invention is directed to a method for maximizing front-end signal attenuation for an automatic gain control circuit. The automatic gain control circuit comprises a keyed automatic gain control circuit and an intermodulation detector. The method comprises the steps of receiving a desired signal and an undesired signal, producing signal interference, detecting the signal interference, generating a detection flag, deactivating the keyed automatic gain control circuit and flushing the undesired signal. BRIEF DESCRIPTION OF THE DRAWINGS [0013] [0013]FIG. 1 is a block diagram of an enhanced automatic gain control (AGC) system according to the present invention; [0014] [0014]FIG. 2 is a representative view of a signal condition when an inband intermodulation (IM) product is produced by two signals; [0015] [0015]FIG. 3 is a representative view of a signal condition including a weak desired signal and a strong undesired signal when no inband IM products are generated; [0016] [0016]FIG. 4 is a block diagram of a conventional wideband AGC (WBAGC) circuit; [0017] [0017]FIG. 5 is a block diagram of a conventional keyed AGC (KAGC) circuit; [0018] [0018]FIG. 6 is a representative view when a desired signal is flushed in the WBAGC circuit of FIG. 4; [0019] [0019]FIG. 7 is a representative view when the KAGC circuit of FIG. 5 prevents the desired signal from being flushed; [0020] [0020]FIG. 8 is a representative view of a signal condition showing an AGC application for the WBAGC circuit of FIG. 4; [0021] [0021]FIG. 9 is a representative view of a signal condition showing an AGC application for the KAGC circuit of FIG. 5 that generates an out-of-band intermodulation product; and [0022] [0022]FIG. 10 is a representative view of a signal condition showing an AGC application for the KAGC circuit of FIG. 5 that generates an inband intermodulation product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0023] The AGC system, which is shown generally at 10 in FIG. 1, enhances the capabilities of the conventional KAGC circuit 50 by detecting a spurious response at a desired frequency. Once this is accomplished, it will allow the front-end to exert full attenuation on the incoming signals by essentially turning the KAGC function off without being limited by the KAGC function. In the following description of the preferred embodiment, it is assumed that the WBAGC and the KAGC are fully turned on. [0024] The detection of signal interference can be accomplished as follows: a typical FM detector (i.e. an FM demodulator) is a circuit whose output voltage is proportional to the difference between a reference frequency and the frequency of an input signal. Hence, large frequency excursions or deviations of the input signal produces large voltage swings at the output. One source of large frequency variations beyond the standard FM deviations is the direct result of IM products being present on the desired signal (FIG. 10). Fast voltage swings at the output generate broad frequency spectrums that are used to generate ultra sonic noise 14 (USN). In the AGC system 10 , means for detecting front-end signal interference, such as an IM detector 12 , detects the USN 14 . Means for generating, such as the IM detector 12 , generates an intermodulation (IM) detection flag 19 . Means for controlling the KAGC circuit 50 , such as the IM detection flag 19 , is used as a control signal for controlling the KAGC action (i.e. turning off the KAGC function) at the front-end of the receiver. [0025] Because there are several other conditions that can result in USN activity, this particular IM detection flag 19 alone that is generated by the IM detector 12 in the presence of USN 14 is not sufficient to reliably predict the IM product presence. It should be noted however, that the USN activity that is generated as a result of the IM situation is appreciably higher than any other scenario that may result in USN activity. This is readily observed from the fact that IM products are typically generated with higher order harmonics. A higher order harmonic will imply that the frequency deviations of the FM signals are also being amplified with the order of the harmonics involved. Hence, this will typically give rise to a higher quantitative amount of USN 14 . [0026] To further limit the probability of a false trigger of the KAGC system, a level signal or field strength signal indicator 16 can also be used as an input for the IM detector 12 in order to generate the IM detection flag 19 . The field strength indicator 16 is used to set the KAGC threshold and is located at the output of the long amplifier in the KAGC circuit 50 . With this vital information available, it can be readily determined when the desired signal has reached a low RF level at the point of the AGC set threshold. This information, coupled with the knowledge that the WBAGC is active, can provide one of the triggers for turning off the KAGC function. [0027] Another source of signal interference that can also be used in order to generate the IM detection flag 19 is the AM wideband (AMWB) signal. As the name would indicate, AMWB is the measure of AM that is created on a FM signal due to the presence of multipath interference. The field strength indicator 16 may be sent to an AMWB detector (not shown) when the desired signal is rapidly changing. Hence, the field strength indicator 16 attempts to track the AMWB signal, which results in a full-wave rectified AM signal that is proportional to the amount of amplitude of the desired signal. The AMWB detector generates a DC voltage that is projected off of the AMWB signal from the field strength indicator 16 . The AMWB detector essentially detects the DC average of the field strength indicator 16 , which in turn provides an amount of variation in the desired signal. Although the AMWB detector is not shown, it may be similarly located where the IM detector 12 is shown in FIG. 1. [0028] AMWB is commonly used in the receiver design to detect the presence of multipath interference in the FM signal transmission. It would appear that in the presence of an IM signal, there would be less multipath interference generated. In an IM situation, it is already established that the desired signal is very weak. Thus, the amount of AM on this signal is also less when compared to a relatively high desired signal. Hence, a lesser amount of AMWB indication can also be used as an IM detection flag 19 in controlling the KAGC function. [0029] Another source of signal interference that can also be used in order to generate the IM detection flag 19 in the AGC system 10 is the IF frequency 18 itself. Over-modulations of the IF that effect the IM signals can also be detected at the IF. [0030] For the AGC system 10 described above, there are two situations that produce IM products that are at the frequency of the desired channel. In a first situation as seen in FIG. 2, when the desired signal 20 (shown at 98.1 MHz) is weak and the undesired signals 22 are strong (shown at 98.9 MHz and 99.7 MHz), an inband IM product 24 is generated and the IM detector 12 is triggered (i.e. FM(IM)=2F 1 −F 2 ; FM(IM)=2*98.9−99.7=98.1). When the IM product 24 is generated, the audio level of the IM product 24 will be twice of what it's being broadcast. Thus, the KAGC function does not turn on, and the AGC system 10 applies attenuation to eliminate the undesirable signal 22 by applying enough AGC to bring the undesired signal to the start of AGC because the IM product 24 is competing with the desired signal 20 . [0031] In a second situation as seen in FIG. 3, when the desired signal 30 (shown at 98.1 MHz) is very weak (i.e. the S/N is below a listenable level) and the undesired signal 32 (shown at 98.5 MHz) is strong, no inband IM products are generated. Thus, the KAGC does not turn on, and the AGC system 10 applies attenuation to flush the undesirable signal 32 . [0032] This approach may desensitize the desired signal 30 . However, the desensitization of the desired signal 30 does not have a major importance in the AGC system 10 if it is below a listenable level. If this did happen, the output of the receiver would be static (i.e. no signal present). From a user's standpoint, it would be preferable to listen to static than the IM product. [0033] As shown above, the AGC system 10 uses the detection flags 14 , 16 , and 18 to help determine the presence of IM products, and when present, allow the KAGC function to switch off with controlling means, such as a control signal 19 , so that the undesirable signal may become flushed. While maintaining the implementation of the KAGG circuit 50 when no inband IM products are present, the AGC system 10 employs the advantage of turning the KAGC function off when inband IM products are generated. Thus, the front-end of the receiver exerts maximum attenuation in order to minimize the effects of the undesired signal. The KAGC function also turns off when a desired signal that is below the KAGC threshold level is very weak and when a strong undesired signal that turns the WBAGC on is present. Thus, the result is a limited amount of front-end attenuation because there is little or no KAGC signal present to control the amount of the attenuation. If the KAGC is turned off completely, the front-end will fully attenuate the undesired signal. Thus, when the KAGC is completely turned off, it does not matter if the desired signal is attenuated with the undesired signal because it had poor listening quality to begin with. [0034] It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is intended that the following claims define the scope of the invention and that the method and apparatus within the scope of these claims and their equivalents be covered thereby.
An automatic gain control circuit that maximizes front-end signal attenuation is disclosed. The automatic gain control circuit comprises a keyed automatic gain control circuit and an intermodulation detector. The intermodulation detector detects signal interference and generates an intermodulation detection flag. The keyed automatic gain control circuit uses the intermodulation detection flag to control front-end signal attenuation. A method for maximizing front-end signal attenuation for the automatic gain control circuit is also disclosed.
7
BACKGROUND OF THE INVENTION The invention relates to a method for receiving signals characteristic of cardiac activities in the atrium and/or ventricle of a heart and for evaluating the signals to obtain a control signal for a heart pacemaker and/or defibrillator. The invention also relates to a device for performing the method. Implantable heart pacemakers and defibrillators have an input stage connected to an intracardial electrode for receiving and amplifying intracardially picked-up cardiac activity potentials and an evaluation unit for evaluating them and deriving control signals for operating the pacemaker or defibrillator. If signals from the heart chamber (ventricle) as well as the atrial area (atrium) are required for the control, then one electrode is provided for each, and the input stages (if necessary also components of the evaluation unit) generally form separate channels, for which the processing characteristics (sensitivity or detection threshold, filtering and amplification parameters) can be adjusted separately. With automatic defibrillators and double-function pacemakers, which function as defibrillators if necessary, the initial stages must also detect and preprocess as signals the cardiac action potentials or signals that appear with normal cardiac action (sinus rhythm), such as occur with the various arrhythmic conditions of the heart. The signal amplitudes for the intracardially picked-up signals, which characterize the different heart rhythm conditions, differ considerably from each other, as can be seen in FIG. 2. Graph I here illustrates a typical sinus rhythm with normal heart function, Graph II the electrogram for a ventricular tachycardia and Graph III that of a heart chamber fibrillation (ventricular fibrillation). A suitable detection threshold TI, TII, TIII is respectively marked here with a dashed line (Graph I), a dash-dot line (Graph II) or a double dash-dot line (Graph III). An embodiment of the initial stage of a pacemaker with an automatic gain control (AGC) is known--for example from EP 0 349 130 A1. It is designed to improve the signal/noise ratio when operating jointly with a band-pass filtering. Furthermore, it is known from U.S. Pat. No. 4,184,493 A1 to provide an automatic gain control with an automatic, implantable defibrillator. Together with a high-pass filtering, this causes a far-reaching suppression of S and T components of the electrogram and thus prevents a possible faulty interpretation of a "normal" electrogram as ventricular fibrillations, based on the detection of these signal components. In an implantable cardioverter/pacemaker according to DE 37 39 014 A1, the AGC can be used further in connection with the detection of signal components with low amplitude and thus a ventricular fibrillation. Such a function of the AGC is illustrated in FIG. 3, where the drawn-out graph represents an electrogram where a sinus rhythm can be seen in the left segment (range A), a ventricular tachycardia in the center segment (range B) and ventricular fibrillations in the right segment (range C). The upper, dashed line represents the effective detection threshold as it is adjusted by the AGC, and the events demonstrated for the illustrated, time-dependent course of the detection threshold are shown in the lower section of the Figure. Certain appearances of ventricular fibrillation are characterized in the intracardial electrogram by the occurrence of a relatively low-frequency signal pattern with comparably high amplitude, superimposed on the fibrillation signals with considerably higher frequency and weaker fibrillation signals; compare in this case perhaps U.S. Pat. No. 4,523,595, especially FIGS. E12 and E13. Such an electrogram is shown (diagrammatically) in FIG. 4, for which the layout is analogous to FIG. 3. As is illustrated with this Figure, with the relatively slow rise of the amplification and the correspondingly slow decline of the detection threshold after each signal of the superimposed signal pattern that respectively increases the threshold, the AGC prevents a detection of the signals that characterize the fibrillation. As a result of this, the defibrillator cannot become operational, even though it may be needed. With an automatic defibrillator, the automatic gain control (AGC) therefore can possibly result in grave operational defects--not to mention the fact that its realization for strongly differentiated signal images in the form of cardiac electrograms is not simple and is rather costly. SUMMARY OF THE INVENTION It is therefore the object of the invention to present a method and a device of the aforementioned type, which permit a reliable detection and differentiation of various cardiac conditions on the basis of an intracardial electrogram with justifiable expenditure, as well as an automatic defibrillator that uses this method or this device. The solution to this object includes the idea of undertaking a signal processing of intracardially picked-up heart signals by using two different, permanently effective detection thresholds that do not change during the measuring, one of which is tailored exclusively to the detection of fibrillation signals. This eliminates an unavoidable danger in the automatic gain control of "overlooking" signals with small amplitudes, which indicate a ventricular fibrillation, with the simultaneous appearance of signals with considerably larger amplitude, and the design for the detection circuit can be simplified at the same time owing to the elimination of the involved AGC. The signals on which this is based can be picked-up in particular by using at least one intracardially arranged sensing electrode--wherein they represent the time-dependent course of a cardiac activity potential at the sensing location--or if necessary with one or several intracardially arranged pressure transducers--wherein an electric signal spectrum exists that reflects intracardially time-dependent pressure fluctuations. However, other sensors can be used as well, which basically can supply signals indicating the appearance of fibrillation events. The various detection thresholds are realized respectively in a separate input stage with a design that is known per se, wherein the signal spectrum received in dependance on the time is subjected to an evaluation with the threshold value comparison result in order to gain a statement with respect to the occurrence of sinus-type cardiac activities or ventricular fibrillations, and finally a control signal is generated that characterizes the evaluation result, which in particular can serve to control a pacemaker and/or stand-by defibrillator. The processing method with the low detection threshold advisably comprises a preprocessing step with (wide-band) gain and a high gain factor, wherein cutting the signal components off above a predetermined limit that is selected above the level of the lower detection threshold--in particular also of stimulus pulse artefacts--improves the transfer characteristics for the weak fibrillation signals. Another improvement with respect to this can be achieved by blanking out the signal components during a predetermined time interval, following the appearance of a signal component located above the predetermined limit. The pre-processing step advantageously includes digitizing, at least in the signal path with the low threshold, wherein the digitizing takes place after signal components with higher amplitude are cut off, if such is planned. This permits in a cost-effective way the use of an A/D converter with low accuracy or processing width and subsequently the use of a digital comparator for the threshold value discrimination and a simple digital analysis in a microprocessor or an integrated evaluation circuit. Furthermore, it permits in a simple way the temporary storage of the signals for a later, different analysis. The adjustment of the lower detection threshold can be made favorably during an initial measuring, depending on the result of an analysis of the maximum or an average amplitude or the signal energy for that component of the total signal spectrum, which is not cut off. In order to be able to distinguish the weak fibrillation signals with sufficient certainty from the noise and thus prevent possibly dangerous false alarms of a defibrillator, it is useful to distinguish between the signals fed to the second input stage or preprocessed there and the noise, based on an amplitude and/or frequency discrimination. It is useful to do this with the aid of digitized signals. In case of an amplitude discrimination, a limit is preset, for which the signals located above are classified as significant and signals located below are classified as noise. The (low) threshold is then set, for example, to 75% of the peak level of the signals classified as significant. The evaluation interval can also have a timed averaging with respect to the detection signal train for a preset number of signals, preprocessed with the low threshold, or a predetermined time cycle for noise suppression and the determination of an average rate for these signals, wherein a signal is output that characterizes the existence or non-existence of fibrillations, depending on the average rate. Furthermore, it is possible to determine the signal peak values or a signal mean value or the average signal output or the root-mean-square value of the signal amplitude for the signals above the second detection threshold and to output a signal that characterizes the existence or non-existence of fibrillations depending on the average rate and the signal peak value, the signal average value or the root-mean-square value. This presupposes the existence of typical or comparative signal images, which the cardiologist generally is familiar with or which can be determined--patient specific--for example with provoked fibrillations. For one particularly advantageous use of the two-threshold principle according to the invention, the evaluation includes a timed message with respect to the detection signal train obtained with the higher threshold attuned to the signals stemming from sinus-type cardiac events, via a predetermined number of signals or a predetermined time cycle for determining an average rate for these signals, that a time window is determined from the average rate (escape interval, perhaps specific for bradycardia), and that a signal is issued within the time window that characterizes the type of actual cardiac activity (maybe also a bradycardia), depending on the appearance or non-appearance of signal components located above the first detection threshold as well as located above the second detection threshold. With the inventive device, a separate evaluation unit with a control signal output for issuing a control signal characterizing the respective evaluation results can be coordinated with each input stage. However, it is also possible to have a joint or linked evaluation in sections--for example within the meaning of the previous paragraph. The input stage with the low threshold can have in particular a wide-band amplifier with a high amplification factor. For advantageous embodiments--corresponding to advantageous embodiments of the measuring method--it can also have a level limiter circuit for cutting off signal components located above a predetermined limit that is selected above the level for the second detection threshold and, if necessary, a scanning or blanking circuit for blanking out the signal components during a predetermined time interval, following the appearance of a signal component above the predetermined limit. Furthermore, it is advisable to have an A/D converter for digitizing the picked-up or already preprocessed signals. In that case, the comparator unit for threshold value discrimination can be configured as digital comparator. If a level limiter circuit exists, the input for the A/D converter is connected to the output for the level limiter circuit and the A/D converter can be a model with relatively low processing range. A signal memory can also be provided, for which the data input can be connected to the A/D converter output and its data output with an internal or external evaluation unit. Timing means (timers) can be assigned to the first and second input stage for determining evaluation time intervals, and they respectively have a rate determination circuit for determining an average rate for the signal components located above the respective detection threshold. Alternatively or additionally, means can be provided during a preceding measuring cycle for the amplitude discrimination and, if necessary, amplitude mean value formation as well as means for adjusting the second detection threshold, depending on the result of an evaluation of the maximum or an average amplitude of the total signal spectrum component that is not cut off. The means for amplitude discrimination are--if a digital signal processing takes place--usefully connected in series after the A/D converter. The inventive device can be used with an automatic defibrillator, specifically also one that additionally functions as a demand pacemaker. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a very simplified block diagram of a two-chamber demand pacemaker with standby defibrillator for which one embodiment of the invention is realized; FIG. 2 is a representation of intracardially picked-up electrograms (ECG signals) of various cardiac activities; FIG. 3 is a diagrammatic representation of an electrogram of various chronologically successive cardiac activities characterizing the course for the detection threshold and the detected signals for a detection method based on the Prior Art (with AGC); FIG. 4 is a diagrammatic representation of a special electrogram characterizing the chronological course of the detection threshold and the detected signals for a detection method based on the Prior Art (with AGC); FIG. 5 is a diagrammatic representation of the electrogram according to FIG. 4 characterizing the chronological course of the detection thresholds and the respective detected signals for a detection method based on one embodiment of the invention; FIG. 6 is a diagrammatic representation of the electrogram according to FIGS. 4 and 5 with higher amplification, peak cut-off and scanning of signal components for a detection method according to another embodiment of the invention; and FIG. 7 is a very simplified block diagram of a read circuit based on an embodiment of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a very simplified representation--in particular by omitting the components for a power supply, programming, etc.--of a twin-chamber pacemaker 3 connected with electrodes 1 in the atrium A and 2 in the ventricle V of a heart H, having a pacemaker pulse unit 4 and an integrated defibrillator discharge stage 5. The pacemaker pulse unit 4 has a control input 4a and two separate pulse outputs 4b and 4c for atrial or ventricular stimulation pulses. The output 4b is connected via a node K1 with the atrial electrode 1 and the output 4c via a node K2 with the ventricular electrode 2. The defibrillator discharge stage 5 has a control input 5a and a pulse output 5b for cardiac stimulation pulses, which is also connected via the node K2 to the ventricular electrode 2. (In its function as a defibrillation electrode, the electrode 2 here is shown only diagrammatically; additional intracardial or subcutaneous electrodes can also be provided for the cardiac stimulation) In addition to is functioning as stimulating electrodes, the electrodes 2 and 3 function also as signal sensors for atrial or ventricular recorded electrograms (intracardial ECG signals). That is why they are connected via the nodes K1 or K2 with a read and evaluation circuit 6 of the pacemaker/defibrillator 3. Their output signals travel via scanning or "blanking" stages 7a and 7b that can be switched on and off (maybe triggered directly by transmitted stimulation or defibrillation pulses) as protection against overload through stimulating pulses to nodes K3 or K4, where the signal path for the atrial and ventricular signal respectively branches off. From node K3, the atrial signal is fed to two separate input stages 8 and 9, and the ventricular signal is fed from node K4 to two separate input stages 10 and 11. The continued signal path for both signals is in principle the same--except for specific adjustments of the modules--so that in the following only the signal path for the signal obtained in the atrium is described. For input stages 10 and 11, the modules with analogous numbering correspond to the individual modules for inputs stages 8 and 9, that is the modules 10.1 and 11.1 corespond to modules 9.1 and 8.1. The first input stage 8 for the atrial signal has a read amplifier 8.1, which can be switched on and off through corresponding control signals referred to as "E/A" or "VS(A)" with adjustable amplification, and the input stage 9 has a read amplifier 9.2. The latter has a wide-band design, can also be switched off selectively via a signal "E/A" and has a relatively high amplification factor that can be adjusted via a control signal ("VL(A)"). Within the first input stage 8, the amplified signal from the read amplifier 8.1 travels to a filtering stage 8.3--which can also be switched on/off via a signal "E/A"--and from there to a threshold value detector circuit 8.4 with a detection threshold that can be adjusted via a control signal "TS(A)," which lies within the standard detection threshold range for pacemaker input circuits for sinus-type cardiac event (without AGC). In addition, a tapping point for an unfiltered intracardial ECG signal "ECG(A)" is provided between the read amplifier 8.1 and the filtering stage 8.3. Within the second input stage 9, the input signal initially travels to an integrated level limiter stage and scanning or blanking circuit 9.1, which can be activated via a control signal from the threshold value detector circuit 8.4 of the first input stage 8 and which prevents overloads in this signal path. From the output of this stage it travels to the read amplifier 9.2 and from there as wide-band amplified signal to a filtering stage 9.3, which also can be switched on/off via a signal "E/A." From there, it finally arrives at a threshold value detector circuit 9.4 with a detector threshold that can be adjusted via a control signal "TL(A)," which is located below the threshold for the first threshold value detector circuit 8.4 and the standard detector thresholds of pacemaker input circuits (without AGC). The modules 8.1, 8.3 and 8.4 form the first input circuit and the modules 9.1, 9.2 9.3 and 9.4 from the second input circuit for the atrial measuring signal. In the threshold value detector stages 8.4 or 9.4 and based on the detector threshold adjustment, the input signal is respectively converted as known per se into a train of individual pulses. The pulse trains are initially fed via the signal outputs 8a or 9a to separate evaluation stages 12 or 13, where they are used for classifying or identifying the cardiac events detected through the atrial measurement. The ventricular signals, which are processed in the stages 10.1 to 10.4 or 11.1 to 11.4 analogous to the above description, are analyzed in a similar way in evaluation stages 14 or 15, and all evaluation or intermediate data are subsequently fed to a central processing and control unit 16, which finally readies at the output 16a and 16b control signals for operating the pacemaker pulse unit 4 or the defibrillator stage 5. The operation of the arrangement shown in FIG. 1 is explained by referring to FIG. 5, which is a diagrammatic representation of an (atrial or ventricular) recorded electrogram by characterizing the course in time of the detection thresholds of the two input stages 8 and 9 or 10 and 11, which are assigned to the electrodes 1 or 2, as well as providing their output signal trains. Deviating from the adjustments normally made in practical operations, the simplifying assumption is made in FIG. 5 that both read amplifiers have the same amplification factor and that no level cut-off, scanning or varied filtering occurred in both signal paths. In that case, the same signal spectrum is present at the input for threshold value detectors 8.4 and 9.4 (or 10.4 and 11.4). The discrimination of the detection thresholds TS U , TS L and TL U , TL L results in the detection signal trains "TS" or "TL," which are indicated in the lower section of the Figure--with the same time scale as in the upper section. A comparison with FIG. 4, which is explained at the beginning of the description and shows the same electrogram, illustrates the gain achieved through the use of two detection thresholds with constant time: While it is not possible with the standard method for processing the inputs signals in an input stage with AGC to detect the signal components which are located below the larger signals and indicate a cardiac fibrillation, this is easily possible by means of the above-described device. In addition, it is possible--and this is not the case when using only one, low threshold--to have a pre-classification of the signals, which in the electrogram shown is a separation between the fibrillation signals and the signals indicating a superimposed, regular cardiac activity. This permits an exact analysis of the heart condition in the following evaluation stages and the correct control of the pacemaker or the defibrillator. The use of level limiters and scanning circuits 9.1 and 10.1 further improves the transmission behavior in the signal paths with the low detection threshold. While input signals with high level exceed the standard detection threshold of input stage 8, their activation permits a high amplification in the input stage 9, which equals a low effective threshold. This can be used in such a way that the detector threshold adjusted in the threshold value detector 9.4, can be in the normal range, while the input stage 9 still has a low, effective detection threshold. An electrogram processed with level limiting and scanning corresponding to FIGS. 4 and 5 is shown in FIG. 6. The upper and lower detection thresholds TL U or TL L correspond to FIG. 5. However, the high amplification assumed in FIG. 6 necessitates another scale for the ordinate as compared to FIG. 5. The electrogram ranges where a level limiting to a preset level value C u has started are shown. The Figure shows that one each scanning range follows. The level limiting otherwise facilitates a digitizing and continued digital processing of the signals, since this reduces the number of required quantization stages and the processing width. In particular, the threshold value detection stages then can have digital comparators, and the evaluations can take place in a microprocessor configuration. A corresponding read and evaluation circuit 100 as an additional embodiment of the inventive device is shown diagrammatically in FIG. 7. A cardiac activity potential picked-up via a sensing electrode 2 in the ventricle V of a heart H travels via a node K101 on the one hand to a traditional read amplifier 101 and from there to a first integrated threshold value detector and rate determination circuit 102, from which output signals gained following the threshold value discrimination and a rate determination of the signal components with high amplitude are transmitted to a microprocessor 103. On the other hand, the input signal travels to an integrated blanking and wide-band amplifier circuit 104 with high amplification, for which the blanking behavior is controlled from the stage 102. The amplified signal will be transmitted by a switching unit 105 selectively to a threshold value detector (analog) and rate determination circuit 106, from which output signals gained as a result of the threshold value discrimination and a rate determination of the signal components with small amplitude are transmitted to the microprocessor 103, or are initially fed to an A/D converter 107. The output for the A/D converter 107 is connected via a node K102 with the inputs of a digital threshold value detector and rate determination circuit 108, a digital signal processor 109 and a digital ECG memory 110, which are all linked via a bus 111 with the microprocessor 103. In addition, the output for stage 108 is connected to the microprocessor via a standard signal line, through which the results of the digital processing in stage 108 are transferred (alternative to results gained through the analog signal processing in stage 106). The microprocessor 103 makes signals 112 available for subsequent processing and/or control stages or an output to the outside (perhaps for an external ECG analysis). The modules 101 and 102 form a first input stage 100A with a standard threshold and the modules 104 to 109 a second input stage 100B with a low threshold. Insofar as it differs from the one shown in FIG. 1, this circuit operates as follows: In the first threshold value detector and rate determination stage 102, the signal components with high level are initially measured and their average rate determined. In comparison to stored values, it is possible to initially conclude from this (in cooperation with the microprocessor configuration 103, which also includes a corresponding data memory) that a normal sinus rhythm, a tachycardia or a possible fibrillation are present. In the second (analog) threshold value detector and rate determination circuit 106, the rate for low-level signals is determined correspondingly--by including an accumulation or taking the mean--and from this (again in cooperation with the microprocessor and a data memory), it can be determined whether fibrillations are present. If such are detected, the result obtained through the high threshold processing is ignored, the result obtained on the path with low threshold is verified by shortening the time interval for taking the mean and--if it is confirmed--a defibrillation is initiated. Similar steps are taken with the third (digital) threshold value detection and rate determination circuit 108, wherein the signal peaks are possibly evaluated additionally and are consulted for the decision on whether fibrillations are present. This method of processing makes it also possible in a simple way to verify the existence of a bradycardia in that a time window (bradycardia escape interval) is given, to which all evaluations are applied. If no signal with high amplitude appears during this time window and if the signal peak value for signals with low amplitude is essentially the equal to the average signal level or is below a predetermined limit--which is selected advantageously equal to the low threshold value--then no fibrillations, but only noise are detected. Thus, it is possible to infer the presence of a bradycardia, and the respective pacemaker therapy can be initiated. With the arrangement according to FIG. 7, several or if necessary all of the microprocessor functions concerning the signal processing can be taken over by a client specific processing circuit. The adjustment of the low detection threshold for both arrangements according to FIG. 1 or FIG. 7, can be made based on a measurement of the non-limited signal level or the amplitude mean value or the root-mean-square value, wherein signals that may be in the saturation range and certain signal components surrounding the saturated areas must be factored out. If the threshold itself is adjusted, the amplification factor does not need to be changed, which can be a considerable advantage for digital threshold value processing and a wide-band amplifier with high amplification factor. In its design, the invention is not limited to the aforementioned, preferred embodiment. Rather, a number of variations are conceivable, which make use of the solution presented, even if it is a totally different embodiment.
A method for processing a signal characteristic of cardiac activity in the atrium (A) and/or ventricle (V) of a heart (H) and for evaluating this signal with a view to obtaining a control signal for a cardiac pacemaker and/or defibrillator (3) can be carried out by: receiving a time dependent signal from at least one intracardial signal sensor (1, 2) in the atrium and/or ventricle; feeding the signal picked up by each signal sensor (1, 2) to a read and evaluation circuit (6) with a threshold characteristic; comparing the signals with a detection threshold; evaluating the result of the comparison to obtain an indication as to the presence of normal sinus-type cardiac activity or fibrillations; and producing the control signal, which characterizes the comparison result. The signal from the at least one sensor (1, 2) is fed to a first input stage (8, 11) which has a first adjustable detection threshold (TS(A), TS(V) that is constant in time and to a second input stage (9, 10) which has a second adjustable detection threshold TL(A), TL(V) that can be adjusted independently of the first detection threshold but is constant in time once set. The signal from the at least one intracardial signal sensor is processed in these first and second input stages.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority as a continuation-in-part of U.S. Non-Provisional Patent Application Serial No. 13/591,802, filed on Aug. 22, 2012, which in turn claims priority from U.S. Provisional Patent Application Serial No. 61/526,145, filed on Aug. 22, 2011, the entirety of which are each expressly incorporated by reference herein. BACKGROUND [0002] 1. Field [0003] This invention relates generally to flowing electrolyte battery systems, and more particularly, to material formulations for battery electrodes employed in flowing electrolyte batteries. [0004] 2. Background Information [0005] The performance of electrochemical storage devices involves complex, interrelated physical and chemical processes between electrode materials and electrolytes. [0006] Flowing electrolyte batteries may include a stack of flow frame assemblies where electrodes and separators are bonded to the flow frames. There are flow channels in the frames designed to direct electrolyte flow over the anode and cathode side of each electrode. On one side of each electrode, a component of the electrolyte is deposited and consumed during each cycle, while the other side of the electrode may include a carbon felt to support the catholyte evolution and consumption reactions. [0007] There is a need for improvement in many aspects of the design of flowing electrolyte batteries, including materials and manufacturing processes. One of the key areas with room for improvement relates to the formulation of electrodes. [0008] Zinc-bromine batteries are an example of rechargeable batteries. Rechargeable batteries may have their energy content restored by being charged, however deterioration of the battery may occur on each charge-discharge cycle. The deterioration may occur due to the interaction between the electrolyte and the electrodes within the battery cell. Electrolyte causes the electrode material to degrade, thus decreasing the active surface of the electrode while increasing internal resistance and diminishing battery capacity. [0009] Other limitations of existing battery electrodes is the inefficient bond between the frame and the electrode, which causes failures in battery performance. Another drawback is the fact that solids content represents a considerable percentage of the material's formulation. Some solids tend to absorb present reagents; producing an expansion of the electrode in the frame, thus creating warpage, which negatively affects battery performance. By reducing the amount of solids in the formulation, development of warpage may be decreased, while also improving the bonding between the electrode and the frame. Moreover, larger amounts of solids in the formulation may also cause the electrode to be brittle, so it is necessary to add components capable of increasing flexibility and tensile strength of the electrodes. [0010] Therefore, battery electrodes currently employed in flow batteries have performance and durability limitations. Electrodes employed in flowing electrolyte batteries and other electrochemical devices need to have low electrical resistivity, high chemical stability, good mechanical properties, and for some applications low weight and volume. Additionally, electrodes should be resistant to deformation due to the presence of reagents, such as bromine, or any other product employed during battery operation. [0011] More efficient battery electrodes are key to the advancement of energy storage technology, thus there is a need for material formulations which may provide battery electrodes with good flex strength, high conductivity, and resistance to expansion due to reagent exposure. BACKGROUND ART [0012] U.S. Pat. No. 4,125,680 Shropshire et al., Bipolar carbon-plastic electrode structure-containing multicell electrochemical device and method of making same (Aug. 18, 1977) [0013] Abstract A novel multicell electrochemical device having a plurality of bipolar carbon-plastic electrode structures and a novel method of making the device are described. A plurality of bipolar carbon-plastic electrode structures are formed by first molding thin conductive carbon-plastic sheets from heated mixtures of specified carbon and plastic, and then establishing frames of dielectric plastic material around the sheets and sealing the frames to the sheets so as to render the resulting structures liquid impermeable. A plurality of electrochemical cell elements in addition to the electrode structures, e.g. separators, spacers and the like, are also formed with dielectric plastic frames. The frames of both the electrode structures and the additional elements have projections on at least ne surface. The electrode structures and the additional elements are stacked to form a group of items in an electrochemically functional arrangement. The arrangement is such that the projection of each frame contacts a frame surface of the next item in the stack. The items in the stack are joined to one another, e.g. by heat welding or ultrasonic welding, at these areas of contact so as to form a multicell electrochemical device capable of holding liquid therein. [0014] U.S. Pat. No. 4,379,814 Tsien et al., Sheet electrode for electrochemical systems (Apr. 12, 1983) [0015] Abstract: An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture. [0016] U.S. Pat. No. 4,496,637 Shimada et al., Electrode for flowcell (Dec. 22, 1983) [0017] Abstract: An electrode for an flowcell comprising electrode material made of carbon fiber having average &It;002> spacing of quasi-graphite crystalline structure of not more than 3.70 .ANG., and the average C-axis size of crystallite of not less than 9.0 .ANG. and at least 3% by mole of oxygen atom bound to the fiber surface based on carbon atom, whereby the electrode has remarkable high electrical conductivity, current efficiency handling characteristics and hydrodynamic characteristics, and is adapted to flowcell. [0018] U.S. Pat. No. 5,591,532 Eidler et al, Zinc-bromine battery with non-flowing electrolyte (Jul. 7, 1995) [0019] Abstract: A battery including a plurality of bipolar electrodes and non-conductive separators, each having first and second surfaces. A carbon coating is applied on the first surface of each of the plurality of carbon plastic electrodes, and each separator is disposed in spaced, sandwich relation with respect to two of the plurality of electrodes. The electrodes and separators define a plurality of electrochemical cells, including a plurality of anodic half-cells, and a plurality of cathodic half-cells. A high surface area carbon material is disposed in, and completely fills, each cathodic half-cell, and an electrolyte is disposed in each half-cell. A spacer is disposed in each anodic half-cell. The spacer may be a mesh or screen made from polymeric material. The spacer may also be an aggregated glass mat. [0020] JP 07057740 Miyagawa et al., Electrode material of zinc-bromine battery (Mar. 3, 1995) [0021] Purpose: To provide an electrode material of zinc-bromine battery, which can prevent increase in the internal resistance while eliminating the warping caused by a swollen electrode material, and which can improve the service life and the reliability of the battery. [0022] Constitution: An electrode material to be arranged in the battery m in body of a zinc-bromine battery, comprises a four-component sheet form molding consisting of kneaded material, for which a predetermined composition ratio of carbon black, graphite and ion trapping agent are added to a high density polyethylene resin. The composition ratio of this electrode material is 45-49 wt. % of high density polyethylene resin, approximate 15 wt. % of carbon black, approximate 35 wt. % of graphite, and 1-5 wt. % of ion trapping agent. The ion trapping agent is of bismuth negative ion exchange type, and has acid resistance and alkali resistance and an inorganic ion exchanger, the form of which is selected among powder, paste and granular or tape all having heat resistance of not lower than 400° C. SUMMARY [0023] According to various embodiments, a chemical composition and manufacturing process are provided for fabricating battery electrodes which may be used in flowing electrolyte batteries. Flowing electrolyte batteries may be used as means to store and transport energy. The disclosed chemical composition of battery electrodes may include a mixture of polypropylene, glass fiber, carbon fiber, graphite, carbon black, elastomer, among others. This mixture may be later extruded to form electrode sheets. [0024] According to an aspect of the present disclosure, the invention addresses the deficiencies in the prior art by providing a chemical composition of battery electrodes which may reduce warpage and degradation that may be present when electrodes come in contact with bromine. That is, by minimizing the amount of carbon black in the chemical composition and adding graphite instead, the swelling of the battery electrode in the presence of bromide may be minimized. As a result, zinc-bromine batteries integrating the disclosed battery electrodes may exhibit improved efficiency and longer life span. In addition, by reducing warpage in the battery electrode, the electrolyte flow distribution within the battery may be also improved, therefore increasing battery performance and stability. [0025] Yet, according to another aspect of the present disclosure, by employing the disclosed material formulation, nucleation of battery electrodes may be reduced, thus diminishing dendrite formation and branching between battery cells, which may translate into separator failure and internal leakage within the flowing electrolyte battery. [0026] In other embodiments, chemical composition of battery electrode may further include components such as, but not limited to, carbon nanotubes, carbon nano-fibers, graphene, micro-graphites, insert molding adhesion promoters, glass beads, talc, mica, coupling agents, stabilizing fillers, crystallinity promoters, anti-oxidants among others. [0027] Numerous other aspects, features and advantages of the present invention may be made apparent from the following detailed description taken together with the drawing figures. LIST OF FIGURES [0028] Non-limiting embodiments of the present invention are described by way of example with reference to the accompanying figures which are schematic and are not intended to be drawn to scale. Unless indicated as representing the background art, the figures represent aspects of the invention. [0029] FIG. 1 shows a flowchart of a manufacturing method for battery electrodes, according to an embodiment. [0030] FIG. 2 depicts an illustrative embodiment of a battery electrode. [0031] FIG. 3 illustrates an embodiment of second extrusion process. [0032] FIG. 4 represents an illustrative embodiment of a battery cell stack. DETAILED DESCRIPTION [0033] Disclosed herein is a composition for electrodes that may be employed in flowing electrolyte batteries, according to an embodiment. The present disclosure is hereby described in detail with reference to embodiments illustrated in the drawings, which form a part hereof. In the drawings, which are not necessarily to scale or to proportion, similar symbols typically identify similar components, unless context dictates otherwise. Other embodiments may be used and/or other changes may be made without departing from the spirit or scope of the present disclosure. The illustrative embodiments described in the detailed description are not meant to be limiting of the subject matter presented herein. Definitions [0034] As used herein, “battery cell” may refer to an enclosure provided with at least a pair of electrodes and at least one inlet and one outlet configured to allow the flow of electrolyte through the enclosure. [0035] As used herein, “battery cell stack” may refer to one or more battery cells, placed between a pair of terminal electrodes or end caps, that share a common electrolyte path. [0036] As used herein, “flow battery” or “flowing electrolyte battery” may refer to an electrochemical device that includes at least one battery cell stack and is capable of storing energy. [0037] As used herein, “flow frame” may refer to a flow battery component that forms at least a portion of the enclosure of a battery cell, containing at least a portion of paths configured to control the flow of electrolyte through a battery cell stack. [0038] As used herein, “battery electrode” may refer to a structure inside the battery through which electric current is passed. [0039] As used herein “warpage” may refer to at least one distortion in a battery component. [0040] As used herein “bromine expansion” may refer to the expansion suffered by an electrode due to exposure to bromine. DESCRIPTION OF DRAWINGS [0041] Disclosed herein is a material formulation and method for producing battery electrodes which, according to an embodiment, may be employed in the manufacturing of electrochemical devices such as flowing electrolyte batteries. [0042] FIG. 1 shows a flowchart of manufacturing method 100 , according to an embodiment. Manufacturing method 100 may start with formulation components 102 which may include polypropylene, glass fiber, graphite, carbon black, elastomers, and other additives. Formulation components 102 may be compounded in first extrusion process 104 to obtain pellets 106 . Subsequently, pellets 106 may pass through second extrusion process 108 in order to obtain electrode film 110 ; where electrode film 110 may exhibit a uniform thickness ranging from about 0.1 mm to about 4 mm, with 0.6 mm being preferred. Afterwards, electrode film 110 may pass through die cutting process 112 in order to form electrode sheets 114 within preferred dimensions. [0043] Following the process in FIG. 1 , electrode sheets 114 may be coated with activation layer 116 which may include, in some embodiments, carbon and adhesives. Activation layer 116 may be pressed onto electrode sheet 114 to form a proper bond. Required pressure to bond activation layer 116 onto electrode sheet 114 may range from about 10 psi to about 200 psi, with 100 psi being preferred. Finally, in order to obtain smooth plastic surface for appropriate bonding with the flow frame of a flow battery, electrode sheets 114 coated with activation layer 116 may pass through edging process 118 , where a rubber blade may remove the carbon from all the perimeter of electrode sheet 114 . and forming battery electrode 120 . [0044] FIG. 2 depicts an illustrative embodiment of battery electrode 120 obtained from manufacturing method 100 . As seen in FIG. 2 , battery electrode 120 may include electrode sheet 114 coated with activation layer 116 , along with edged perimeter 202 formed during edging process 118 . Bonding between battery electrode 120 and frame may be improved by removing activation layer 116 as edged perimeter 202 may have a good probability of achieving a suitable bonding with the frame. [0045] The dimensions of battery electrode 120 depicted in FIG. 2 may vary according to the size and application of the flowing electrolyte battery that may integrate battery electrode 120 . [0046] Formulation Components 102 [0047] Chemical formulation of battery electrodes 120 may include formulation components 102 such as polypropylene, glass fiber, carbon fiber, graphite, carbon black, elastomers and other additives. Two types of polypropylene compounds may be employed: 1) polypropylene with low Melt Flow Index (MFI) and 2) polypropylene with high MFI. Low MFI polypropylene is required to achieve an extrusion grade material while improving the dispersion of carbon fillers, which may increase the conductivity of battery electrode 120 . High MFI polypropylene is employed in order to improve molding process of battery electrode 120 . Low MFI polypropylene may have a MFI between 1 and 10 gm/10 min at 230° C., 2.16 Kg, while high MFI polypropylene may have a MFI between 10 and 130 gm/10 min at 230° C., 2.16 Kg. Suitable suppliers for high MFI polypropylene and low MFI polypropylene may include Himont Inc. [0048] Carbon black may be added in the mixture of formulation components 102 in order to improve the electrical conductivity of battery electrodes 120 . Suitable suppliers for carbon black may include Akzo Chemie America. Carbon black tends to swell in the presence of bromine, producing an expansion of battery electrode 120 . As such, in order to reduce the expansion in battery electrode 120 , graphite may be used as one of the formulation components 102 . The addition of a suitable amount of graphite may allow a reduction in the amount of carbon black needed in the formulation. Graphite may also provide stability and conductivity to battery electrode 120 . Graphite may be purchased from SGL and Timcal. [0049] Carbon fiber may be also added to formulation components 102 to increase conductivity of battery electrode 120 . Suitable suppliers for carbon fiber may include Akzo Chemie America. To enhance the strength of the resultant battery electrode 120 , formulation components 102 may also include glass fiber which may add stability and resistance to bromine and thermal expansion. Glass fiber may be purchase from Owens Corning. [0050] Furthermore, bonding additives may be added to formulation components 102 to enhance bonding properties and improve insert molding process during the fabrication of flowing electrolyte batteries that may integrate battery electrode 120 . In some embodiments, a polyolefin elastomer may be employed as bonding additive. A suitable polyolefin elastomer may be ethylene octene copolymer which may be provided by Dow Chemical. Ethylene octene copolymer increases the mobility and miscibility of polypropylene resulting in greater cohesion between battery electrode 120 and the frame in which battery electrode 120 may be placed. [0051] According to an embodiment formulation components 102 may include low MFI polypropylene in concentrations ranging from about 35% wt to about 65% wt; high MFI polypropylene in concentrations ranging from about 5% wt to about 1.5% wt; glass fiber in concentrations from about 3% wt to about 10% wt; carbon fiber in concentrations from about 2% wt to about 10% wt; graphite in concentrations from about 5% wt to about 15% wt; carbon black in concentrations from about 7% wt to about 20% wt; and polyolefin elastomer in concentrations ranging from about 2% wt to about 10% wt. [0052] In other embodiments formulation components 102 may also include carbon nanotubes, carbon nanofibers, graphene, micro-graphites, insert molding adhesion promoter glass beads, talc, mica, coupling agents, stabilizing fillers, crystallinity promoters and anti-oxidants in varied concentrations. [0053] Formation of Pellets 106 [0054] According to an embodiment, manufacturing method 100 for battery electrodes 120 may include first extrusion process 104 where formulation components 102 such as, but not limited to, high MFI polypropylene (PP), low MFI polypropylene and carbon black may be mixed to form a first mixture. Subsequently, first mixture may be blended in an internal mixer at a blade speed of about 200 rpm, at a temperature ranging from about 300° F. to about 500° F. Graphite may be slowly added to first mixture with the remaining formulation components 102 to obtain a pre-compounded mixture. The resulting pre-compounded mixture may be extruded into pellets 106 . Suitable temperature for first extrusion process 104 of pellets 106 may vary from about 300° F. to about 500° F., while clamping pressure applied during first extrusion process 104 molding may vary from about 20 psi to about 70 psi. [0055] Second Extrusion Process 108 [0056] FIG. 3 illustrates an embodiment of second extrusion process 108 where pellets 106 may be supplied to hopper 302 and melted in heated chamber 304 which contains rotating screw 306 . Suitable temperature for heated chamber 304 may range from about 300° F. to about 500° F., with 400° F. being preferred, After heated chamber 304 , melted pellets 308 are obtained. Subsequently, melted pellets 308 may go through cooling chamber 310 which may operate at a temperature between 250° F. and 450° F., with 350° F. being preferred. Subsequently, melted pellets 308 may go through extruder 312 to obtain electrode film 110 having a uniform thickness. Extruder 312 may exert a pressure of about 50 psi. [0057] After second extrusion process 108 , electrode film 110 may undergo die cutting process 112 in order to obtain rectangular electrode sheets 114 of varied dimensions depending on the specifications needed for the flowing electrolyte batteries. [0058] Manufacturing Techniques for Coating Activation Layer 116 onto Electrode Sheet 114 [0059] There may be three techniques that can be employed for the application of activation layer 116 onto electrode sheet 114 . [0060] In one embodiment, conductive glue may be applied onto one surface of electrode sheet 114 by means of a porous roller. Subsequently, electrode sheet 114 may be immediately immersed in a fluidized bed of granular activated carbon. Afterwards, electrode sheet 114 may be dried and then pressed at temperatures ranging from about 290° F. to about 400° F., with 320° F. being preferred. [0061] In other embodiment, activation layer 116 in sheet form may be applied to electrode sheet 114 in a laminating process during second extrusion process 108 . Depending on the type of activation layer 116 employed, the process may require a transfer sheet for providing stability during the transfer process. Activation layers 116 in sheet form may include paper, felt, gas diffusion layers, among others. [0062] In another embodiment activation layer 116 may be placed or glued, by means of a porous roller, on electrode sheet 114 and then may be pressed under pressure and heat. Pressure may range from about 10 psi to about 200 psi, with 100 psi being preferred; while temperature may range from about 290° F. to about 400° F., 320° F. being preferred. This process partially submerges activation layer 116 into electrode sheet 114 , thus creating a permanent mechanical bond. [0063] After coating process of activation layer 116 , electrode sheet 114 may undergo edging process 118 where a rubber blade may be employed in order to remove activation layer / 16 from the perimeter of electrode sheet 114 and prepare electrode sheet 114 for bonding with the frame of a flowing electrolyte battery. The amount of activation layer 116 removed from electrode sheet 114 during edging process 118 may depend on the surface dimensions and bonding properties of the frame in which battery electrode 120 may be bonded. [0064] Battery Electrode 120 Properties [0065] Battery electrodes 120 manufactured employing the disclosed formulation components 102 and manufacturing method 100 may have a melt flow index ranging from about 0 gm/10 min at 230° C. 5 Kg to about 5 gm/10 min at 230° C. 5 Kg. [0066] Electrical performance of battery electrode 120 may include a bulk resistivity ranging between 0 Ω·cm and 5 Ω·cm; and a surface resistivity in ranges from 1 Ω·cm 2 to 15 Ω·cm 2 . [0067] Mechanical tests on battery electrode 120 may reveal a tensile strength between 3500 psi and 6000 psi; a tensile modulus between 500000 psi and 800000 psi; a tensile elongation ranging from about 1.0% to about 5.0%; flexural strength of about 9000 psi; a tensile strength reduction due to bromine exposure ranging from about 0% to about 10%; a tensile modulus reduction due to bromine exposure between 0% and 20%; a flexural modulus ranging from about 150000 psi to about 750000 psi; and a bromine expansion between 0.0% and 1.5%. [0068] FIG. 4 represents an illustrative embodiment of battery cell stack 400 for zinc-bromine batteries. Battery cell stack 400 may include micro-porous separators 402 , flow frames 404 , half-cell spacers 406 and battery electrodes 120 . In order to assemble battery cell stack 400 , a pair of micro-porous separators 402 which are previously bonded to flow frame 404 may be placed between two flow frames 404 containing a pair of battery electrodes 120 each. Subsequently, half-cell spacer 406 is placed between flow frames 404 containing micro-porous separators 402 and flow frames 404 containing battery electrodes 120 . Half-cell spacers 406 may be employed in order to maintain a constant cell gap and prevent the contact between battery electrode 120 and micro-porous separator 402 , thus allowing a constant electrolyte flow throughout the flow channels (not shown in FIG. 4 ) of flow frames 404 . Zinc-bromine batteries are useful transportable means for energy storage, and may include a series of battery cell stacks 400 depending on the power capacity of the battery. EXAMPLES [0069] Example #1 is an embodiment of battery electrode 120 where battery electrode 120 may exhibit the following properties: a melt flow index of fess than 1 gm/10 min at 230° C. 5 Kg, a bulk resistivity of 0.8 Ω·cm, a surface resistivity of 3.5 Ω·cm 2 , a tensile strength of 4800 psi, a tensile modulus of 660000 psi, a tensile elongation of 2.5%, a flexural strength of 9000 psi, a tensile strength reduction due to bromine exposure of less than 5%, tensile modulus reduction due to bromine exposure of less than 10%, a flexural modulus of 600000 psi, and a bromine expansion of 0.5%. In order to obtain these properties, battery electrode 120 may be manufactured using formulation components 102 containing 53% wt low MFI polypropylene, 10% wt high MFI polypropylene, 5% wt glass fiber, 5% wt carbon fiber, 10% wt graphite, 12% wt carbon black and 5% wt polyolefin elastomer. [0070] Example #2 is an embodiment of battery electrode 120 where battery electrode 120 may exhibit the following properties: a melt flow index of than 1 gm/10 min at 230° C. 5 Kg, a bulk resistivity of 2.3 Ω·cm, a surface resistivity of 10 Ω·cm 2 , a tensile strength of 4300 psi, a tensile modulus of 450000 psi, a tensile elongation of 2.2%, a flexural strength of 8600 psi, a tensile strength reduction due to bromine exposure of less than 10%, tensile modulus reduction due to bromine exposure of less than 10%, a flexural modulus of 450000 psi, and a bromine expansion of 0.5%. In order to obtain these properties, battery electrode 120 may be manufactured using formulation components 102 containing 50% wt low WWI polypropylene, 10% wt high MFI polypropylene, 5% wt glass fiber, 5% wt carbon fiber, 13% wt graphite, 10% wt carbon black and 7% wt polyolefin elastomer. [0071] Example #3 is an embodiment of battery electrode 120 where battery electrode 120 may exhibit the following properties: a melt flow index of than 1 gm/10 min at 230° C. 5 Kg, a bulk resistivity of 1.5 Ω·cm, a surface resistivity of 9 Ω·cm 2 , a tensile strength of 4300 psi, a tensile modulus of 480000 psi, a tensile elongation of 3.6%, a flexural strength of 8200 psi, a tensile strength reduction due to bromine exposure of less than 10%, tensile modulus reduction due to bromine exposure of less than 10%, a flexural modulus of 530000 psi, and a bromine expansion of 0.5%. In order to obtain these properties, battery electrode 120 may be manufactured using formulation components 102 containing 50% wt low MFI polypropylene, 10% wt high MFI polypropylene, 5% wt glass fiber, 10% wt carbon fiber, 10% wt graphite, 10% wt carbon black and 5% wt polyolefin elastomer. [0072] While various aspects and embodiments have been disclosed herein, other aspects and embodiments may be contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
An improved chemical composition and manufacturing process for a battery electrode are disclosed. This battery electrode may be later arranged in flowing electrolyte battery cells. Battery electrode material formulation may include a mixture of polypropylene, carbon black, graphite, bonding additives and other substances in different concentrations. The inclusion of graphite may reduce the amount of carbon black in the mixture, thereby reducing the swelling of the battery electrode in the presence of bromine. Moreover, material formulation may reduce warpage caused by the swelling of electrode material, and may additionally improve the performance and properties of flowing electrolyte batteries. An extrusion molding process may be employed in order to fabricate the disclosed battery electrode.
8
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application is the U.S. National Stage of International Application No. PCT/DE2005/001840 filed Oct. 15, 2005, which claims priority of German Application No. 10 2004 051 974.9 filed Oct. 25, 2004. FIELD OF THE INVENTION [0002] The present invention relates to a knife holder for microtome blades, the knife holder being of a type having a body including an abutment surface, and a pressure plate connected to the body and adjustable relative to the body for clamping a microtome blade received against the abutment surface. BACKGROUND OF THE INVENTION [0003] Microtomes serve to produce thin sections of various samples in the fields of medicine, biology, and botany, materials research, and quality control of engineering materials. These thin sections are produced with knives of different configurations and types. Steel knives made of selected tool steels, manufactured with various types of edge grinding, are known. In addition to these solid regrindable knives, blade-like cutting knives (so-called disposable blades) are widely used. Disposable blades are usually replaced by new ones once their service life has been exceeded. In addition, glass knives and diamond knives are in use for specific applications. [0004] For all types of knife, a plurality of knife carriers and knife holders are known in microtome technology; these additionally differ, in terms of their configuration, depending on the type of microtome for which they are provided. The knife holders that are used perform the principal function of retaining the particular microtome blade in stable fashion in order to achieve the desired sectioning result. [0005] A knife holder having a pressure plate for retaining a blade-like cutting knife is known from DE 44 35 072 C1. The knife holder contains a body and a retaining jaw having an abutment edge on which the back side of the cutting knife rests. The cutting knife is pressed, with the pressure plate, against the retaining jaw. The length of the abutment edge can be greater than the length of the cutting knife. By appropriate positioning of the cutting knife along the abutment edge, a respectively sharper region of the blade cutting edge can be associated with the specimen to be sectioned. [0006] A knife holder for a solid regrindable wedge-shaped steel knife is depicted and described in DE 195 06 837 C1. The steel knife of itself generally exhibits sufficient stability that it is usually retained only in its end regions. [0007] In addition to a stable retaining system that is intended to prevent vibrations at the knife, most knife holders possess devices for setting the relief angle between the knife cutting edge and sample. A device of this kind can be made up, for example, of a circular-segment curved member mounted pivotably on a base, on which member the body of the knife holder is secured. When a user is working with microtomes, the risk always exists of cutting injuries to his or her hand because the blade cutting edge of the microtome knife protrudes from the knife holder. Especially in the context of sample changes, the operator must manually exchange, in the vicinity of the microtome knife, sample cassettes that are located in a clamping system. To avoid injuries, the blade length selected is preferably so short that it does not project laterally from the body. In the retained state, only the blade edge protrudes out of the body. In addition, knife holders can comprise a so-called finger protector. A finger protector of this kind can be made up of a rectangular frame, articulated pivotably on the body of the knife holder, whose bridge joining the two limbs of the U extends, in one end position, over the blade cutting edge and thereby prevents inadvertent contact against the blade cutting edge. A finger protector of this kind may be inferred, for example, from DE 198 24 024 A1. [0008] The risk of injury to the operator is greatest, however, when the maximum service life of the cutting knives has been reached, i.e. they no longer have the sharpness necessary for thin sections and must be replaced. For this, the finger protector must be swung back, the pressure plate must be released, and the microtome blade must be pushed laterally out of the knife holder, using an aid such as a brush handle or the like, until the blade can be grasped with the fingers. To simplify this cumbersome procedure while avoiding the need for assistance from additional aids, in known knife holders the blade length was often selected, specifically in the case where disposable blades were used, so that in the retained state it protrudes to the left and right, but at least on one side, beyond the width of the body with its pressure plate, so as thereby to be more easily graspable. A disadvantage here is that because stable retention is lacking, the microtome knife is not usable in the projecting peripheral region, and this simultaneously constitutes an additional source of risk during the cutting operation and when samples are changed. SUMMARY OF THE INVENTION [0009] It is therefore the object of the present invention to make available a knife holder for microtome blades in which on the one hand the risk of injury is reduced as much as possible, and on the other hand worn-out microtome blades can easily be brought, without additional separate aids, into a position in which they are easily graspable outside the blade cutting edge. [0010] This object is achieved according to the present invention, in the context of a knife holder of the kind cited initially, in that an ejection apparatus, associated with one side edge of the blade cutting edge, is connected to the body. Advantageous refinements of the knife holder according to the present invention are the subject matter of the dependent claims. [0011] The ejection apparatus is equipped for this purpose with an ejection element acting on the blade cutting edge. As long as the ejection apparatus is not actuated by the operator, a spring element holds the ejection element in the idle position outside the side edge. A configuration of the ejection apparatus as a lever mechanism, having a flat ejection lever whose thickness is adapted to the blade thickness, is advantageous. The flat ejection lever can thus be brought, as soon as the pressure plate is released, into working engagement against one of the side edges of the blade. Assuming that complete ejection of the microtome blade is acceptable, it is also possible, in the context of a corresponding configuration of the body, for the ejection lever to act on the lower edge of the microtome blade. [0012] In a further embodiment of the invention, the ejection apparatus contains a plunger mechanism whose plunger head is directed onto a side edge of a protruding cutting edge portion of the blade. A “side edge of a protruding cutting edge portion of the blade” is understood as the region of the microtome blade that, in the retained state, protrudes freely out of the knife holder adjacently to the blade cutting edge. Upon actuation of the plunger mechanism, a motion tangential to the abutment edge of the microtome blade is imparted to a generally pin-shaped plunger, the plunger head is brought into working engagement with the side edge of the protruding cutting edge portion of the blade, and the microtome blade is thus ejected laterally. Because of the orientation of the plunger head with respect to the side edge of the protruding cutting edge portion of the blade, the plunger head can be dimensioned with a larger area. This facilitates alignment of the ejection apparatus. [0013] It is particularly advantageous in this connection to provide, as the actuation element of the plunger mechanism, a pushbutton that is under a spring load and is rigidly joined to the plunger. The spring load can be generated by a variety of spring elements. A helical spring wound around the plunger offers particular advantages in terms of compactness and maximum displacement travel of the plunger mechanism. The ejection apparatus can of course be fixedly joined to the body at any region of the knife holder, provided the microtome blade can be brought, by the actuation of said apparatus, into a position in which it can be securely grasped by the operator. [0014] Further advantages are offered by an arrangement according to the present invention in which a rectangular frame that is pivotable via the pressure plate is connected to the body in such a way that in an end position above the blade cutting edge, the frame's bridge rests on the pressure plate, the ejection apparatus being arranged on the frame in the region of the bridge. The frame can be embodied in such a way that when sections are being produced, its bridge covers the blade cutting edge in such a way that contact therewith is effectively prevented, and said frame thus functions as a finger protector. As soon as the pressure plate is released, a used microtome blade can be ejected laterally from the knife holder by actuation of the ejection apparatus, without exposing the operator to the risk of contacting the blade cutting edge. As soon as the microtome blade has been laterally ejected far enough, it can be grasped for blade-changing purposes and removed. If the blade should not have been ejected far enough beneath the frame, the frame can be swung back; this on the one hand simplifies lateral removal of the used blade, and on the other hand additionally and advantageously exposes the knife holder for introduction of a new microtome blade. BRIEF DESCRIPTION OF THE DRAWINGS [0015] An exemplifying embodiment of the knife holder according to the present invention is depicted schematically in the drawings and will be described in further detail below with reference to the Figures, further advantages being presented. In the drawings: [0016] FIG. 1 shows a knife holder with a frame swung downward; [0017] FIG. 2 shows the knife holder with a frame swung upward; [0018] FIG. 3 shows a microtome blade pushed out laterally; [0019] FIG. 4 is a rear view of the knife holder, with the ejection apparatus in the idle position; [0020] FIG. 4A is a partial rear view of the knife holder, showing an ejection apparatus formed in accordance with an alternative embodiment of the invention, in the idle position; [0021] FIG. 5 shows an ejection apparatus in the pushed-in state; [0022] FIG. 6 is a rear view of the knife holder as in FIG. 3 ; [0023] FIG. 7 shows a detail of a lateral view of the knife holder; and [0024] FIG. 8 shows a section through the ejection apparatus. DETAILED DESCRIPTION OF THE INVENTION [0025] FIG. 1 is a view of a knife holder 1 according to the present invention in which a microtome blade 2 abuts against an abutment edge 4 and is clamped in between body 3 and pressure plate 5 with the aid of a clamping toggle 16 . The length of microtome blade 2 is selected to be sufficiently short that it is retained over its entire length and is thus completely usable. Only blade cutting edge 6 protrudes out of knife holder 1 . In order to make blade cutting edge 6 usable over its entire length, body 3 is laterally displaceable on a segmental curved member 17 parallel to blade cutting edge 6 . Segmental curved member 17 is mounted, in known fashion, pivotably along its cylindrical rear surface on a base 18 , so that the so-called relief angle, i.e. the orientation of microtome blade 2 relative to the specimen (not depicted further) to be sectioned, is adjustable. [0026] Articulated on pressure plate 5 is a rectangular frame 14 that is pivotable about a pivot axis 19 and is in a swung-back position. A ejection apparatus 8 is mounted on one side of bridge 15 that connects the two limbs of the U. Ejection apparatus 8 is made up of a guide 20 in which pushbutton 13 , joined rigidly to an ejection element in the form of a plunger 12 , is movably mounted. The axis of plunger 12 proceeds parallel to abutment edge 4 . [0027] FIG. 2 shows knife holder 1 with a frame swung upward. In this end position, bridge 15 extends over microtome blade 2 (not visible in this depiction) and thus prevents inadvertent contact with the otherwise exposed blade cutting edge 6 . As a result of inward pressure on pushbutton 13 which is under spring load, plunger 12 is displaced in the direction of microtome blade 2 , plunger head 10 is brought into working engagement with microtome blade 2 , and the latter is ejected by further inward pressure. [0028] In FIG. 3 , microtome blade 2 is illustrated in an ejected position. It protrudes laterally beyond body 3 sufficiently far that it can easily be grasped by the operator for complete removal. Frame 14 is once again in the same position as depicted in FIG. 1 . [0029] The rear view of knife holder 1 depicted in FIG. 4 shows frame 14 swung upward, with ejection apparatus 8 mounted thereon in the idle position as in FIG. 2 . Pushbutton 13 and plunger 12 constitute an axis that proceeds through guide 20 . [0030] FIG. 4A shows knife holder 1 having an ejection apparatus 8 ′ formed according to an alternative embodiment wherein an ejection element (plunger 12 ′) is carried by a lever 22 and includes a plunger head 10 ′ for engaging a side edge of the protruding cutting edge portion of blade 2 . Lever 22 is pivotally mounted on a leg of frame 14 by a pivot pin 23 , and a detent pin 26 is arranged on the leg of frame 14 to limit pivotal movement of the lever. As may be understood, lever 22 can be pivoted in a counter-clockwise direction as shown in FIG. 4A to cause plunger head 10 ′ to engage blade 2 . A spring element, not visible, may be provided to bias lever 22 in a clockwise direction to maintain plunger 12 ′ in an idle position away from contact with the blade when the ejection apparatus 8 ′ is not in use. For example, a torsion spring at pivot pin 23 , or a compression or extension spring between lever 22 and frame 14 , may be used. [0031] FIG. 5 shows knife holder 1 in a further rear view; pushbutton 13 is pushed completely into ejection apparatus 8 and plunger 12 therefore protrudes well out of the guide. Microtome blade 2 is in an ejected position. [0032] FIG. 6 depicts knife holder 1 with an ejected microtome blade 2 . Pivotable frame 14 is in a swung-down position and thus exposes the laterally ejected microtome blade 2 to be grasped by the operator. [0033] FIG. 7 shows an enlarged side detail of knife holder 1 looking perpendicularly at plunger head 10 . The end surface of plunger head 10 is associated with a side edge 7 ( FIG. 1 ) of a protruding cutting edge portion 11 of microtome blade 2 . Guide 20 , mounted on frame 14 in the region of bridge 15 , is clearly visible in the enlarged view. [0034] FIG. 8 depicts ejection apparatus 8 in section. Pushbutton 13 is rigidly joined to plunger 12 via a threaded connection 21 . In guide 20 , a spring element 9 generates a preload that holds the plunger head, in the idle position, in abutment against guide 8 . PARTS LIST [0000] 1 Knife holder 2 Microtome blade 3 Body 4 Abutment edge 5 Pressure plate 6 Blade cutting edge 7 Side edge 8 , 8 ′ Ejection apparatus 9 Spring element 10 , 10 ′ Plunger head 11 Protruding cutting edge portion of blade 2 12 , 12 ′ Plunger 13 Pushbutton 14 Frame 15 Bridge 16 Clamping toggle 17 Segmental curved member 18 Base 19 Pivot axis 20 Guide 21 Threaded connection 22 Lever 23 Pivot pin 24 Knob 26 Detent pin
A knife holder ( 1 ) for microtome blades ( 2 ) is described, which holder has a body ( 3 ) for reception of the blade ( 2 ) against an abutment edge ( 4 ) and a pressure plate ( 5 ) for retention of the blade, such that in the retained state, only the blade cutting edge ( 6 ) protrudes from the body ( 3 ), and an ejection apparatus ( 8 ), associated with one side edge ( 7 ) of the blade cutting edge ( 6 ), is arranged on the body ( 3 ).
8
FIELD OF THE INVENTION [0001] This invention relates to an Applied Kinesiology method for curing mild Multiple Sclerosis, memory impairment and Seasonal Affective Disorder. BACKGROUND [0002] Seasonal Affective Disorder (“SAD”) is a phenomenon whereby many people become sad and depressed during the winter months. People tend to have elevated levels of melatonin in their bodies during the winter months due to the lesser amount of daylight in the winter months. Melatonin is a chemical that is generated by the body in dark conditions. During the winter months there is less daylight, which leads to the body's production of greater amounts of melatonin, and thus to the body having an elevated melatonin level in the dark, winter months. [0003] The inventor, an applied kinesiologist, has found that people who suffer from SAD have a sensitivity to the elevated melatonin level in their body, which causes them to have an allergic type reaction of depression. SAD, the inventor hypothesizes, is caused by the body's allergic type reaction to the elevated melatonin level, which manifests itself as depression. Prior methods for attempting to treat SAD have recognized that SAD is connected with, inter alia, elevated melatonin levels in the body and have tried to decrease the melatonin levels by exposing SAD patients to artificial light sources to compensate for the lack of sunlight exposure. See, for example, U.S. Pat. No. 5,447,528 by Gerardo. [0004] The inventor herein has invented a method for curing SAD, by desensitizing SAD patients to melatonin using allergy desensitization techniques that are known in the field of applied kinesiology. The inventor has found that his patients who suffered from SAD had improved in their condition after desensitizing those patients to melatonin. [0005] Patients with SAD will show sensitivity to melatonin. This sensitivity may be detected by use of well known Applied Kinesiology methods for testing for the temporary weakening of a patient's muscles. As in known in the field of applied kinesiology, when a patient is exposed to a substance that the patient is sensitive to, which in the case of a patient suffering from SAD is melatonin, the patient's muscles will be temporarily weakened. [0006] The muscle weakness test may involve simply having a patient hold a homeopathic vial containing melatonin in the patient's hand, while the clinician then manually tests the patient's muscle strength. For example, the clinician can test for changes in the patient's ability to hold up the patient's elbow while the clinician tries to push the patient's elbow downward. The clinician can more easily press down the SAD patient's elbow when the SAD patient holds in his/her hand a homeopathic vial containing melatonin. [0007] The inventor further found that all of his patients who suffer from SAD also show an allergic type sensitivity to myelin. The allergic type sensitivity to myelin can be treated by using the same applied kinesiology technique, only with myelin rather than melatonin. The allergic type reaction to myelin causes upper neural lesioning of myelinated nerves, which impairs the patient's memory and causes mild Multiple Sclerosis. Desensitizing the patient to myelin will cure the memory impairment and the mild Multiple Sclerosis. [0008] The inventor's hypothesis is that the SAD patient's allergic type reaction to melatonin results from and stems from the patient's allergic type reaction to myelin. The allergic type reaction to myelin causes upper neural lesioning of myelinated nerves. During the day, when a patient is conscious, there is a conscious avoidance by the patient's body of weak pathways for transmission of information, i.e. an avoidance of damaged myelinated nerves for transmission of information. However at night time, when a patient sleeps and dreams, there is no conscious avoidance of weak pathways for transmission of information over myelinated nerves, and memories are more apt to attempt to travel through the diseased, myelin attacked nerves. At night time there is also an increased presence of melatonin in the body, which functions in the body quantitatively more at night and during sleep. The body thus comes to associate the elevated melatonin level with disfunction, i.e. with the attempted transmission of memories over damaged, myelinated nerves. The body's association of melatonin with disfunction leads the body to want to attack the melatonin, leading the body to develop an allergic type reaction to melatonin develops. The allergic type reaction causes SAD. [0009] As stated above, the effect of the allergic type reaction to myelin in the patient is memory loss and mild Multiple Sclerosis. The mild Multiple Sclerosis can usually be clinically observed by the symptom of the patient having a weak tibialis anticus, often with cog-wheel rigidity illicit on a second muscle test. For example, first the strength of a patient's right tibialis anticus is tested, and will test strong. Immediately afterwards the strength of the left tibialis anticus is tested, and will test weak. Cog-wheel rigidity is when on passive motion of a limb the examiner feels the patient's muscular resistance as a series of jerks, alternating with periods of arrest. After a patient is desensitized to myelin, the patient's cog-wheel rigidity will disappear completely. SUMMARY OF THE INVENTION [0010] To cure a patient from mild Multiple Sclerosis, memory impairment and SAD, an allergy desensitization technique is used to desensitize a patient to myelin and melatonin. The allergy desensitization technique is performed as if the patient were allergic to myelin and melatonin. The myelin and melatonin may, though need not, be combined into a single homeopathic vial. DESCRIPTION OF THE PREFERRED EMBODIMENT [0011] The curative method for mild Multiple Sclerosis, memory impairment and SAD may be implemented by use of any of a number of allergy desensitization techniques. The preferred allergy desensitization technique known to the inventor for implementing the method for curing SAD is a laser desensitization technique. This technique, in a slightly different form, was originally developed by Dr. Michael Lebowitz. The technique as originally developed by Dr. Lebowitz involved having a patient put an allergen in his mouth or on his philtrum (above the upper lip), muscle testing a previously weak muscle and then applying a laser to four points on the patient's head. The clinician would then test the patient's muscle strength, now showing strength. The clinician would next place a drop of the patient's own blood on the patient's tongue or philtrum, retest the muscle (showing weakness again) and again apply the laser on the four points. [0012] The inventor found as a practical matter that his patients did not like having blood drawn from them, even a small drop. The inventor thus improved upon Dr. Lebowitz' technique by using the patient's saliva placed on the patient's philtrum, rather than the patient's blood. Some of the patient's saliva is collected on a cotton applicator (commonly know as a Q-tip), and the cotton applicator is then placed on the patient's philtrum (the groove just above the center of the upper lip) while the laser is applied to the four points. [0013] The laser should be a red laser of wavelength 635 nm, 650 nm or 675 nm. Other frequencies may also be effective. The patient holds in his/her hand a closed homeopathic vial containing the myelin and melatonin. While the patient holds the vial in his/her hand, (this causes a strong muscle to weaken for a patient with SAD) a laser is applied at four points: just above the two eyebrows, at the anterior fontanel (also called governing vessel 21) and at the posterior fontanel (also called governing vessel 20). The patient's muscle strength is then retested, (showing strong). Now a cotton applicator, dampened by the patient's saliva, is placed on the patient's philtrum, while patient holds the vial (muscle tests weak again) and the laser is again applied to the four point: just above the two eyebrows, at the anterior fontanel (also called governing vessel 21) and at the posterior fontanel (also called governing vessel 20). The muscle is retested, showing strength again. [0014] An alternative allergy desensitization technique that may be used involves applying pressure to a patient's eyes. This technique is fully described in “The Thirty-Second Allergy Cure,” Collected Papers of the Members of the International College of Applied Kinesiology—U.S.A., Volume I, 1988-89, by Harvey Lang. As will be obvious to those skilled in the art, other desensitization techniques may also be used in place of the laser technique, as part of the method for curing SAD. [0015] There is a causative condition of mercury toxicity that has to also be dealt with because it effects the permanence or relative permanence of the cure. There are known drugs, such as Metaplex by Thorne Reasearch, Inc., or Mercury Detox by Tyler (Integrated Therapeutics, Inc.), or even the use of the herb Cilantro, that can be used for correcting mercury toxicity. It is the overload of mercury in the patient's system that generally will cause the allergic type reaction to myelin. [0016] With respect to memory loss, a muscle test can be performed using physical contact with known memory drugs both to diagnose the condition and to show that desensitization to myelin worked to cure the condition. Known memory drugs such as phosphatidylserine capsules, donepezil hydrochloride tablets or aricept phosserine (the “Memory Drugs”) can be used for the muscle test. The clinician elicits a weak muscle from the patient, and observes that the patient's physical contact with the Memory Drugs then cause the weak muscle to strengthen only in patients who suffer from memory impairment. After a patient is desensitized to myelin, the Memory Drugs will no longer cause the weak muscle to strengthen in those same patients, showing that the memory impairment is cured and that the body no longer has need for the Memory Drugs because it is cured. [0017] It is important to point out, however, that not all patients that have a sensitivity or allergy to myelin and melatonin will exhibit the need for Memory Drugs.
A method for curing mild Multiple Sclerosis, memory impairment and Seasonal Affective Disorder. An Applied Kinesiology technique, used to desensitize a patient to allergies, is used to desensitize a patient to myelin and melatonin. Desensitizing the patient to myelin and melatonin cures mild Multiple Sclerosis, memory impairment and Seasonal Affective Disorder.
0
BACKGROUND OF THE INVENTION This invention relates to an interconnected combustion system and more particularly to a cross-ignition assembly for interconnecting adjacent combustors in a gas turbine. A combustion system for a gas turbine commonly includes a number of generally cylindrical combustors disposed about the turbine in an annular arrangement, with each combustor supplying a motive fluid to an arcuate section of a turbine nozzle. It is common practice to interconnect the combustion chambers of adjoining combustors by means of short conduits or "cross-fire tubes" as part of a cross-ignition assembly, the purpose of which is to provide for the ignition of fuel in one chamber from ignited fuel in an adjacent chamber in order to obviate the need for providing a spark plug or the like for each combustor. Additionally, the cross-ignition assembly to some extent also effects an equilization of pressures in adjacent combustors. A conventional cross-ignition assembly includes cross-fire tubes extending between adjacent combustors. The cross-fire tubes are generally held in place by mounting means which position the opposite ends of the cross-fire tubes in fluid passages formed in the combustion chambers. However, in some such conventional arrangements, the mounting means can inaccurately position the tube ends with respect to the combustion chambers, extending them too far into the combustion gas flow paths therein. This results in damage of cross-fire tubes in the form of end burning. Additionally, cross-fire tubes are often loosely retained in their respective mounting means and are subject to vibration and rotation therein. Typically these mounting means are also loosely affixed to their respective combustor housings or combustion chamber liners, and they are induced to vibrate therein by the oscillation of the retained cross-fire tubes. Such vibration of cross-fire tubes and the mounting means has been found to cause wear and distortion in the cooperating combustor housings and chamber liners, requiring their repair or replacement. The maximum operating temperature of a cross-fire tube is typically located at its midsection. This is also the most highly stressed structural section of a tube in a conventional cross-ignition assembly wherein the tube is supported at both ends. This combination of temperature and stress makes the cross-fire tube prone to collapse at its midsection. Upon collapse of a cross-fire tube, the combustion gases normally channeled thereby between adjacent combustors may be released to impinge upon the combustor housings. In the past this has lead to overheating and rupture of combustor housings. In an attempt to lower the operating temperature at the midsection of the cross-fire tube, cooling holes or apertures have been provided around the midsection to enable cooling air to enter the tube at that section; however, the cooling obtained by this approach is non-uniform. Additionally, attempts have been made to locate the critical structural sections of cross-fire tubes away from their midsections. This typically has involved use of a cantilever support design wherein the tube members are welded to combustor housings. Such an assembly is disclosed in U.S. Pat. No. 3,001,366 issued Sept. 26, 1961, to L. W. Shutts. However, the welding of a cross-fire tube to a combustor housing gives rise to costly weld repairs, made necessary by thermal cracking or handling damage at the welds, which complicates cross-fire tube replacement. Furthermore, combustor maintenance in a conventional interconnected combustion system requires that the cross-fire tube ends cooperating with the combustor of interest be withdrawn therefrom. In those systems employing single piece cross-fire tubes, the withdrawl of the tubes from one combustor necessitates their further insertion into the adjacent interconnected combustors. This in turn requires the disassembly of the mounting means in the interconnected combustors in order to obtain access to the combustor of interest, which procedure greatly complicates maintenance efforts. Accordingly, an object of the present invention is to provide a new and improved cross-ignition assembly for interconnecting adjacent combustors in a gas turbine. Another object of the present invention is to provide a new and improved cross-ignition assembly including a cross-fire tube especially adapted for facilitating combustion system maintenance. Another object of the present invention is to provide a new and improved cross-ignition assembly for reducing cross-fire tube end burning and vibration induced wear problems. Still another object of the present invention is to provide a cross-ignition assembly including improved means for supporting the ends of the cross-fire tube and for cooling the midsection thereof in a manner effective for preventing tube collapse and the attendant damage to combustor housings. SUMMARY OF THE INVENTION The above and other objects and advantages are achieved in a cross-ignition assembly comprising a pair of mounting means disposed about aligned fluid passages of adjacent combustors and a pair of coaxial telescoping cross-fire tube members each having its outer end positioned in one of the mounting means and releasably held therein by a leaf spring. Thusly, each of the tube sections is mounted in a cantilever fashion on a respective combustor. The tube members and mounting means are constructed and arranged to define an air passage in the mounting means allowing cooling air to flow along the exterior of the cross-fire tube through a channel defined by a sleeve surrounding the cross-fire tube and extending between the combustors. This flow of air is also caused to flow into the interior of the cross-fire tube through an annular space provided between the telescoping portions of the tube members. The outer one of the telescoping tube members has a reduced cross-section which defines a shoulder adjacent the mentioned annular space and which is effective to alter the direction of the air flow such that it is directed along the interiors of both tube members toward the outer ends of the cross-fire tube. Additionally, each of the springs is of a predetermined length terminating with an end tab which cooperates with an orientation means affixed to each combustor such that the spring tab is received and releasably retained by the orientation means only when it is in a predeterminately oriented position operatively engaged with the cross-fire tube. BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the invention reference may be had to the acccompanying drawings wherein: FIG. 1 is an aft transverse view of a segment of an interconnected combustion system employed in a gas turbine; FIG. 2 is a partial sectional view of a cross-ignition assembly constructed in accordance with an embodiment of the invention; FIG. 3 is a fragmentary sectional view of a portion of the cross-ignition assembly of FIG. 2 taken along line 3--3 in FIG. 1 and looking in the direction of the arrows; FIG. 4 is a perspective view of a cross-fire tube end and a mounting plate shown prior to assembly; FIG. 5 is a view taken along line 5--5 in FIG. 3, looking in the direction of the arrows and illustrating a leaf spring in supporting engagement with a cross-fire tube section; and FIG. 6 is a perspective view of a flow sleeve illustrating a flanged end thereof apertured to receive and retain the ends of properly oriented leaf springs. DESCRIPTION OF THE INVENTION Illustrated in FIG. 1 is a segment of a combustion system comprising three of a usually greater plurality of cylindrical combustors 1 arranged in spaced relation about a turbine not shown. One of the combustors 1 is provided with a spark plug assembly 2 for igniting a mixture of fuel and air in a combustion chamber therein. Cross-ignition assemblies generally designated 3 are positioned between adjacent combustors in alignment with combustion chamber fluid passages 4 contained therein and seen in FIGS. 2 and 3. Cross-fire tubes 5 included in the cross-ignition assemblies 3 have ends positioned in respective combustion chamber fluid passages 4. Thusly, the tubes 5 are adapted to serve as conduits between adjacent combustors to enable hot combustion gases of one combustor to ignite the fuel-air mixture in the combustion chamber of an adjacent combustor 1. This arrangement obviates the need for additional spark assemblies 2. Both ends of the cross-fire tubes are mounted in the same manner and thus for simplicity of disclosure the mounting of only one end will be described. Accordingly, it is to be understood from FIGS. 2 and 3 that each end of a telescoping cross-fire tube 5 is accurately positioned in a combustion chamber fluid passage 4 through an abutting cooperative relationship with respect to a mounting means 6. By means of this arrangement the over-insertion of the tube end into a combustion gas flow path in the combustion chamber and resultant tube end burning is prevented. The cross-fire tube 5 is also thereby centered in aligned apertures of a combustor housing 7, a flow sleeve 8 and a combustion chamber liner 9 all of which are parts of each combustor 1. Each of the mounting means 6 comprises an annular mounting plate centered about an aperture in one of the combustor housings 7 to which it is securely affixed. Thus, the wear and distortion that might otherwise be caused by the vibration of loosely affixed mounting means is avoided and the accurate positioning of the cross-fire tube by the mounting means 6 is further assured. The abutting relationship between each cross-fire tube 5 and its respective mounting plate 6 is accomplished by the provision of a counterbore 10 in each mounting plate and a shoulder 11 formed on each end of the cross-fire tube and which is adapted to be seated in one of such counterbores. Each shoulder 11 is disposed in a spaced relation with a second shoulder 12 which together define a spring retaining slot 13. In a preferred embodiment of this invention depicted in FIG. 4, a central opening 14 in the mounting plate 6 is constructed in the form of diametrically opposed arcs 15 joined by parallel chords 16, and the cross-fire tube shoulders 11 and 12 are similarly configured. Furthermore, the opening 14 in the mounting plate is dimensioned such that during assembly, shoulder 11 can be inserted through its respective mounting plate opening 14, and the end of the cross-fire tube 5 can be rotated 90 degrees about the retaining slot 13 before the tube end is further inserted to place shoulder 11 in its operative position seated in and abutting the bottom of the mounting plate counterbore 10. As depicted in FIGS. 3 and 5, each cross-fire tube end is retained in its operative position by a leaf spring 17. Each of the retaining leaf springs comprises two substantially parallel prongs 18 straddling the end of the cross-fire tube 5 in the retaining slot 13 formed thereon, and in resilient engagement with both the cross-fire tube shoulder 12 and the associated mounting plate 6. The leaf spring 17 also includes a third prong or detent 19 located intermediate the parallel prongs 18 and cooperating with a flattened portion 20 on the outer shoulder 12 of a retained cross-fire tube end to restrain rotation thereof. The leaf spring 17 is inserted into its operative position through an aperture 21 formed in a flange 22 on the combustor flow sleeve 8. As depicted in FIG. 6, the apertures 21 are each complimentarily configured with respect to an end tab 23 on each of the leaf springs 17 to allow the insertion of the respective spring only when it is properly oriented for effectively engaging and retaining a cooperative end of the cross-fire tube 5. Furthermore, each leaf spring 17 is of a predetermined length from the detent 19 to its termination at the end tab 23 such that the end tab 23 is securely seated in its respective aperture 21 in the flange 22 when the leaf spring 17 is operatively positioned. As best seen in FIGS. 3 and 4, each cross-fire tube inner shoulder 11 cooperates with the central opening 14 in a respective mounting plate 6 to define cooling air passages 24 therebetween. The cooling air passages 24 allow air to flow outwardly from an annular region 25 defined by the combustor housing 7 and the combustion chamber liner 9. Cooperating with the cooling air passages 24 disposed in adjacent interconnected combustors 1 is a bolted sleeve 26 which is an integral part of combustor housing 7. The bolted sleeve 26 is positioned in a spaced relation about the associated cross-fire tube 5 and disposed between the respective mounting plates 6. The bolted sleeve 26 channels air flowing through the cooling air passages 24 across the exterior of the surrounded cross-fire tube 5. Each cross-fire tube 5 also includes an annular space 27 defined by the exterior of a male cross-fire tube member 28 and the interior of an expanded portion or larger diametered section 29 of a telescopically cooperating female cross-fire tube member 30. In this arrangement, the aforementioned cooling air flows through the annular space 27 and into the interior of the cross-fire tube 5 for the effective cooling thereof. Additionally, the female cross-fire tube member 30 is formed with an internal shoulder 31 at the termination of the annular space 27 to redirect the cooling air flowing therethrough. In this manner the air which would normally flow toward the outer end of the tube member 30 is directed into the interior of the cross-fire tube 5 wherein it is substantially equally distributed toward both ends of the cross-fire tube 5 by a pressure drop in each combustion chamber. Thusly, the combustors in a combustion system for gas turbines are interconnected by means of cross-fire tubes 5 comprising telescoping tubular sections or members 28 and 30 accurately positioned by the mounting plates 6 with respect to combustion chamber fluid passages 4. Each of the retaining leaf springs 17 resiliently engages the shoulder 12 of one of the cross-fire tube members and the respective mounting plate 6 to effect an independent cantilever support for each of the tubular members comprising the cross-fire tube 5. Additionally, the cooling air flowing from the annular region 25 through the cooling air passage 24 and into the cross-fire tube interior through the annular space 27 provides cooling for both the exterior and the interior of each cross-fire tube. From the foregoing, it will be seen that the present invention comprises an accurately and securely positioned cross-ignition assembly including coaxially telescoping, cantilever supported tube members which avoids those problems of cross-fire tube end burning and of component wear and collapse attendant the use of conventional designs and facilitates combustion system maintenance. The above-described embodiment of this invention is intended to be exempletive only and not limiting, and it will be appreciated from the foregoing by those skilled in the art that many substitutions, alterations, and changes may be made to the disclosed structure without departing from the spirit or scope of the invention.
A cross-ignition assembly with a cross-fire tube supported intermediate two adjacent combustors by mounting plates affixed thereto so as to provide a conduit for the flow of hot combustion gases therebetween. The cross-fire tube comprises coaxial telescoping tubular members. A leaf spring retains the outer end of each tubular member in its operative position to effect a cantilever support for each end of the cross-fire tube. A series of cooperating air passageways and channels allow cooling air to flow across the outside and along the inside of the cross-fire tube.
5
CROSS-REFERENCE TO RELATED PATENT APPLICATION This is a Continuation of U.S. patent application Ser. No. 10/449,526, filed May 30, 2004, which application is incorporated herein in its entirety by reference, and which application in turn claims priority under 35 USC section 119(e) to U.S. Provisional Application Ser. No. 60/384,478, filed May 31, 2002, which application is also incorporated by reference herein as if fully set forth. FIELD OF THE INVENTION The invention relates to a process for preparing polycyclic xanthine phosphodiesterase V (“PDE V”) inhibitors. The invention further relates to compounds useful for preparing PDE V inhibitors. BACKGROUND Processes for preparing PDE V inhibitor compounds can be found in U.S. Pat. No. 6,207,829, U.S. Pat. No. 6,066,735, U.S. Pat. No. 5,955,611, U.S. Pat. No. 5,939,419, U.S. Pat. No. 5,393,755, U.S. Pat. No. 5,409,934, U.S. Pat. No. 5,470,579, U.S. Pat. No. 5,250,534, WO 02/24698, WO 99/24433, WO 93/23401, WO 92/05176, WO 92/05175, EP 740,668 and EP 702,555. One type of PDE V inhibitor compound contains a xanthine functionality in its structure. Xanthines can be prepared as described by Peter K. Bridson and Xiaodong Wang in 1- Substituted Xanthines, Synthesis, 855 (July, 1995), which is incorporated herein by reference in its entirety. WO 02/24698, which is incorporated herein by reference in its entirety, teaches a class of xanthine PDE V inhibitor compounds useful for the treatment of impotence. A general process disclosed therein for preparing xanthine PDE V inhibitor compounds having the formula (I) follows: (i) reacting a compound having the formula (III) with an alkyl halide in the presence of a base (introduction of R II or a protected form of R II ); (ii) (a) debenzylating and then (b) alkylating the compound resulting from step (i) with an alkyl halide, XCH 2 R III ; (iii) (a) deprotonating and then (b) halogenating the compound resulting from step (ii); (iv) reacting the compound resulting from step (iii) with an amine having the formula R IV NH 2 ; and (v) removing a protecting portion of R II , if present, on the compound resulting from step (iv) to form the compound having the formula (I). R I , R II , R III and R IV correspond to R 1 , R 2 , R 3 and R 4 , respectively, in WO 02/24698, and are defined therein. WO 02/24698 (pages 44 and 68-73) also teaches a synthesis for the following xanthine compound (identified therein as Compound 13 or Compound 114 of Table II): 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione: It would be beneficial to provide an improved process for preparing polycyclic xanthine PDE V inhibitor compounds. It would further be beneficial if the process provided high yields without the need for chromatographic purification. It would still further be beneficial if the process provided compounds of high thermodynamic stability. It would be still further beneficial to provide intermediate compounds that can be used in the improved process. The invention seeks to provide these and other benefits, which will become apparent as the description progresses. SUMMARY OF THE INVENTION One aspect of the invention is a method for preparing a Compound 13, comprising: (a) reacting glycine ethyl ester or a salt thereof with  to form  wherein Et is CH 3 CH 2 —, (b) reducing  to form a Compound 1: (c) reacting cyanamide with an excess of triethylorthoformate to form a Compound 2: (d) reacting the Compound 2 with the Compound 1 to form a Compound 3: (e) reacting the Compound 3 with a base to form a Compound 4: (f) reacting the Compound 4 with R 2 NHCO 2 R 1 in the presence of a metallic base to form a Compound Salt 5K:  wherein M + is a metal ion, (g) optionally, reacting the Compound Salt 5K with an acid to form a Compound 5: (h) reacting the Compound Salt 5K or the Compound 5 with BrCH 2 L in the presence of a phase transfer catalyst to form a Compound 6: wherein L is R 3 or a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl; (i) dihalogenating the Compound 6 to form a Compound 7: (j) reacting the Compound 7 with R 4 NH 2 , and adding a base thereto, to form a Compound 9: (k) (i) when L is R 3 , the Compound 9 is a Compound 13, and (ii) when L is a protected form of R 3 , reacting the Compound 9 with a base to form the Compound 13: wherein, R 1 , R 2 and R 3 are each independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, allyl, —OR 5 , —C(O)OR 5 , —C(O)R 5 , —C(O)N(R 5 ) 2 , —NHC(O)R 5 and —NHC(O)OR 5 , wherein each R 5 is independently H or alkyl; provided that R 2 and R 3 are not both —H; R 4 is an alkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group; wherein R 1 , R 2 , R 3 and R 4 are optionally substituted with one or more moieties independently selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl, halo, thio, nitro, oximino, acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 , —OR 50 , —NR 50 R 51 , —C(O)OR 50 , —C(O)R 50 , —SO 0-2 R 50 , —SO 2 NR 50 R 51 , —NR 52 SO 2 R 50 , ═C(R 50 R 51 ), ═NOR 50 , ═NCN, ═C(halo) 2 , ═S, ═O, —C(O)N(R 50 R 51 ), —OC(O)R 50 , —OC(O)N(R 50 R 51 ), —N(R 52 )C(O)(R 50 ), —N(R 52 )C(O)OR 50 and —N(R 52 )C(O)N(R 50 R 51 ), wherein each R 5 is independently H or alkyl and R 50 , R 51 and R 52 are each independently selected from the group consisting of: H, alkyl, cycloalkyl, heterocycloalkyl, heteroaryl and aryl, and when chemically feasible, R 50 and R 51 can be joined together to form a carbocyclic or heterocyclic ring; Et is CH 3 CH 2 —; Hal is a halogen group; and L is a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl. A further understanding of the invention will be had from the following detailed description of the invention. DETAILED DESCRIPTION Definitions and Usage of Terms The following definitions and terms are used herein or are otherwise known to a skilled artisan. Except where stated otherwise, the definitions apply throughout the specification and claims. Chemical names, common names and chemical structures may be used interchangeably to describe the same structure. These definitions apply regardless of whether a term is used by itself or in combination with other terms, unless otherwise indicated. Hence, the definition of “alkyl” applies to “alkyl” as well as the “alkyl” portions of “hydroxyalkyl,” “haloalkyl,” “alkoxy,” etc. Unless otherwise known, stated or shown to be to the contrary, the point of attachment for a multiple term substituent (two or more terms that are combined to identify a single moiety) to a subject structure is through the last named term of the multiple term substituent. For example, a cycloalkylalkyl substituent attaches to a targeted structure through the latter “alkyl” portion of the substituent (e.g., structure-alkyl-cycloalkyl). The identity of each variable appearing more than once in a formula may be independently selected from the definition for that variable, unless otherwise indicated. Unless stated, shown or otherwise known to be the contrary, all atoms illustrated in chemical formulas for covalent compounds possess normal valencies. Thus, hydrogen atoms, double bonds, triple bonds and ring structures need not be expressly depicted in a general chemical formula. Double bonds, where appropriate, may be represented by the presence of parentheses around an atom in a chemical formula. For example, a carbonyl functionality, —CO—, may also be represented in a chemical formula by —C(O)— or —C(═O)—. Similarly, a double bond between a sulfur atom and an oxygen atom may be represented in a chemical formula by —SO—, —S(O)— or —S(═O)—. One skilled in the art will be able to determine the presence or absence of double (and triple bonds) in a covalently-bonded molecule. For instance, it is readily recognized that a carboxyl functionality may be represented by —COOH, —C(O)OH, —C(═O)OH or —CO 2 H. The term “substituted,” as used herein, means the replacement of one or more atoms or radicals, usually hydrogen atoms, in a given structure with an atom or radical selected from a specified group. In the situations where more than one atom or radical may be replaced with a substituent selected from the same specified group, the substituents may be, unless otherwise specified, either the same or different at every position. Radicals of specified groups, such as alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups, independently of or together with one another, may be substituents on any of the specified groups, unless otherwise indicated. The term “optionally substituted” means, alternatively, not substituted or substituted with the specified groups, radicals or moieties. It should be noted that any atom with unsatisfied valences in the text, schemes, examples and tables herein is assumed to have the hydrogen atom(s) to satisfy the valences. The term “chemically-feasible” is usually applied to a ring structure present in a compound and means that the ring structure (e.g., the 4- to 7-membered ring, optionally substituted by . . . ) would be expected to be stable by a skilled artisan. The term “heteroatom,” as used herein, means a nitrogen, sulfur or oxygen atom. Multiple heteroatoms in the same group may be the same or different. As used herein, the term “alkyl” means an aliphatic hydrocarbon group that can be straight or branched and comprises 1 to about 24 carbon atoms in the chain. Preferred alkyl groups comprise 1 to about 15 carbon atoms in the chain. More preferred alkyl groups comprise 1 to about 6 carbon atoms in the chain. “Branched” means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. The alkyl can be substituted by one or more substituents independently selected from the group consisting of halo, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, —NH(alkyl), —NH(cycloalkyl), —N(alkyl) 2 (which alkyls can be the same or different), carboxy and —C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, heptyl, nonyl, decyl, fluoromethyl, trifluoromethyl and cyclopropylmethyl. “Alkenyl” means an aliphatic hydrocarbon group (straight or branched carbon chain) comprising one or more double bonds in the chain and which can be conjugated or unconjugated. Useful alkenyl groups can comprise 2 to about 15 carbon atoms in the chain, preferably 2 to about 12 carbon atoms in the chain, and more preferably 2 to about 6 carbon atoms in the chain. The alkenyl group can be substituted by one or more substituents independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano and alkoxy. Non-limiting examples of suitable alkenyl groups include ethenyl, propenyl, n-butenyl, 3-methylbut-enyl and n-pentenyl. Where an alkyl or alkenyl chain joins two other variables and is therefore bivalent, the terms alkylene and alkenylene, respectively, are used. “Alkoxy” means an alkyl-O-group in which the alkyl group is as previously described. Useful alkoxy groups can comprise 1 to about 12 carbon atoms, preferably 1 to about 6 carbon atoms. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy and isopropoxy. The alkyl group of the alkoxy is linked to an adjacent moiety through the ether oxygen. The term “cycloalkyl” as used herein, means an unsubstituted or substituted, saturated, stable, non-aromatic, chemically-feasible carbocyclic ring having preferably from three to fifteen carbon atoms, more preferably, from three to eight carbon atoms. The cycloalkyl carbon ring radical is saturated and may be fused, for example, benzofused, with one to two cycloalkyl, aromatic, heterocyclic or heteroaromatic rings. The cycloalkyl may be attached at any endocyclic carbon atom that results in a stable structure. Preferred carbocyclic rings have from five to six carbons. Examples of cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like. The term “hydrocarbon,” as used herein, means a compound, radical or chain consisting of only carbon and hydrogen atoms, including aliphatic, aromatic, normal, saturated and unsaturated hydrocarbons. The term “alkenyl,” as used herein, means an unsubstituted or substituted, unsaturated, straight or branched, hydrocarbon chain having at least one double bond present and, preferably, from two to fifteen carbon atoms, more preferably, from two to twelve carbon atoms. The term “cycloalkenyl,” as used herein, means an unsubstituted or substituted, unsaturated carbocyclic ring having at least one double bond present and, preferably, from three to fifteen carbon atoms, more preferably, from five to eight carbon atoms. A cycloalkenyl goup is an unsaturated carbocyclic group. Examples of cycloalkenyl groups include cyclopentenyl and cyclohexenyl. “Alkynyl” means an aliphatic hydrocarbon group comprising at least one carbon-carbon triple bond and which may be straight or branched and comprising about 2 to about 15 carbon atoms in the chain. Preferred alkynyl groups have about 2 to about 10 carbon atoms in the chain; and more preferably about 2 to about 6 carbon atoms in the chain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkynyl chain. Non-limiting examples of suitable alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl. The alkynyl group may be substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of alkyl, aryl and cycloalkyl. The term “aryl,” as used herein, means a substituted or unsubstituted, aromatic, mono- or bicyclic, chemically-feasible carbocyclic ring system having from one to two aromatic rings. The aryl moiety will generally have from 6 to 14 carbon atoms with all available substitutable carbon atoms of the aryl moiety being intended as possible points of attachment. Representative examples include phenyl, tolyl, xylyl, cumenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, or the like. If desired, the carbocyclic moiety can be substituted with from one to five, preferably, one to three, moieties, such as mono- through pentahalo, alkyl, trifluoromethyl, phenyl, hydroxy, alkoxy, phenoxy, amino, monoalkylamino, dialkylamino, or the like. “Heteroaryl” means a monocyclic or multicyclic aromatic ring system of about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the atoms in the ring system is/are atoms other than carbon, for example nitrogen, oxygen or sulfur. Mono- and polycyclic (e.g., bicyclic) heteroaryl groups can be unsubstituted or substituted with a plurality of substituents, preferably, one to five substituents, more preferably, one, two or three substituents (e.g., mono- through pentahalo, alkyl, trifluoromethyl, phenyl, hydroxy, alkoxy, phenoxy, amino, monoalkylamino, dialkylamino, or the like). Typically, a heteroaryl group represents a chemically-feasible cyclic group of five or six atoms, or a chemically-feasible bicyclic group of nine or ten atoms, at least one of which is carbon, and having at least one oxygen, sulfur or nitrogen atom interrupting a carbocyclic ring having a sufficient number of pi (π) electrons to provide aromatic character. Representative heteroaryl (heteroaromatic) groups are pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, furanyl, benzofuranyl, thienyl, benzothienyl, thiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, isothiazolyl, benzothiazolyl, benzoxazolyl, oxazolyl, pyrrolyl, isoxazolyl, 1,3,5-triazinyl and indolyl groups. The term “heterocycloalkyl,” as used herein, means an unsubstituted or substituted, saturated, chemically-feasible cyclic ring system having from three to fifteen members, preferably, from three to eight members, and comprising carbon atoms and at least one heteroatom as part of the ring. The term “heterocyclic ring” or “heterocycle,” as used herein, means an unsubstituted or substituted, saturated, unsaturated or aromatic, chemically-feasible ring, comprised of carbon atoms and one or more heteroatoms in the ring. Heterocyclic rings may be monocyclic or polycyclic. Monocyclic rings preferably contain from three to eight atoms in the ring structure, more preferably, five to seven atoms. Polycyclic ring systems consisting of two rings preferably contain from six to sixteen atoms, most preferably, ten to twelve atoms. Polycyclic ring systems consisting of three rings contain preferably from thirteen to seventeen atoms, more preferably, fourteen or fifteen atoms. Each heterocyclic ring has at least one heteroatom. Unless otherwise stated, the heteroatoms may each be independently selected from the group consisting of nitrogen, sulfur and oxygen atoms. The term “carbocyclic ring” or “carbocycle,” as used herein, means an unsubstituted or substituted, saturated, unsaturated or aromatic (e.g., aryl), chemically-feasible hydrocarbon ring, unless otherwise specifically identified. Carbocycles may be monocyclic or polycyclic. Monocyclic rings, preferably, contain from three to eight atoms, more preferably, five to seven atoms. Polycyclic rings having two rings, preferably, contain from six to sixteen atoms, more preferably, ten to twelve atoms, and those having three rings, preferably, contain from thirteen to seventeen atoms, more preferably, fourteen or fifteen atoms. The term “hydroxyalkyl,” as used herein, means a substituted hydrocarbon chain preferably an alkyl group, having at least one hydroxy substituent (-alkyl-OH). Additional substituents to the alkyl group may also be present. Representative hydroxyalkyl groups include hydroxymethyl, hydroxyethyl and hydroxypropyl groups. The terms “Hal,” “halo,” “halogen” and “halide,” as used herein, mean a chloro, bromo, fluoro or iodo atom radical. Chlorides, bromides and fluorides are preferred halides. The term “thio,” as used herein, means an organic acid radical in which divalent sulfur has replaced some or all of the oxygen atoms of the carboxyl group. Examples include —R 53 C(O)SH, —R 53 C(S)OH and —R 53 C(S)SH, wherein R 53 is a hydrocarbon radical. The term “nitro,” as used herein, means the —N(O) 2 radical. The term “allyl,” as used herein, means the —C 3 H 5 radical. The term “phase transfer catalyst,” as used herein, means a material that catalyzes a reaction between a moiety that is soluble in a first phase, e.g., an alcohol phase, and another moiety that is soluble in a second phase, e.g., an aqueous phase. The following abbreviations are used in this application: EtOH is ethanol; Me is methyl; Et is ethyl; Bu is butyl; n-Bu is normal-butyl, t-Bu is tert-butyl, OAc is acetate; KOt-Bu is potassium tert-butoxide; NBS is N-bromo succinimide; NMP is 1-methyl-2-pyrrolidinone; DMA is N,N-dimethylacetamide; n-Bu 4 NBr is tetrabutylammonium bromide; n-Bu 4 NOH is tetrabutylammonium hydroxide, n-Bu 4 NH 2 SO 4 is tetrabutylammonium hydrogen sulfate, and equiv. is equivalents. In certain of the chemical structures depicted herein, certain compounds are racemic, i.e., a mixture of dextro- and levorotatory optically active isomers in equal amounts, the resulting mixture having no rotary power. General Synthesis One aspect of the invention comprises a general synthesis of xanthines based on a one-pot, five-step sequence from cyanamide and N-aryl glycine ester. Compound 1 can be prepared from glycine ethyl ester or a salt thereof (e.g., hydrochloric or sulfuric acid salt) and an aromatic aldehyde. As shown in Scheme I below, Compound 1 is prepared from glycine ethyl ester hydrochloride and an aromatic aldehyde. Compound 2 is prepared by reacting cyanamide with an excess of triethylorthoformate. Compound 3 is prepared by reacting Compound 2 with Compound 1. Compound 3 is converted into Compound 4 by reacting it with a base (e.g., potassium tert-butoxide). Compound 4 is reacted with a N—R 2 -substituted carbamate (e.g., urethane) in the presence of a base to obtain Compound Salt 5K. Based on the N—R 2 -substituent of the carbamate used, a desired N-1-R 2 -substituted xanthine Compound Salt 5K is obtained. Compound Salt 5K is then N-3-L-substituted with an L-halide using a phase transfer catalyst to provide a tri-substituted (R 1 , R 2 and L) xanthine Compound 6. Alternatively, Compound Salt 5K can be neutralized to Compound 5, which can then be selectively N-L-substituted to provide Compound 6. A selective dihalogenation of Compound 6 leads to a dihalo Compound 7, which is then coupled with an R 4 -substituted amine, followed by an addition of a base (e.g., sodium bicarbonate), to provide a tetrasubstituted (R 1 , R 2 , R 3 and R 4 ) xanthine Compound 13 when L is the same as R 3 . If L is a protected form of R 3 , intermediate Compound 9 is deprotected with a base (e.g., tetrabutylammonium hydroxide) to provide the tetrasubstituted (R 1 , R 2 , R 3 and R 4 ) xanthine Compound 13. Scheme I depicts this process: wherein, R 1 , R 2 and R 3 are each independently selected from the group consisting of: H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, allyl, —OR 5 , —C(O)OR 5 , —C(O)R 5 , —C(O)N(R 5 ) 2 , —NHC(O)R 5 and —NHC(O)OR 5 , wherein each R 5 is independently H or alkyl; provided that R 2 and R 3 are not both —H; R 4 is an alkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group; wherein R 1 , R 2 , R 3 and R 4 are optionally substituted with moieties independently selected from the group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl, halo, thio, nitro, oximino, acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 , —OR 50 , —NR 50 R 51 , —C(O)OR 50 , —C(O)R 50 , —SO 0-2 R 50 , —SO 2 NR 5 OR 51 , —NR 52 SO 2 R 50 , ═C(R 50 R 51 ), ═NOR 50 , ═NCN, ═C(halo) 2 , ═S, ═O, —C(O)N(R 50 R 51 ), —OC(O)R 50 , —OC(O)N(R 50 R 51 ), —N(R 52 )C(O)(R 50 ), —N(R 52 )C(O)OR 50 and —N(R 52 )C(O)N(R 50 R 51 ), wherein each R 5 is independently H or alkyl and R 50 , R 51 and R 52 are each independently selected from the group consisting of: H, alkyl, cycloalkyl, heterocycloalkyl, heteroaryl and aryl; Hal is a halogen group; L is R 3 or a protected form of R 3 comprising R 3 with a protective substituent selected from the group consisting of acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 and —SC(O)R 5 group, wherein R 5 is H or alkyl; and M + is a metal ion. While some compounds are shown in Scheme I as non-isolated intermediates, it is understood that they can be isolated using routine chemistry techniques. Preferred embodiments of the invention utilize compounds with the following R 1 , R 2 , R 3 and R 4 radicals: R 1 is preferably alkyl, aryl, heteroaryl, —OR 5 , —C(O)OR 5 , —C(O)R 5 or —C(O)N(R 5 ) 2 , wherein R 5 is H or alkyl. Each R 1 group is optionally substituted as defined above. More preferably, R 1 is —OR 5 , wherein R 5 is H or alkyl. Even more preferably, R 1 is alkoxy, such as methoxy. R 2 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, aryl or heteroaryl. Each R 2 group is optionally substituted as defined above. More preferably, R 2 is C 1-6 alkyl, optionally substituted as defined above. Even more preferably, R 2 is ethyl. R 3 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, aryl, heteroaryl, allyl, —NHC(O)R 5 or —NHC(O)OR 5 , wherein R 5 is H or C 1-12 alkyl. Each R 3 group is optionally substituted as defined above. More preferably, R 3 is C 1-6 alkyl, optionally substituted with one of the groups defined above. Even more preferably, R 3 is C 1-6 alkyl, substituted with —OR 50 , wherein R 50 is H, such as hydroxymethyl. R 4 is preferably C 1-12 alkyl, C 3-8 cycloalkyl, C 5-8 cycloalkenyl, heterocycloalkyl, aryl or heteroaryl. Each R 4 group is optionally substituted as defined above. More preferably, R 4 is C 3-8 cycloalkyl, optionally substituted as defined above. Even more preferably, R 4 is C 4-7 cycloalkyl, substituted with —OR 50 , wherein R 50 is defined as above. For example, R 4 can be 2-hydroxy cyclopentyl. In some embodiments of the invention, L is the same as R 3 . In other embodiments of the invention, L is a protected form of R 3 , in which case the protective substituent on R 3 is preferably an acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 group, wherein R 5 is H or C 1-12 alkyl. Hal is preferably chlorine, bromine and fluorine. More preferably, Hal is chlorine or bromine. Even more preferably, Hal is bromine. M + is, preferably, an alkali metal or alkaline earth metal ion. More preferably, M + is a potassium or sodium ion. Compound 1 can be prepared by reacting about equimolar amounts of p-anisaldehyde and glycine ethyl ester hydrochloride (or its free form) in the presence of a base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, potassium butoxide, or the like) and in an alcoholic solvent (e.g., ethanol, isopropanol, or the like). Preferably, up to about 2 moles (e.g., about 1.3-1.5 moles) of glycine ethyl ester hydrochloride and up to about 2 moles (e.g., about 1 mole) of inorganic salt can each be used per mole of p-anisaldehyde. The reaction proceeds through an intermediate imine (not shown), which is reduced with a reducing agent (e.g., NaBH 4 , catalytic hydrogenation, H 2 /Pd/C, or the like), preferably, a borohydride reducing agent. The reaction can be run at room temperature. Preferably, the reaction is run at about 20-45° C., more preferably, about 30-40° C. At the end of the reaction, Compound 1 is isolated in a solution form in an organic solvent (e.g., toluene), and used as such for the next step. Compound 2 is N-cyanomethanimidic acid ethyl ester, and is prepared by reacting cyanamide with an excess of triethylorthoformate. Preferably, from about 1.2 to about 1.5 moles of triethylorthoformate (e.g., 1.33 moles) are reacted with about 1 mole of cyanamide. Preferably, the reaction mixture is gradually heated up to about 85-95° C. for about 2 hours. Compound 2 is not isolated, and is used in-situ for the next step. The structure of Compound 3 is novel. An equimolar reaction mixture of Compound 2 (obtained in-situ above) is added to a solution of Compound 1 in an anhydrous, ethereal organic solvent (e.g., tetrahydrofuran (“THF”), diethyl ether, monoethyl ether, monoglyme, diglyme, ethylene glycol, or the like), and heated to about 65-70° C. for about 1 hour. About 1.1 to about 1.3 moles (e.g., 1.2 moles) of Compound 2 is used per mole of Compound 1. At the end of the reaction, the product is not isolated, and is used in-situ for the next step. The structure of Compound 4 is novel. Compound 4 is prepared by reacting Compound 3 (obtained in-situ above) with a base (e.g., potassium tert-butoxide, potassium pentoxide, potassium tert-amylate, sodium ethoxide, sodium tert-butoxide, or the like) in an alcoholic solvent (e.g., anhydrous EtOH). A catalytic amount of base is preferably used, generally, about 5-20 mol % per mol of Compound 3 in the alcoholic solvent. More preferably, about 15 mol % of base is used. Preferably, the reaction mixture is heated to about 75-85° C. for about 1 hour. At the end of reaction, the product is not isolated, and is used in-situ for the next step. The structure of Compound Salt 5K is novel. Compound 4 can be converted to Compound Salt 5K by reacting it in-situ with from about 1 to about 3 moles (e.g., 1.5 moles) of a N—R 2 -substituted carbamate, R 2 NHCO 2 R 1 (e.g., the urethane EtNHCO 2 Et), and from about 1 to about 3 moles (e.g., 2.1 moles) of a base (e.g., potassium tert-butoxide, potassium pentoxide, potassium tert-amylate, sodium ethoxide, sodium tert-butoxide, or the like), in an ethereal organic solvent (e.g., THF, diethyl ether, monoethyl ether, monoglyme, diglyme, ethylene glycol, or the like) or a sulfolane, at 80-130° C. (preferably 115-125° C.), wherein R 1 and R 2 are each independently defined as above. The base provides a metal ion (M + ) to Compound Salt 5K. Potassium tert-butoxide provides a potassium ion (K + ), while sodium tert-butoxide provides a sodium ion (Na + ) to Compound Salt 5K. The inventive methodology provides an efficient synthesis for directly converting (in one step) Compound 4 to Compound Salt 5K in solution without the use of any toxic chemicals or harsh thermal conditions. The potassium Compound Salt 5K is isolated by filtration, but not dried. Compound Salt 5K is selectively N-3 alkylated in-situ to Compound 6 with BrCH 2 -L (e.g., 2-bromoethyl acetate in an anhydrous, organic solvent (e.g., THF, methyl tert-butyl ether, or the like) in the presence of a phase transfer catalyst (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, or the like), wherein L is defined as above. The reaction takes place rapidly (e.g., about 1 hour at about 65-70° C.), and no base is required. This is in contrast to known N-alkylation reactions, many of which use dimethylformamide (“DMF”) and potassium carbonate or an organic base (e.g., triethylamine, diisopropylethylamine, etc.) to achieve the N-alkylation, and which generally take from several hours to days to complete. Alternatively, the potassium Compound Salt 5K can be neutralized with an acid (e.g., aqueous acetic acid, dilute hydrochloric acid, dilute sulfuric acid, or the like) to provide Compound 5. Under this alternative process, Compound 5 can be selectively N-3 alkylated by treatment with an inorganic base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, potassium butoxide, or the like) in a polar solvent (e.g., acetonitrile and its higher homologs, DMF, N,N-dimethylacetamide (“DMA”), 1-methyl-2-pyrrolidinone (“NMP”), or the like) in the presence of a phase transfer catalyst (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, or the like) and an alkylating agent (e.g., BrCH 2 -L, where L is defined as above) to provide Compound 6. The structure of Compound 6 is novel. The conversion from Compound 1 to Compound 6 is a 5-step process that can be carried out in one pot or container. The overall yield for Compound 6 is generally about 45-55%. The structure of Compound 7 is novel. Compound 6 is regioselectively dihalogenated (e.g., dibrominated or dichlorinated) to Compound 7 under mild conditions with about 2-3 moles (preferably, about 2.7-2.8 moles) of a dihalogenating agent (e.g., a dibrominating agent, such as N-bromo succinimide (“NBS”), dibromo-1,3-dimethyl hydantoin or N-bromo acetamide). The use of a strong acid (e.g., triflic or sulfuric acid) as a catalyst in an amount of about 1-10 mol %, preferably, about 3 mol %, allows the reaction to proceed at room temperature. Alternatively, tetrabutylammonium hydrogensulfate can be used as the catalyst, but it would require an application of heat (e.g., about 80° C.) to drive the reaction to completion. It is preferred that the reaction is run in a dry polar solvent, such as acetonitrile, DMF, NMP, DMA, or a mixture thereof. Under these conditions, the amounts of mono- and tri-bromo side products are minimized. Compound 7 is coupled with Compound 8 (an R 4 NH 2 amine) to form Compound 13 via Compound 9, a novel intermediate. Typical coupling reaction conditions for this step generally require the use of a polar, aprotic solvent (e.g., NMP, DMA, or the like), an inorganic base (e.g., potassium carbonate, sodium carbonate, sodium bicarbonate, or the like), and an excess of Compound 8, preferably, up to about 3 moles of Compound 8 per mole of Compound 7. A preferred mild, inorganic base is sodium bicarbonate. The application of heat will drive the reaction to completion faster. For example, at about 130-140° C., the reaction time can be shortened in half, from about 24 hours to about 12 hours. L is R 3 or a protected form of R 3 (i.e., where a moiety is attached to R 3 for protecting it from reacting with other ingredients). When L is the same as R 3 , Compound 9 is the same as Compound 13, so the addition of an inorganic base to the intermediate Compound 9 (step (k) (ii) of the summary of the invention) is not necessary. On the other hand, when L is a protected form of R 3 , deprotection can be accomplished in the same pot, without isolating Compound 9, by using a catalytic amount of an inorganic base (e.g., potassium carbonate, tetrabutylammonium hydroxide, or the like). Protected forms of R 3 include R 3 moieties substituted with protective groups such as acetate, propionate, pivaloyl, —OC(O)R 5 , —NC(O)R 5 or —SC(O)R 5 groups, wherein R 5 is H or C 1-12 alkyl. When the protecting substituent is an acetate group, deprotection is preferably carried out with tetrabutylammonium hydroxide because it results in a faster and cleaner reaction, and product isolation is facile. In another embodiment of the invention, a pivaloyl protecting group can be used in place of the acetate protecting group, and the application of similar chemistry will lead from Compound 5K (or Compound 5) to Compound 13. The deprotection and work-up conditions are adjusted so as to minimize formation of isomeric impurities. For instance, care should be taken to monitor the basicity of the reaction during deprotection because when the deprotection steps are carried out under very strong basic conditions, diastereomers may form. Specific Synthesis The general synthesis of Scheme I can be applied to prepare specific xanthines. For example, if R 1 is —OCH 3 , R 2 is —CH 2 CH 3 , L is —CH 2 CO 2 CH 3 , R 3 is —CH 2 OH, and R 4 is ,then the product obtained from Scheme I (Compound 13) can be called 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione (Compound 13A), a PDE V inhibitor useful for the treatment of erectile dysfunction. An illustration of this synthesis is shown in the following Scheme II, which allows for an efficient, commercial scale preparation of Compound 13A, without the need for chromatographic purification of intermediates: The experimental conditions disclosed herein are preferred conditions, and one of ordinary skill in the art can modify them as necessary to achieve the same products. EXAMPLES Compound 1A: glycine-N-[(4-methoxyphenyl)methyl]ethyl ester To a mixture of glycine ethyl ester hydrochloride (about 1.4 equiv) and potassium carbonate (about 1.0 equiv) was added anhydrous ethanol. The mixture was stirred at about 40-45° C. for about 3 hours. Then, p-anisaldehyde (about 1.0 equiv.) was added, and the reaction mixture was stirred for a minimum of about 3 hours to provide an imine (not shown). Upon reaction completion (about ≦5.0% p-anisaldehyde remaining by GC analysis), the reaction mixture was cooled to about 0-10° C. Then, an aqueous solution of sodium borohydride (about 0.50 equiv) was added to the reaction mixture at a temperature of between about 0° C. and about 20° C., and stirred for about 1 hour to provide Compound 1A. Upon completion of the reduction reaction, the reaction mixture was quenched with the slow addition of an aqueous solution of aqueous glacial acetic acid. After quenching, the reaction mixture was warmed to room temperature and filtered to remove solids. The filtrate was then concentrated under vacuum, followed by the addition of toluene and water to facilitate layer separation. Aqueous potassium carbonate solution was added to adjust the pH of the mixture to about 8-9. The organic layer was separated and the aqueous layer was extracted with toluene. The combined toluene extracts were concentrated to provide the product in about a 80-85% yield (based on GC and HPLC in solution assay). 1 H NMR 400 MHz (CDCl 3 ): δ 7.23 (d, J=8.5 Hz, 2H), 6.85 (d, J=8.5 Hz, 2H), 4.17 (q, J=7.1 Hz, 2H), 3.78 (s, 3H), 3.73 (s, 2H), 3.38 (s, 2H), 1.88 (s, br, 1H), 1.26 (t, J=7.1 Hz, 3H); 13 C NMR 100 MHz (CDCl 3 ): δ 172.8, 159.2, 132.0, 129.9, 114.2, 61.1, 55.6, 53.1, 50.4, 14.6. Compound 2: N-cyanomethanimidic acid ethyl ester To cyanamide (about 1.2 mole) was added triethylorthoformate (about 1.33 mole), and the reaction mixture was heated to about 85-95° C. for approximately 2 hours to form Compound 2. Estimated in-solution yield was about 95-100%. The product was optionally purified by vacuum distillation. 1 H NMR 400 MHz (CDCl 3 ): δ 8.38 (s, 1H), 4.28 (t, J=6.7 Hz, 2H), 1.29 (t, J=6.8 Hz, 3H); 13 C NMR 100 MHz (CDCl 3 ): δ 171.5, 113.4, 65.5, 13.1. Compound 3A: cis- and trans-glycine N-[(cyanoimino)methyl]-N-[(4-methoxyphenyl)methyl]ethyl ester A solution of Compound 1A (about 1.0 mole) in toluene was concentrated under vacuum to distill off toluene. Anhydrous tetrahydrofuran (“THF”) was added to the concentrate, then Compound 2 (about 1.2 moles, obtained above) was added to that, and the solution was heated at reflux for about 1 hour. At this stage, the formation of Compound 3A was complete. Estimated in-solution yield was about 95% (about 2:1 mixture of cis and trans isomers). Compound 4A: 1H-imidazole-5-carboxylic acid, 4-amino-1-[(4-methoxyphenyl)methyl]ethyl ester Compound 3A (obtained above) was concentrated by distilling off THF. Then, anhydrous ethanol was added to afford a reaction mixture solution. Separately, potassium t-butoxide (about 0.15 mole) was dissolved in anhydrous ethanol to afford a solution. The potassium t-butoxide solution was added to the reaction mixture solution and heated to about 75-85° C. for about 1 hour. The overall in-solution yield of Compound 4A was about 85-90%. 1 H NMR 400 MHz (CDCl 3 ): δ 7.16 (s, 1H), 7.08 (d, J=8.6 Hz, 2H), 6.82 (d, J=8.7 Hz, 2H), 5.23 (s, 2H), 4.93 (s, br, 2H), 4.23 (q, J=7.1, 2H), 3.76 (s, 3H), 1.26 (t, J=7.1 Hz, 3H); 13 C NMR 400 MHz (CDCl 3 ): δ 160.9, 159.2, 139.0, 128.6, 128.5, 114.0, 101.8, 59.5, 55.2, 50.1, 14.4. Compound 5AK: 1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-Purine-2,6-dione potassium salt The reaction mixture containing Compound 4A in ethanol (obtained above) was added to diglyme and distilled under vacuum to remove the ethanol. After being cooled to room temperature, N-ethylurethane (about 1.2 equiv.) was added and the reaction mixture was heated to about 110-120° C. A solution of potassium t-butoxide (2.2 equiv.) in diglyme was added to the hot solution. The reaction mixture was cooled to room temperature. THF was added to precipitate additional product, which was filtered and washed to provide Compound Salt 5AK in 55-65% overall yield. The wet cake can be used as such for conversion to Compound 6A. 1 H NMR (DMSO-d 6 , 400 MHz): δ 7.73 (s, 1H) 7.31 (d, J=8.6 Hz, 2H) 6.86 (d, J=8.6 Hz, 2H) 5.24 (s, 1H) 3.88 (q, J=6.8 Hz, 2H) 3.71 (s, 3H) 1.07 (t, J=6.8 Hz, 3H); 13 C NMR (DMSO-d 6 , 100 MHz): δ 161.1, 159.0, 158.4, 157.2, 141.4, 131.0, 129.5, 114.1, 105.6, 55.4, 48.2, 34.4, 14.3. Optional Neutralization of Compound Salt 5AK to Compound 5A: Compound 5A: 1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-Purine-2,6-dione The wet cake filtered solid of Compound Salt 5AK (obtained above) was suspended in water and then acidified to a pH of about 5 using glacial acetic acid. The resulting slurry was filtered to obtain the neutralized product, which was then washed with water and dried. The overall isolated yield of neutralized Compound 5A from Compound 1A was about 45-55%. Spectroscopic data for neutralized Compound 5A was identical to that of Compound Salt 5AK. Compound 6A: 3-[2-(acetyloxy)ethyl]-1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-purine-2,6-dione To the wet cake filtered solid of Compound Salt 5AK (obtained above) were added tetrabutylammonium bromide (about 0.05 mole) and 2-bromoethyl acetate (about 1.2 moles) in THF. After being heated to reflux for about 2 hours, part of the THF was distilled off, and isopropyl alcohol was added to the reaction mixture. The reaction mixture was then concentrated under reduced pressure and cooled to around room temperature. Water was added to precipitate the product. After being cooled to about 0-5° C. for about a few hours, the product was isolated by filtration. The wet cake was washed with aqueous isopropyl alcohol (about 30% in water), and dried under vacuum to afford Compound 6A as a pale yellow solid in about a 45-55% overall yield (based on Compound 1A). The crude product may be purified further by decolorizing with Darco in methanol, followed by filtration and concentration to afford crystalline Compound 6A. 1 H NMR (CDCl 3 , 400 MHz): δ 7.54 (s, 1H) 7.32 (d, J=8.6 Hz, 2H) 6.90 (d, J=8.6 Hz, 2H) 5.43 (s, 2H) 4.41 (m, 2H) 4.38 (m, 2H) 4.10 (q, J=7.2 Hz, 2H) 3.79 (s, 3H) 1.96 (s, 3H) 1.25 (t, J=7.2 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz): δ 171.1, 160.2, 155.3, 151.4, 148.9, 140.9, 130.1, 127.7, 114.8, 107.5, 61.7, 55.6, 50.2, 42.4, 36.9, 21.2, 13.6. After Optional Neutralization of Compound Salt 5AK to Compound 5A: Compound 6A: 3-[2-(acetyloxy)ethyl]-1-ethyl-3,7-dihydro-7-[(4-methoxyphenyl)methyl]-1H-purine-2,6-dione Acetonitrile was added to a mixture of Compound 5A (about 1.0 mole), anhydrous potassium carbonate (about 1.5 moles) and tetrabutylammonium hydrogen sulfate (about 0.05 mole). 2-bromoethyl acetate (about 1.5 moles) was added in three separate portions (0.72 mole in the beginning, another 0.45 mole after about 2 hours of reaction, and then the remaining 0.33 mole after about another 1 hour of reaction) during the course of the reaction at about 80-85° C. The total reaction time was about 7 hours. The reaction mixture was cooled to about room temperature and filtered. The filtrate was concentrated. Aqueous isopropanol was added to crystallize the product. The product was filtered, washed with aqueous isopropanol, and dried to provide Compound 6A in about a 75-80% yield. Compound 7A: 8-bromo-1-ethyl-3-[2-(acetyloxy)ethyl]-3,7-dihydro-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-Purine-2,6-dione Compound 6A (about 1 mole) and NBS (about 2.8 moles) were dissolved in dry acetonitrile and agitated at about 15-20° C. To this reaction mixture, a solution of sulfuric acid (about 0.03 mol) in acetonitrile was added, while maintaining the reaction temperature below about 25° C. The reaction mixture was agitated at about 20-25° C. for about 12-15 hours until complete consumption of the starting material was indicated. The reaction mixture was cooled to about 0-5° C. and a cold (about 5-10° C.) aqueous solution of sodium sulfite was added, keeping the temperature below about 10° C. The reaction was agitated for about 2 hours at about 0-10° C., and then filtered. The isolated cake was washed with water, followed by methanol, then dried under a vacuum to obtain Compound 7A in about an 85% yield. 1 H NMR (CDCl 3 , 400 MHz): □ 7.60 (d, J=2.0 Hz, 1H), 7.35 (dd, J=8.4 Hz, 2.0 Hz, 1H), 6.83 (d, J=8.4 Hz, 1H), 5.43 (s, 2H), 4.35 (m, 4H), 4.05 (q, J=7.0 Hz, 2H), 3.85 (s, 3H), 1.96 (s, 3H), 1.23 (t, J=7.0 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz): □ 171.0, 156.2, 154.2, 150.8, 148.2, 138.3, 128.9, 128.7, 127.5, 112.1, 112.0, 109.1, 61.5, 56.5, 49.3, 42.5, 37.0, 21.0, 13.3. MS (ES) m/e 545.2 (M+H) + . Compound 13A: 1-ethyl-3,7-dihydro-8-[(1R,2R)-(hydroxycyclopentyl)amino]-3-(2-hydroxyethyl)-7-[(3-bromo-4-methoxyphenyl)methyl]-1H-purine-2,6-dione Compound 7A (about 1 mole) was combined with (R,R)-2-amino-1-cyclopentanol hydrochloride (Compound 8A, about 1.2 moles) and sodium bicarbonate (about 3 moles). To this reaction mixture was added N,N-dimethylacetamide (“DMA”), and the reaction mixture was agitated at about 135-140° C. for about 15-17 hours until complete consumption of the starting material was indicated. Compound 9A is an intermediate that is formed, but not isolated, from the reaction mixture. The reaction mixture was then cooled to about 45-50° C., and tetrabutylammonium hydroxide (about 0.05 moles of about a 40% solution in water) was charged therein, followed by methanol. The reaction mixture was refluxed at about 80-85° C. for about 8-9 hours until complete deprotection of the acetate group was indicated. The reaction mixture was cooled to about 40-45° C. and concentrated under vacuum. The pH of the reaction mixture was adjusted to about 5-6 with dilute acetic acid, and the reaction mixture was heated to about 55-65° C., and seeded with a small amount of Compound 13A. The reaction mixture was then cooled to about 30-35° C. over a period of about 2 hours, and water was added over a period of about 1 hour. The reaction mixture was further cooled to about 0-5° C. over a period of about 1 hour, and agitated at that temperature for about 4 hours. The Compound 13A product was isolated by filtration, washed with water and dried to provide about an 85-90% yield. 1 H NMR (CDCl 3 , 400 MHz): □ 7.47 (d, J=2.1 Hz, 1H), 7.18 (dd, J=8.4 Hz, 2.0 Hz, 1H), 6.87 (d, J=8.4 Hz, 1H), 5.23 (s, 2H), 5.01 (s, 1H), 4.22 (m, 2H), 4.15 (m, 1H), 4.05 (q, J=7.0 Hz, 2H), 3.93 (m, 3H), 3.88 (s, 3H), 3.77 (m, 1 H), 2.95 (m, 1H), 2.15 (m, 1H), 2.05 (m, 1H), 1.60-1.80 (m, 4H), 1.35 (m, 1H), 1.23 (t, J=7.0 Hz, 3H); 13 C NMR (CDCl 3 , 100 MHz): □ 156.2, 154.0, 153.5, 151.8, 148.3, 132.6, 129.1, 127.9, 112.5, 103.2, 79.5, 77.8, 63.2, 61.3, 56.7, 46.5, 45.9, 36.8, 32.9, 31.5, 21.4, 13.8. MS (ES) m/e 523.4 (M+H) + . Micronization Materials prepared by the above-described processes without further processing can exhibit particle sizes that are greater than optimal for purposes of bioabsorption, and thus, bioavailability. In certain preferred embodiments of the invention, the compounds disclosed herein are subject to a micronization process to generate particle size distributions more favorable for bioabsorption. Form 2 of Compound 13 (disclosed in the co-pending patent application “Xanthine Phosphodiesterase V Inhibitor Polymorphs,” incorporated by reference thereto) was micronized on a fluid energy mill (Jet Pulverizer Micron Master, model 08-620). A feeder (K-Tron Twin Screw Feeder) was used to feed material to the mill at a rate of about 80 grams/min. A mill jet pressure of 110 psig was used. The resulting material was then heated to convert amorphous material generated during micronization to crystalline material. The setpoint on the dryer (Stokes Tray Dryer, model 438H) was set to 95° C. The batch was heated at a temperature between 90 and 100° C. for 8 hours. Differential Scanning Calorimetry (“DSC”) analysis indicated no amorphous material was present. The particle size distribution of the resulting material was characterized, using a Sympatec particle size analyzer, as having a volume mean diameter of 8.51 μm and a median particle diameter of 5.92 μm. Cryogenic micronization processes may result in even more favorable particle size distributions. The above description is not intended to detail all modifications and variations of the invention. It will be appreciated by those skilled in the art that changes can be made to the embodiments described above without departing from the inventive concept. It is understood, therefore, that the invention is not limited to the particular embodiments described above, but is intended to cover modifications that are within the spirit and scope of the invention, as defined by the language of the following claims.
A process for preparing xanthine phosphodiesterase V inhibitors, and compounds utilized in said process. The process includes a five-step methodology for efficient synthesis of Compound 5 without intermediate purifications or separations, a dihalogenation step to synthesize Compound 7, and a coupling reaction to produce Compound 9.
2
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates generally to the field of connecting computer systems by a common communication interface. More particularly, the present invention provides a generic HTTP interface that may be utilized by a variety of different computer systems. [0003] 2. Description of the Related Art [0004] In traditional computing architecture, when it was necessary for disparate computer systems to communicate with each other, developers would produce a layer of software or hardware known as “middleware”. This middleware would translate communication protocols (i.e. ways of communicating) so that one system could exchange data with another. For example, a program running on an International Business Machines mainframe needing to extract data from Digital Equipment Corporation database server would make use of middleware as a standard interface. Over time, the use of such interfaces, known as Application Programming Interfaces (APIs) proliferated. Each with its own special syntax and interface. For networked systems that included a variety of different types of hardware and software interfaces. This quickly became an issue for software development. Most organizations simply do not have the resources to maintain a plurality of different interfaces between the machines their software products need to communicate with. [0005] To address this problem, IBM Canada Ltd. filed a patent application in Canada, namely patent application number 2,248,634 (the '634 application) which was published on Mar. 24, 2000. The '634 application discloses a framework to allow an application program running on one system to communicate through a standardized communication protocol with a backend running on another system. In our previous example, the IBM mainframe would be running the application, and the DEC database would be the backend application. [0006] Currently, the most ubiquitous computing network is the Internet. A significant portion of the Internet makes use of the Hypertext Transfer Protocol (HTTP), this is the protocol recognized by web browsers such as Netscape and Internet Explorer and is utilized by web pages on the World Wide Web (WWW). As the use of the WWW increases, the use of HTTP increases as well. In particular, HTTP has become a protocol of choice for the exchange of data between business enterprises connected to the Internet. [0007] A wide variety of HTTP implementations exist, all of which are very specific. In essence they provide a specific API interface as discussed above. Because of this, existing applications would need to be changed to adapt to each different HTTP implementation. [0008] Thus, there is a need for a seamless, open and flexible HTTP interface that shields an application from the protocol details and allows existing applications to easily function with a variety of HTTP implementations. SUMMARY OF THE INVENTION [0009] The present invention relates to a method and system for utilizing an HTTP connector implementation to allow computer systems to communicate using a generic HTTP interface. [0010] One aspect of the present invention is a system for communicating with one or more target systems by using an HTTP connector, the system having an infrastructure, an application component and an HTTP connector, the application component connected to the HTTP connector via a client view, the HTTP connector connected to the infrastructure by an infrastructure view, and the HTTP connector connected to the one or more target systems for the purpose of exchanging data with the one or more target systems. [0011] In another aspect of the present invention, there is provided an HTTP connector method, the method having the steps of: requesting a connection to a target system, using an HTTP connector; determining if the connection to the target system has been established, if not, terminating the method; determining the type of interaction desired with the target system and acting upon the type; and returning control to the requesting step. [0012] In another aspect of the present invention there is provided a system for establishing an HTTP connection, the system comprising: request means for establishing a connection to a target system, using a HTTP connector; testing means to determine if the connection to the target system has been established; selection means for determining the type of interaction desired with the target system; and communication means for communicating with the target system in a manner based upon the type of interaction. [0013] In another aspect of the present invention there is provided a J2EE Connector Architecture compliant connector, the connector comprising the classes: HTTPConnection, HttpConnectionFactory, HttpConnectionMetaData, HttpConnectionRequestInfo, HttpConnectionSpec, HttpContentRecord, HttpInteraction, HttpInteractionSpec, HttpManagedConnection, HttpManagedConnectionFactory, HttpManagedConnectionMetaData, and HttpResourceAdapterMetaData. [0014] In another aspect of the present invention there is provided a computer readable medium containing instructions for implementing an HTTP connector method, the instructions comprising the steps of: requesting a connection to a target system, using HTTP; determining if the connection to the target system has been established, if not, terminating the method; determining the type of interaction desired with the target system and acting upon the type; and returning control to the requested step. [0015] In yet another aspect of the present invention there is provided a computer readable medium containing instructions for creating a J2EE Connector Architecture compliant connector, said instructions comprising the classes: HTTPConnection, HttpConnectionFactory, HttpConnectionMetaData, HttpConnectionRequestInfo, HttpConnectionSpec, HttpContentRecord, HttpInteraction, HttpInteractionSpec, HttpManagedConnection, HttpManagedConnectionFactory, HttpManagedConnectionMetaData, and HttpResourceAdapterMetaData. BRIEF DESCRIPTION OF THE DRAWINGS [0016] For a better understanding of the present invention, and to show more clearly how it may be carried into effect, reference will now be made, by way of example, to the accompanying drawings which aid in understanding an embodiment of the present invention and in which: [0017] [0017]FIG. 1 is a block diagram of a system utilizing the present invention; and [0018] [0018]FIGS. 2 a to 2 c comprise a flowchart illustrating the logical flow of an embodiment of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0019] To aid the reader in understanding the architecture in which the present invention may be implemented we now refer to FIG. 1. FIG. 1 is a block diagram of a system utilizing the present invention, shown as 10 . [0020] System 10 comprises: infrastructure 12 , application component 14 , CCF connector 16 , CCF client view 18 and CCF infrastructure view 20 . Infrastructure 12 is the computer system on which the present invention runs and all the services to which system 10 has access. Application component 14 is a client application running within infrastructure 10 . CCF connector 16 is an interface which allows component 14 to communicate with one or more target systems 22 . Specific to the present invention, component 14 would be communicating with target system 22 to obtain data via an HTTP connection. Connector 16 is the portion of system 10 in which the present invention resides. More specifically the present invention is a connector 16 that provides an HTTP interface. Client view 18 allows application 14 to use well defined and consistent interfaces with a plurality of target systems 22 , via connector 16 . CCF infrastructure view 20 provides an interface between CCF connector 16 and infrastructure 12 so that connector 16 may access such services as error handling, trace logging, security controls or remote access services (RAS). [0021] The implementation of the present invention follows the specification described in the Java 2 Enterprise Edition (J2EE) Connector Architecture, Proposed Final Draft 2 document. The J2EE specification provides a distributed services-based architecture for implementing electronic business applications. The present invention is a non-transactional connector that implements HTTP communication protocol version 1.0 as specified in Request for Comments (RFC) 1945. Most computer software standardization processes involve the publication of RFC's to which those interested reply and provide suggestions. [0022] The present invention has been implemented in Java and as such the description of the preferred embodiment will be Java based. It will be appreciated by those skilled in the art that the use of Java facilitates the description and implementation of the preferred embodiment. However, the preferred embodiment can be adapted to other computer languages. Similarly, the preferred embodiment need not run in the architecture described in FIG. 1, as one skilled in the art will recognize any number of system architectures may make use of the present invention. [0023] In the preferred embodiment, the present invention consists of the following classes: [0024] 1) HttpConnection [0025] 2) HttpConnectionFactory [0026] 3) HttpConnectionMetaData [0027] 4) HttpConnectionRequestInfo [0028] 5) HttpConnectionSpec [0029] 6) HttpContentRecord [0030] 7) HttpInteraction [0031] 8) HttpInteractionSpec [0032] 9) HttpManagedConnection [0033] 10) HttpManagedConnectionFactory [0034] 11) HttpManagedConnectionMetaData [0035] 12) HttpResourceAdapterMetaData [0036] We will now discuss the functionality of each of these classes. [0037] 1) HttpConnection [0038] The following is a list of methods and their signatures implemented by the HttpConnection class: [0039] HttpConnection(ManagedConnection) [0040] void call(Interaction, InteractionSpec, Record, Record) [0041] void close( ) [0042] Interaction createInteraction( ) [0043] boolean getAutoCommit( ) [0044] LocalTransaction getLocalTransaction( ) [0045] HttpManagedConnection getManaged( ) [0046] ConnectionMetaData getMetaData( ) [0047] ResultSetInfo getResultSetInfo( ) [0048] void logTrace(String) [0049] void setAutoCommit(boolean) [0050] void setLogWriter(PrintWriter) [0051] void setManaged(HttpManagedConnection) [0052] This class represents an application handle to a physical connection. It is created by HttpConnectionFactory and is associated with a particular HttpManagedConnection instance through which the communication With a target system 22 is executed. HttpConnection creates HttpInteraction objects, by the createInteraction method. Since the present invention does not support transactional behaviour, HttpConnection throws a javax.resource.NotSupportedException from the following methods: [0053] setAutoCommit(boolean) [0054] getLocalTransaction( ) [0055] getAutoCommit( ) [0056] HttpConnection also throws a NotSupportedException from the getResultSetInfo( ) method. The close request (in the close( ) method implementation) passes the close request to the associated HttpManagedConnection. HttpConnection handles interaction requests, from the HttpInteracton objects it created, in the call( . . . ) method, implemented in addition to the required interface methods. In this method, HttpConnection passes the execution request, along with its instance to the associated HttpManagedConnection. [0057] 2) HttpConnectionFactory [0058] The following is a list of methods and their signatures implemented by the HttpConnectionFactory class. [0059] HttpConnectionFactory( ) [0060] HttpConnectionFactory(ConnectionManager) [0061] Connection getConnection( ) [0062] Connection getConnection(ConnectionSpec) [0063] ManagedConnectionFactory getManagedConnectionFactory( ) [0064] ResourceAdapterMetaData getMetaData( ) [0065] RecordFactory getRecordFactory( ) [0066] Reference getReference( ) [0067] void logTrace(String) [0068] void setConnectionManager(ConnectionManager) [0069] void setManagedConnectionFactory(ManagedConnectionFactory) [0070] void setReference(Reference) [0071] The HttpConnectionFactory class represents objects capable of creating active HttpConnections. It is instantiated by and maintains association with the instance of the HttpManagedConnectionFactory. It also contains the instance of the ConnectionManager class which it uses to obtain connections during the connection request, in the getConnection( ) method implementation. If the new connection is requested passing the ConnectionSpec object (getConnection( ) method with the argument), the HttpConnectionFactory verifies that the passed object is an instance of the HttpConnectionSpec, then creates the new instance of the HttpConnectionRequestInfo object, sets its properties using values from the ConnectionSpec and then invokes the allocateConnection method of its associated ConnectionManager instance. HttpConnectionFactory also stores the Referenceable object, providing its accessors in support for factory creation in the server environment. HttpConnectionFactory also stores the instance of the Referenceable object, with accessor methods to support factory creation in the managed environment [0072] [0072] 3 ) HttpConnectionMetaData [0073] The following is a list of methods and their signatures implemented by the HttpConnectionMetaData class. [0074] HttpConnectionMetaData(HttpConnection) [0075] String getEISProductName( ) [0076] String getEISProductVersion( ) [0077] String getUserName( ) [0078] HttpConnectionMetaData is an object storing the connection information. It contains accessor methods to retrieve the following information: [0079] EISProductName [0080] EISProductVersion [0081] UserName [0082] 4) HttpConnectionRequestInfo [0083] The following is a list of methods and their signatures implemented by the HttpConnectionRequestInfo class. [0084] boolean equals(Object) [0085] String getPassword( ) [0086] String getUserName( ) [0087] int hashCode( ) [0088] void setPassword(String) [0089] void setUserName(String) [0090] HttpConnectionRequestInfo is a class containing the connection specific information that does not change the characteristics of the HttpManagedConnection i.e. the same instance of the HttpManagedConnection can be used to create HttpConnection instances with different HttpConnectionRequestInfo. HttpConnectionRequestInfo contains user name and password properties and implements hashCode and equals methods using these properties to calculate hash value and compare two instances for equality, respectively. [0091] 5) HttpConnectionSpec [0092] The following is a list of methods and their signatures implemented by the HttpConnectionSpec class. [0093] boolean equals(Object) [0094] String getPassword( ) [0095] String getUserName( ) [0096] int hashCode( ) [0097] void setPassword(String) [0098] void setUserName(String) [0099] HttpConnectionSpec represents the application level access to the connection specific information corresponding to the information contained in HttpConnectionRequestInfo. During the servicing of a connection request (getConnection( ) method implementation), HftpConnectionFactory copies values from HttpConnectionSpec to HttpConnectionRequestInfo. HttpConnectionSpec contains user name and password properties and implements hashCode and equals method that use these properties to calculate hash value and compare two instances for equality respectively. [0100] 6) HttpContentRecord [0101] The following is a list of methods and their signatures implemented by the HttpContentRecord class. [0102] Object clone( ) [0103] String getRecordName( ) [0104] String getRecordShortDescription( ) [0105] void read(InputStream) [0106] void setRecordName(String) [0107] void setRecordShortDescription(String) [0108] void write(OutputStream) [0109] HttpContentRecord is a class implementing javax.resource.cci.Record and javax.resource.cci.Streamable interfaces from the J2EE specification. It represents the data object passed to the execute method of the HttpInteraction class and containing the information received from target system 22 . The present invention uses this object internally to handle requests of the execution from applications that do not provide the output record i.e. invoke the execute( . . . ) method in HttpInteraction with only an input record argument. [0110] 7) HttpInteraction [0111] The following is a list of methods and their signatures implemented by the HttpInteraction class. [0112] HttpInteraction(Connection) [0113] void clearWarnings( ) [0114] void close( ) [0115] Record execute(InteractionSpec, Record) [0116] boolean execute(InteractionSpec, Record, Record) [0117] Connection getConnection( ) [0118] RecordFactory getRecordFactory( ) [0119] ResourceWarning getWarnings( ) [0120] void logTrace(String) [0121] void setLogWriter(PrintWriter) [0122] HttpInteraction represents objects used by an application 14 to perform interaction with target system 22 through the use of the present invention. A HttpInteraction object is created by HttpConnection and HttpConnection maintains a reference to the created object. The execution request, implemented through either of the execute methods of HttpInteraction is passed to the associated HttpConnection instance for further processing through the invocation of the protected call method and passing the arguments of the execute method, HttpInteractionSpec, input record and output record. If the execute method with only input record was invoked, HttpInteraction creates a new instance of the HttpContentRecord and passes it to the call method as the output record. Since HttpInteraction does not maintain any state, the implementation of the close method does not perform any operation except verifying that it is not in an already closed state. If it is, i.e. the close method had been previously invoked, the method throws javax.resource.spi.IllegalStateExcepton. This exception is also thrown if one of the execute methods is invoked when the HttpInteraction has been closed. [0123] 8) HttpInteractionSpec [0124] The following is a list of methods and their signatures implemented by the HttpInteractionSpec class. [0125] HttpInteractionSpec( ) [0126] String getContentType( ) [0127] Hashtable getHeaderFields( ) [0128] int getInteractionVerb( ) [0129] void setContentType(String) [0130] void setHeaderFields(Hashtable) [0131] void setInteractionVerb(int) [0132] The HttpInteractionSpec class implements interaction specific properties of the present invention. These properties include the interaction mode (mapped to the appropriate request method in the HttpManagedConnection), a value indicating one of the following interaction types: [0133] a) synchronous send and receive—the request is sent through connector 16 to target system 22 and the reply is passed back to the invoking application 14 ; [0134] b) synchronous send—the data is sent to target system 22 ; and [0135] c) synchronous receive—the data is received from target system 22 . [0136] These values are referred to in the J2EE Connector Architecture as: SYNC_SEND_RECEIVE, SYNC_SEND and SYNC_RECEIVE. In the interest of readability in the figures and the specification, we refer to these values as: “send_receive”, “send”, and “receive” respectively. [0137] Another property characterizing the interaction that can be specified on the HttpInteractionSpec are request headers. An application 14 using the present invention through connector 16 provides these as a hash table of keys and values. The class implementation also provides direct accessors to the contents type of the request, which is then automatically written as one of the http headers with the key “Content-Type”. [0138] 9) HttpManagedConnection [0139] The following is a list of methods and their signatures implemented by the HttpManagedConnection class. [0140] HttpManagedConnection(Subject, ConnectionRequestInfo, String) [0141] void addConnectionEventListener(ConnectionEventListener) [0142] void associateConnection(Object) [0143] void call(HttpConnection, InteractionSpec, Record, Record) [0144] void cleanup( ) [0145] void close(HttpConnection) [0146] void destroy( ) [0147] void errorOccurred(Exception) [0148] Object getConnection(Subject, ConnectionRequestInfo) [0149] LocalTransaction getLocalTransaction( ) [0150] PrintWriter getLogWriter( ) [0151] ManagedConnectionMetaData getMetaData( ) [0152] Subject getSecurityContext( ) [0153] String getUserName( ) [0154] XAResource getXAResource( ) [0155] boolean isDirty( ) [0156] void logTrace(String) [0157] void receive(Streamable, InputStream) [0158] void removeConnectionEventListener(ConnectionEventListener) [0159] void send(Streamable, OutputStream) [0160] void setDirty(boolean) [0161] void setLogWriter(PrintWriter) [0162] HttpManagedConnection is the class representing the HTTP protocol physical connection to target system 22 , specified through a URL. The application level access to the connection is provided through the application level handles HttpConnection which it can instantiate. HttpManagedConnection supports multiple handles, however only the most recently created handle can be used to perform interactions. The access from any other handle, before the last handle created issues close notification, is treated as an error and causes an IllegalStateException to be thrown. The validation and current handle maintenance is implemented through storing handles in a stack data structure with the valid handle at the top. The stack data structure is internal to the class implementation, and is not exposed outside the class and only used by its methods. Each access from the HttpConnection is validated against this data structure and the appropriate action is taken. The main methods implemented by the Http ManagedConnection class as are follows: [0163] a) void associateConnection(Object)—in this method, the passed HttpConnection object is disassociated from its current HttpManagedConnection, using the close method invocation and then associated with the managed connection as the most recent application level handle on top of the handles stack. [0164] b) void call(HttpConnection, InteractionSpec, Record, Record)—this method is used by HttpConnection to pass an execution request. HttpManagedConnection first verifies that the request has a valid handle passed as an argument and that the passed InteractionSpec object is the instance of the HttpInteractionSpec. Next, it creates a connected HttpURLConnection to the target system 22 URL using standard java.net library method invocation URL.openConnection( ). After the HttpURLConnection is created, the headers set on the HttpInteractionSpec are set on the HttpURLConnection as request properties the next action depends on the InteractionVerb property specified in HttpInteractionSpec. For send_receive the HttpURLConnection request method is set to “POST” and both doInput and doOutput properties of HttpURLConnection are set to true. For the send, the request method is set to PUT, doOutput to true and dolnput to false, and finally, for the receive, the request method is set to GET, doOutput to false and doInput to true. [0165] An input record is a record that is sent to target system 22 . Application 14 fills the input record with request data and sends it to the target 22 via connector 16 . Thus, it is input data to target system 22 . Similarly, an output record contains data output from target system 22 which is provided to application 14 . [0166] At the next step, the HttpURLConnection is connected and then the contents of the input record (extracted by viewing record as an implementation of the Streamable interface) is written to its output stream For send_receive and send and/or the content of the output record is read from the HttpURLConnection input stream for the send_receive and receive. Next, the headers returned by the HttpURLConnection are copied to the hash table and set in the HttpInteractionSpec to be returned to the application. The last step in the method is disconnecting the HttpURLConnection. If, during its execution the call method encounters a communication error, it sets an ERROR_OCCURRED event and then throws a CommException to the invoker. [0167] c) void cleanup( ) this method cleans up the internal state of the HttpManagedConnection by emptying the handles stack. [0168] d) void close(HttpConnection)—this method is invoked to forward an application close request on the connection handle. The HttpManagedConnection removes the handle that invoked the method from the top of the stack and sets a CONNECTION_CLOSED event. [0169] e) void destroy( )—this method permanently cleans up the internal state of the HttpManagedConnection by emptying and deallocating the handles stack and setting the HttpURLConnection to null. [0170] f) Object getConnection(Subject, ConnectionRequestInfo)—in this method, new connection handle is created and put on the top of the handles stack. [0171] Since the HTTP Connector does not support transactional behaviour, i.e. the ability to roll back units of work, the methods getXARespirce( ) and getLocalTransaction( ) throw the NotSupportedException. [0172] 10) HttpManagedConnectionFactory [0173] The following is a list of methods and their signatures implemented by the HttpManagedConnectionFactory class. [0174] Object createConnectionFactory( ) [0175] Object createConnectionFactory(ConnectionManager) [0176] ManagedConnection [0177] createManagedConnection(Subject, connectionRequestInfo) [0178] boolean equals(Object) [0179] PrintWriter getLogWriter( ) [0180] String getURL( ) [0181] int hashCode( ) [0182] void logTrace(String) [0183] ManagedConnection [0184] matchManagedConnections(Set, Subject, ConnectionRequestInfo) [0185] void setLogWriter(PrintWrter) [0186] void setURL(String) [0187] The HttpManagedConnectionFactory class instance creates HttpManagedConnection objects. Each created object is passed the connection URL of the target system 22 and the logWriter properties of the factory. The logWriter is a class (PrintWriter to be exact) which is used by the HttpManagedConnectionFactory to record its trace and error information. When it is set on the HttpManagedConnectionFactory, the J2EE specification Connector architecture specification, requires it to pass the instance to every managed connection it creates. [0188] 11) HttpManagedConnnectionMetaData [0189] The following is a list of methods and their signatures implemented by the HttpManagedConnectionMetaData class. [0190] HttpManagedConnectionMetaData(HttpManagedConnection) [0191] String getEISProductName( ) [0192] String getEISProductVersion( ) [0193] int getMaxConnections( ) [0194] String getUserName( ) [0195] HttpManagedConnectionMetaData provides information about the connector 16 such as target system 22 product and version, maximum number of connections supported by the target system 22 and the name of the user. [0196] 12) HttpResourceAdapterMetaData [0197] The following is a list of methods and their signatures implemented by the HttpResourceAdapterMetaData class. [0198] String getAdapterName( ) [0199] String getAdapterShortDescription( ) [0200] String getAdapterVendorName( ) [0201] String getAdapterVersion( ) [0202] String [] getInteractionSpecsSupported( ) [0203] String getSpecVersion( ) [0204] boolean supportsExecuteWithInputAndOutputRecord( ) [0205] boolean supportsExecuteWithInputRecordOnly( ) [0206] boolean supportsLocalTransactionDemarcation( ) [0207] HttpResourceAdapterMetaData provides an application 14 with the characteristics of the resource adapter terms such as name, description, vendor name, adapter version and specification version supported. It also contains information describing which optional features of the specification have been implemented, such as names of InteractionSpec implementation classes, which type of execute method connectors are supported and whether it supports local transactions. Here we use the term “resource adapter” as it is the terminology utilized by the J2EE. Connector architecture specification. For the purposes of the present specification and claims, the terms “resource adapter” and “connector” (i.e. connector 16 ), are interchangeable [0208] To illustrate how the above described classes implement the present invention, we refer now to FIGS. 2 a to 2 c which are a series of flowcharts illustrating the process of an embodiment of the present invention. The process is shown generally as 30 . [0209] Referring first to FIG. 2 a , beginning at step 32 an application 14 (see FIG. 1), requests a connection to a target system 22 using the HTTP protocol by invoking: execute(HttpInteractionSpec,inputRecord,outputRecord) of class HttpInteraction at step 34 . At step 36 if an outputRecord was not specified, then one is created at step 38 . At step 40 the call method of class HttpConnection is invoked by: call(HttpInteraction, HttpInteractionSpec, inputRecord, outputRecord). At step 42 the call method of class HttpManagedConnection is invoked by: call(HttpConnection, HttpInteractionSpec, inputRecord, outputRecord). Block 44 serves as a transfer to FIG. 2 b. [0210] Referring now to FIG. 2 b , at step 46 if the current handle (i.e. the instance of HttpConnection) is not the most current, an IllegalStateException is thrown at step 48 and process 30 terminates. Should the current handle be valid, process 30 moves to step 50 where a connection with target system 22 is made by invoking URL.openConnection( ) of the standard java.net library. At step 52 it is determined if a valid connection has been established. If a valid connection has not been established, control moves to step 54 where a CommException is thrown and process 30 ends. If a valid connection has been established, then process 30 continues. Block 56 serves as a transfer to FIG. 2 c. [0211] Referring now to FIG. 2 c , at step 58 the value of the InteractionVerb contained within the HttpInteraction instance is examined. The value of InteractionVerb may be one of: receive, send, or send_receive. For each value one of the following steps are taken: [0212] a) For receive, at step 60 requestMethod of HttpURLConnection is set to GET, dolnput is set to true and doOutput is set to false. Data is then received from the target system 22 at step 68 and provided to application 14 . [0213] b) For send, at step 62 HttpURLConnection request method is set to PUT, doInput is set to false and dooutput is set to true. Data is then sent to the target system 22 at step 70 . [0214] c) For send_receive, at step 64 HttpURLConnection request method is set to POST, doInput is set to true and doOutput is set to true. Properties of the HttpURLConnection data is next sent from application 14 to the target system 22 at step 66 and then data is received for application 14 from the target system 22 at step 68 . [0215] At step 72 process 30 ends and control is returned to application 14 . [0216] Although the above disclosure mentions the Internet or WWW as an example of a network on which the present invention may be utilized, it is not the intent of the inventors to exclude Intranets, Extranets, or any form of network using an HTTP protocol, including but not limited to: wireless, twisted pair, cable and satellite. In a special case, connector 16 and target system 22 may reside on the same system 10 . Similarly System 10 may be any computing device capable of supporting the present invention, including but not limited to: standalone computer systems, handheld devices and television settop boxes. [0217] Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention as outlined in the claims appended hereto.
The present invention provides an HTTP connector implementation to be used by disparate computer systems to communicate with each other over the World Wide Web. In particular, the present invention is directed to business to business communications and meets the specifications of the J2EE Connector Architecture. The present invention provides an HTTP interface that may easily be adapted by existing applications while at the same time shielding the developer from the low level details of the HTTP.
7
TECHNICAL FIELD OF THE INVENTION [0001] This invention relates to a method for controlling at least one fan for the regulation of the cooling demand of at least two cooling elements comprised in a drill rig, the cooling demand of each one of the cooling elements being determined, that the determined cooling demands are weighted together and that the fan is controlled based on said weighting together. [0002] The invention also relates to a drill rig comprising an engine, at least two cooling elements and at least one fan, a control unit being arranged to control the fan based on a weighting together, executed in the control unit, of current cooling demands in the cooling elements. [0003] By drill rigs, in particular drill rigs for drilling in rock are intended and above all drill rigs for drilling in rock above ground. BACKGROUND OF THE INVENTION AND PRIOR ART [0004] The background of the present invention is the need of being able to provide cooling in a drill rig, or in a drilling unit, which is an established synonymous concept in the technical field, to all the cooling-dependent components that are arranged therein. By cooling-dependent components, for instance, engine, compressors and hydraulic-oil pumps are intended, as well as the fluids that circulate in the above-mentioned system and that run the risk of accumulating too much heat upon use. Said components with the appurtenant cooling elements and fans associated therewith are accommodated in an engine house arranged in the drill rig. The cooling elements consist, for instance, of an engine water cooler, a charge-air cooler, a hydraulic-oil cooler and a compressor cooler. [0005] A generally recognized way to solve the above-mentioned problems is to place one or more fans, which presses or sucks air through cooling elements intended for the purpose. Previously, the fans have rotated at the highest rotation speed, highest power, all the time the drill rig has been in operation, without regulation of the same and independently of the cooling demand of the components of the drill rig. [0006] Frequently or always, the different cooling elements have different instantaneous needs of cooling air, which makes the fan, consequently more or less all the time, operating more than necessary in relation to the need for either of the cooling elements or even all cooling elements. [0007] The problem with the above-mentioned way of controlling, or to be precise, not controlling the fans, is that the cooling elements that have lower cooling demand than what the fans provide run the risk of becoming overcooled, above all when the drill rig is used in cold climates. [0008] An additional disadvantage of letting the fan operate at a constantly high rotation speed (highest power) is that the sound level from the fans and thereby also the sound level in the driver's cab is pronounced. OBJECTS AND FEATURES OF THE INVENTION [0009] The present invention aims at obviating the above-mentioned disadvantages of previously known fan controls and presenting an improved solution. A primary object is to present a fan control, which provides a more efficient and more adapted cooling for the cooling elements of the drill rig. A second object is to present a fan control, which allows drill rigs to be used in colder climates without the components included in the drill rig running the risk of becoming overcooled. An additional object is to provide a drilling unit having closer-to-optimal temperature of the fluids that are in need of cooling. Still another object is to present a fan system being more silent in operation. [0010] In a first aspect, this invention relates to a method of the type defined by way of introduction, which is characterized in that at least one cooling element is equipped with a safety thermostat, which, if required, prevents undercooling by the fact that the fluid in question is not allowed to circulate in this cooling element. Preferred embodiments of the inventive method are further seen in the dependent claims 2 to 6 . [0011] In a second aspect, the invention also relates to a drilling unit according to claim 7 for execution of the method. Preferred embodiments of the inventive drill rig are further seen in the dependent claims 8 to 16 . The advantage of said method and device is that the speed of rotation/effect of the fan is adjustable, which entails that the air flow that passes through the cooling elements at each instant of time in a better way corresponds to the cooling demand that the same have at said instant of time. Thanks to the closer-to-optimal fluid temperatures with reduced temperature variations, the stress on the components of the systems decreases, which increases the service life of the same. By regulating the rotation speed of the fan, so that it does not operate with constantly high rotation speed (highest power), also the sound level in and around the drill rig is lowered. A lower rotation speed of the fan further entails a smaller power output from the engine and accordingly reduced fuel consumption. [0012] Additional advantages and features of the invention are seen in the following, detailed description of preferred embodiments. BRIEF DESCRIPTION OF THE APPENDED DRAWINGS [0013] Hereinafter, the invention will be described with an exemplifying purpose, reference being made to the accompanying drawings, in which: [0014] FIG. 1 is a side view of a drill rig according to the invention, [0015] FIG. 2 is a schematic, partially cut view from above of a carrier included in the drill rig, and [0016] FIG. 3 is an alternative embodiment of the carrier corresponding to FIG. 2 . DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0017] In FIG. 1 , a drill rig according to the invention is shown, generally designated 1 . The drill rig 1 comprises a carrier 3 carried by a pair of caterpillars 2 , or the like, and comprising a driver's cab 4 and an engine house-forming chassis 5 . The engine house 5 is in no way tight but comprises holes and openings so that good circulation-of-air therein is allowed. In the front part of the carrier 3 , a feeder 6 is arranged, which is carried by one or more bars 7 and which comprises a drilling equipment 8 , which is carried by the bars 7 . The radius of working and accessibility of the drill rig 1 is determined by the bars 7 and the drilling equipment 8 , which are of conventional type. [0018] Now reference is made primarily to FIG. 2 , in which a partially cut view from above of the carrier 3 of the drill rig 1 (a plurality of components are eliminated for the sake of clarity) is schematically shown. Centrally in the engine house 5 , an engine 9 is arranged, preferably an internal combustion engine and in particular a diesel engine, which is connected to a compressor 10 and one or more hydraulic-oil pumps 11 for the supply of power to, for instance, the drilling equipment 8 of the drill rig 1 . As these components or fluids associated therewith have substantial cooling demands, cooling elements 12 or coolers are further arranged in the rear part of the engine house 5 , which coolers, for instance, consist of engine water coolers, charge-air coolers, hydraulic-oil coolers and compressor-oil cooler. The cooling elements 12 are connected to the respective unit in such a way that the fluids used in the units can circulate between the cooling elements 12 and the units. At the cooling elements 12 , one or more fans 13 are arranged, which, in a preferred embodiment, are hydraulically driven, but alternatively they may, for instance, be driven pneumatically or electrically, i.e., the fans 13 may be arranged to be driven by a suitable power system present on the drill rig 1 . Furthermore, a hydraulic-oil tank 14 is arranged in the engine house 5 and in a suitable way connected to the hydraulic-oil pump 11 and remaining parts of the hydraulic-oil system. [0019] In the embodiment shown, the fans 13 are located downstreams of the cooling elements 12 , since it from a flow point of view, at a short distance, is easier to suck than press air between closely located cooling flanges. However, from a space point of view, it may be preferred to place the fans 13 upstreams of the cooling elements 12 . In the same way, the design of the engine house 5 entails that the cooling elements 12 in the embodiment shown are divided into groups, more precisely two by two, with an individual fan 13 for each group. The cooling elements 12 may advantageously be divided into groups including cooling elements 12 having similar cooling demand in the respective group. In the embodiment example according to FIG. 2 , hence, it is advantageous to place the cooling elements 12 for the hydraulic oil and the compressor oil together and for the engine water and the charge air together. [0020] Now reference is made also to FIG. 3 , in which an alternative embodiment of the carrier 3 of the drill rig 1 is shown. In this alternative embodiment, in contrast to FIG. 2 , the engine 9 , the compressor 10 and the hydraulic-oil pumps 11 are transverse to the longitudinal direction of the drill rig 1 and placed in the rear part of the engine house 5 . Furthermore, the cooling elements 12 are placed centrally in a group and with a common fan 13 , located downstreams of the cooling elements 12 . In addition, the location of the hydraulic-oil tank 14 has also been changed. [0021] Common to the two alternative configurations in FIGS. 2 and 3 is that they comprise a control unit 15 , which in the figures is outlined to be located near the driver's cab 4 . The control unit 15 should be programmable and comprise a plurality of inputs and outputs for signal transfer. The control unit 15 may consist of an ordinary control unit in the drill rig 1 or of a specific control unit only for the control of the fan(s) 13 . In addition, the control unit 15 may be located on any another suitable location than the one shown in the figures, for instance on the proper engine 9 . Furthermore, the drill rig 1 comprises a plurality of sensors to measure operating parameters, such as preferably temperatures, but also other quantities may be measured, such as power output or the like. The temperatures are measured, for instance, of the cooling fluids on suitable places in the respective system. A first sensor 16 is, for instance, located in the engine 9 or in the vicinity thereof in order to measure the temperature of the engine cooling water. A second sensor 17 is arranged to measure the temperature of the hydraulic oil, said second sensor 17 preferably being located in the hydraulic-oil tank 14 . A third sensor 18 is located at the compressor 10 in order to measure the compressor-oil temperature. A fourth sensor 19 is located on a suitable place in order to measure the temperature of the charge air and a fifth sensor 20 is located in such a way that the same can measure the temperature of the surrounding air around the drill rig 1 . Preferably, the measurement of the ambient temperature is carried out in front of the engine house 5 , such as is outlined in the drawings, in order to get as correct and true a measuring as possible. This as a consequence of the warm air that is generated in the engine house 5 being blown out rearward from the same. All sensors 16 - 20 are in a suitable way operatively connected to the control unit 15 that controls the fans 13 in a suitable way. In the preferred embodiment, the sensors 16 - 20 are connected to the control unit 15 via electrical cabling (not shown), but also wireless or optic communication between the units is feasible. [0022] In prior art, the fan that creates an air flow through the cooling elements is switched on if the drill rig is in operation. In other words, when the drill rig operates, the fan operates at a constantly high rotation speed (highest power). Characteristic of the drill rig 1 according to the invention is that the rotation speed of the fan 13 can be varied, within a range of from 0 % to 100 % of the requisite rotation speed, by the control of the same. The fan 13 according to the invention operates all the time when there is a cooling demand, but at a low rotation speed and only exceptionally at the highest rotation speed. The sound that arises during the operation of the fans propagates through the construction and into the driver's cab 4 and creates, at highest rotation speed, noise inside the same, but by means of a regulated fan at a low rotation speed the noise decreases markedly, and furthermore the wear on the same decreases. A decreased power output also entails reduced fuel consumption. [0023] The rotation speed of the fan is controlled or regulated by the control unit 15 based on the determined cooling demands or the lo temperatures in the cooling elements 12 . More precisely, by the fact that the control unit 15 compares or weights together the cooling demands of the cooling elements 12 that constitute a group of cooling elements, after which the individual fan 13 is controlled based on the occurring cooling demand of the cooling elements 12 associated with the respective fan. It is advantageous to control the individual fan 13 that co-operates with the individual group of cooling elements 12 based on the greatest cooling demand among the cooling elements 12 in the group. However, it should be pointed out that also other suitable ways of weighting together the cooling demands are feasible in order to control the fans 13 . [0024] In order to determine the cooling demand of the charge-air cooler, also the ambient temperature is measured, since the maximally allowable the charge-air temperature is closely dependent on the ambient temperature, which gives better determination of the cooling demand and further additionally better precision in the control of the fan 13 . Furthermore, also the cooling demand of the other cooling elements 12 can be more exactly defined with the knowledge about the ambient temperature. [0025] Said sensors 16 - 20 need necessarily not consist of sensors specific to the object discussed above with the purpose of providing temperatures only for the fan control, but in certain applications and embodiments of the inventive drill rig 1 , values from existing sensors may be used in the determination of the cooling demand of the various cooling elements 12 . For instance, the engine water temperature is frequently measured by already existing sensors. [0026] In spite of the fans 13 providing a closer-to-optimal cooling of the cooling elements 12 according to the present invention, some kind of safety thermostats (not shown) should be comprised that make it impossible for the fluids in the different systems to be cooled below a certain limit value, more precisely by the fact that the fluid in question is not allowed to circulate in the cooling element of the same. Feasible Modifications of the Invention [0027] The invention is not only limited to the embodiments described above and shown in the drawings. Thus, the method as well as the drill rig may be modified in miscellaneous ways within the scope of the subsequent claims. It should be especially mentioned that the drill rig not necessarily has to comprise a cab but may still be controlled from a position outside the same. It should also be appreciated that each fan may consist of one or more fan elements. It should also be pointed out that even if the cooling elements are divided into groups, the individual fans do not need to have separate control but the fans may be mutually controlled. By way of introduction, it is mentioned that by drill rigs, in particular drill rigs for the drilling in rock above ground are intended, yet the invention is not limited to this but also drilling in other materials and operation below ground are feasible. It should be pointed out that by the expression, regulation of the cooling demand, both in the claims and in the detailed description, it is meant that the cooling demand of the cooling element can be regulated by letting the fan operate, for instance, at different rotation speed. More precisely, by the fact that a high fan speed entails a lower instantaneous cooling demand and a low fan speed entails a higher instantaneous cooling demand. Thus, the cooling demand should neither be too high or too low but is regulated to a suitable level.
A method for controlling at least one fan ( 13 ) for the regulation of the cooling demand of at least two cooling elements ( 12 ) comprised in a drill rig ( 1 ), the cooling demand of each one of the cooling elements ( 12 ) being determined, that the determined cooling demands are weighted together and that the fan ( 13 ) is controlled based on the weighting together. The invention is characterized in that at least one cooling element is equipped with a safety thermostat, which, if required, prevents undercooling by the fact that the fluid in question is not allowed to circulate in this cooling element. Furthermore, the invention also relates to a drill rig for the execution of the above-mentioned method.
5
This application is a national phase filing under 35 U.S.C. § 371 of international patent application number PCT/IB2015/052672 filed Apr. 13, 2015, which in turn claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 61/984,086 filed Apr. 25, 2014, the disclosure of each of these applications is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION The present invention generally relates to heteroaromatic compounds, which are dopamine D1 ligands, for example dopamine D1 agonists or partial agonists. BACKGROUND OF THE INVENTION Dopamine acts upon neurons through two families of dopamine receptors, D1-like receptors (D1Rs) and D2-like receptors (D2Rs). The D1-like receptor family consists of D1 and D5 receptors which are expressed in many regions of the brain. D1 mRNA has been found, for example, in the striatum and nucleus accumbens. See e.g., Missale C, Nash S R, Robinson S W, Jaber M, Caron M G “Dopamine receptors: from structure to function”, Physiological Reviews 78:189-225 (1998). Pharmacological studies have reported that D1 and D5 receptors (D1/D5), namely D1-like receptors, are linked to stimulation of adenylyl cyclase, whereas D2, D3, and D4 receptors, namely D2-like receptors, are linked to inhibition of cAMP production. Dopamine D1 receptors are implicated in numerous neuropharmacological and neurobiological functions. For example, D1 receptors are involved in different types of memory function and synaptic plasticity. See e.g., Goldman-Rakic P S et al., “Targeting the dopamine D1 receptor in schizophrenia: insights for cognitive dysfunction”, Psychopharmacology 174(1):3-16 (2004). Moreover, D1 receptors have been implicated in a variety of psychiatric, neurological, neurodevelopmental, neurodegenerative, mood, motivational, metabolic, cardiovascular, renal, ophthalmic, endocrine, and/or other disorders described herein including schizophrenia (e.g., cognitive and negative symptoms in schizophrenia), schizotypal personality disorder, cognitive impairment associated with D2 antagonist therapy, ADHD, impulsivity, autism spectrum disorder, mild cognitive impairment (MCI), age-related cognitive decline, Alzheimer's dementia, Parkinson's disease (PD), Huntington's chorea, depression, anxiety, treatment-resistant depression (TRD), bipolar disorder, chronic apathy, anhedonia, chronic fatigue, post-traumatic stress disorder, seasonal affective disorder, social anxiety disorder, post-partum depression, serotonin syndrome, substance abuse and drug dependence, Tourette's syndrome, tardive dyskinesia, drowsiness, sexual dysfunction, migraine, systemic lupus erythematosus (SLE), hyperglycemia, dislipidemia, obesity, diabetes, sepsis, post-ischemic tubular necrosis, renal failure, resistant edema, narcolepsy, hypertension, congestive heart failure, postoperative ocular hypotonia, sleep disorders, pain, and other disorders in a mammal. See e.g., Goulet M, Madras B K “D(1) dopamine receptor agonists are more effective in alleviating advanced than mild parkinsonism in 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine-treated monkeys”, Journal of Pharmacology and Experimental Therapy 292(2):714-24 (2000); Surmeier D J et al., “The role of dopamine in modulating the structure and function of striatal circuits”, Prog. Brain Res. 183:149-67 (2010). New or improved agents that modulate (such as agonize or partially agonize) D1R are needed for developing new and more effective pharmaceuticals to treat diseases or conditions associated with dysregulated activation of D1R, such as those described herein. WO2013026516 reports bicyclic heteroaromatic compounds having the following structure that are kinase inhibitors and can be used, for example, for treating tumors. CN102558147 reports pyridinecarboxamide derivatives of the following formula: as inhibitors of tyrosine kinase and/or serine-threonine kinase for treating cancer. WO2007009524 reports 2-arylbenzothiazoles of the following formula useful as protein kinase inhibitors for treating diseases such as those associated with abnormal and hyperproliferation of cells. US2005/0153989 reports compounds of the following structure useful for treating and/or preventing conditions and diseases associated with kinase activity, e.g., EGFR activity, such as cancer, hyperplasia, psoriasis, cardiac hypertrophy, arthrosclerosis, dermatitis and/or diseases or conditions associated with undesired cellular hyperproliferation. Abou-Zeid, K. A. M. et al, “synthesis of 6-(4-(substituted amino)phenyl)-4,5-dihydropyridazin-3(2H)-ones as potential positive inotropic agents,” Egyptian Journal of Pharmaceutical Sciences (1998), Volume Date 1997, 38(4-6), 319-331, reports some pyridazinones, for example, that were evaluated as inhibitors of cardiac cAMP phosphodiesterase. Demange, L. et. al, “Synthesis and evaluation of new potent inhibitors of CK1 and CDK5, two kinases involved in Alzheimer's disease,” Medicinal Chemistry Research (2013), 22(7), 3247-3258 reports compounds having one of following structures as inhibitors of CK1 and CDK5. In addition, it also reports certain intermediates having one of the following structures: US20100317646 reports pyrazolopyridine compounds of the following structure as kinase inhibitors (e.g., LRRK or LRRK2 inhibitors). US20100247517 reports compounds having one of the following structures useful for the production of pharmaceutical compositions for the prophylaxis and/or treatment of diseases which can be influenced by the inhibition of the kinase activity of Mnk1 and/or Mnk2 (Mnk2a or Mnk2b) and/or variants thereof. Bischoff, F. et. al, “Design and Synthesis of a Novel Series of Bicyclic Heterocycles As Potent γ-Secretase Modulators,” Journal of Medicinal Chemistry (2012), 55(21), 9089-9106 reports certain imidazole containing compounds γ-secretase modulators including the following two compounds: US2012/0022090 reports substituted benzoxazole, benzimidazole, oxazolopyridine, and imidazopyridine derivative of the following structure that are γ-secretase modulators useful in the treatment of diseases. US2011/0281881 reports substituted bicyclic derivative of the following structure wherein Het 2 can be as γ-secretase modulators useful in the treatment of diseases such as Alzheimer's Disease. WO2008067420 reports compounds of one of the flowing structures or pharmaceutically acceptable salts, proudrugs, or tautomers thererof, as caspase activators and inducers of apoptosis. SUMMARY OF THE INVENTION In a first aspect, the present invention provides a method for treating a D1-mediated (or D1-associated) disorder in a mammal, which method comprises administering to said mammal a therapeutically effective amount of a compound of Formula I: or a pharmaceutically acceptable salt thereof, wherein: L 1 is O, S, NR N , C(═O), CH(OH), or CH(OCH 3 ); Q 1 is an N-containing 5- to 10-membered heteroaryl, an N-containing 4- to 12-membered heterocycloalkyl, or phenyl, each optionally substituted with one R 9 and further optionally substituted with 1, 2, 3, or 4 R 10 ; X 1 is O, S, NH, N(C 1-4 alkyl), N(cyclopropyl), or N(—CH 2 -cyclopropyl); X 2 is N or C-T 2 ; X 3 is N or C-T 3 ; provided that when X 1 is O or S, then at least one of X 2 and X 3 is not N; X 4 is N or C-T 4 ; T 1 is H, —OH, halogen, —CN, or optionally substituted C 1-2 alkyl; each of T 2 , T 3 , and T 4 is independently selected from the group consisting of H, —OH, halogen, —CN, optionally substituted C 1-4 alkyl, optionally substituted C 3-4 cycloalkyl, optionally substituted cyclopropylmethyl, and optionally substituted C 1-4 alkoxy; R N is H, C 1-4 alkyl, C 3-4 cycloalkyl, or —C 1-2 alkyl-C 3-4 cycloalkyl, each of R 1 and R 2 is independently selected from the group consisting of H, halogen, —CN, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, and C 3-6 cycloalkyl, wherein each of said C 1-6 alkyl and C 3-6 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from halo, —OH, —CN, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each of R 3 and R 4 is independently selected from the group consisting of H, halogen, —OH, —NH 2 , —NH(CH 3 ), —N(CH 3 ) 2 , —NO 2 , —CN, —SF 5 , C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 haloalkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, a 4- to 10-membered heterocycloalkyl, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , —N(R 7 )(S(═O) 2 R 8 ), —S(═O) 2 —N(R 5 )(R 6 ), —SR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, and heterocycloalkyl is optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CN, —OH, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, C 3-6 cycloalkyl, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —C(═O)—OR 8 , —C(═O)H, —C(═O)R 8 , —C(═O)N(R 5 )(R 6 ), —N(R 7 )(S(═O) 2 R 8 ), —S(═O) 2 —N(R 5 )(R 6 ), —SR 8 , and —OR 8 ; or R 1 and R 3 together with the two carbon atoms to which they are attached form a fused N-containing 5- or 6-membered heteroaryl, a fused N-containing 5- or 6-membered heterocycloalkyl, a fused 5- or 6-membered cycloalkyl, or a fused benzene ring, each optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halo, —CN, —OH, —NH 2 , —NH(CH 3 ), —N(CH 3 ) 2 , C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, and C 1-3 haloalkoxy; R 5 is H, C 1-4 alkyl, C 1-4 haloalkyl, or C 3-7 cycloalkyl; R 6 is H or selected from the group consisting of C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, a 4- to 10-membered heterocycloalkyl, C 6-10 aryl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl-, wherein each of the selections from the group is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of —OH, —NH 2 , —NH(CH 3 ), —N(CH 3 ) 2 , —CN, C 1-4 alkyl, C 3-7 cycloalkyl, C 1-4 hydroxylalkyl, —S—C 1-4 alkyl, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)—O—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , C 1-4 haloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; or R 5 and R 6 together with the N atom to which they are attached form a 4- to 10-membered heterocycloalkyl or a 5- to 10-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —OH, —NH 2 , —NH(CH 3 ), —N(CH 3 ) 2 , oxo, —C(═O)H, —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; R 7 is selected from the group consisting of H, C 1-4 alkyl, and C 3-7 cycloalkyl; R 8 is selected from the group consisting of C 1-6 alkyl, C 3-7 cycloalkyl, a 4- to 14-membered heterocycloalkyl, C 6-10 aryl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl-, wherein each of the selections from the group is optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CF 3 , —CN, —OH, —NH 2 , —NH(CH 3 ), —N(CH 3 ) 2 , oxo, —S—C 1-4 alkyl, C 1-4 alkyl, C 1-4 haloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each of R 9 and R 10 is independently selected from the group consisting of halogen, —OH, —CN, —SF 5 , —NO 2 , Oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 6-10 aryl, a 4- to 10-membered heterocycloalkyl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —S(═O) 2 N(R 5 )(R 6 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , —SR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 6-10 aryl, 4- to 10-membered heterocycloalkyl, 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of halogen, OH, —CN, —NO 2 , C 1-4 alkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, —N(R 5 )(R 6 ), —S—(C 1-4 alkyl), —S(═O) 2 —(C 1-4 alkyl), C 6-10 aryloxy, [(C 6-10 aryl)-C 1-4 alkyloxy-optionally substituted with 1 or 2 C 1-4 alkyl], oxo, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)O—C 1-4 alkyl, —C(═O)NH 2 , —NHC(═O)H, —NHC(═O)—(C 1-4 alkyl), C 3-7 cycloalkyl, a 5- or 6-membered heteroaryl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; or R 9 and an adjacent R 10 together with the two ring atoms on Q 1 to which they are attached form a fused benzene ring or a fused 5- or 6-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 independently selected R 10a ; and each R 10a is independently selected from the group consisting of halogen, —OH, —N(R 5 )(R 6 ), —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, —SF 5 , C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy, with the provisos that (1) when X 4 is N and X 1 is NH, N(C 1-4 alkyl), N(cyclopropyl), N(—CH 2 -cyclopropyl), or S, then L 1 is other than NR N ; (2) when X 1 is NH then X 3 is other than N; (3) when X 2 is N, X 3 is C-T 3 , X 4 is C-T 4 , T 3 is not H, and X 1 is NH, then L 1 is other than O or NR N ; (4) when X 2 is C-T 2 , X 3 is C-T 3 , X 4 is C-T 4 , then X 1 is other than S or O; (5) when L 1 is O, X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than NH; (6) when X 1 is NH, N(C 1-4 alkyl), N(cyclopropyl), N(—CH 2 -cyclopropyl), or O, and X 3 is N then L 1 is other than NR N ; and (7) Q 1 is other than an optionally substituted benzo[d]thiazolyl (e.g., benzo[d]thiazol-2-yl) or an optionally substituted monocyclic 2-oxo-1H-pyridin-1-yl. In some embodiments, when X 4 is N, then L 1 is other than NR N . In some embodiments, L 1 is other than NR N . In some embodiments, when X 4 is N, then X 1 is other than NH, N(C 1-4 alkyl), N(cyclopropyl), or N(—CH 2 -cyclopropyl). In some embodiments, when X 4 is N, then X 1 is other than S. In some embodiments, when X 4 is N, then X 1 is other than NH, N(C 1-4 alkyl), N(cyclopropyl), N(—CH 2 -cyclopropyl), or S. In some embodiments, Q 1 is other than an optionally substituted monocyclic 2-oxo-1H-pyridin-1-yl. In some embodiments, when X 2 is N, X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than NH. In some embodiments, when X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than NH. In some embodiments, L 1 is other than NR N ; Q 1 is other than an optionally substituted benzo[d]thiazolyl; Q 1 is other than an optionally substituted phenyl; when X 4 is N, then X 1 is other than NH, N(C 1-4 alkyl), N(cyclopropyl), N(—CH 2 -cyclopropyl) or S; and when X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than NH. In some further embodiments, Q 1 is other than an optionally substituted monocyclic 2-oxo-1H-pyridin-1-yl. In some yet further embodiments, L 1 is O or S. In still further embodiments, L 1 is O. In some embodiments, the disorder is selected from schizophrenia (e.g., cognitive and negative symptoms in schizophrenia), schizotypal personality disorder, cognitive impairment [e.g., cognitive impairment associated with schizophrenia, cognitive impairment associated with AD, cognitive impairment associated with PD, cognitive impairment associated with pharmacotherapy therapy (e.g., D2 antagonist therapy)], attention deficit hyperactivity disorder (ADHD), impulsivity, compulsive gambling, overeating, autism spectrum disorder, mild cognitive impairment (MCI), age-related cognitive decline, dementia (e.g., senile dementia, HIV-associated dementia, Alzheimer's dementia, Lewy body dementia, vascular dementia, or frontotemporal dementia), restless leg syndrome (RLS), Parkinson's disease, Huntington's chorea, anxiety, depression (e.g., age-related depression), major depressive disorder (MDD), treatment-resistant depression (TRD), bipolar disorder, chronic apathy, anhedonia, chronic fatigue, post-traumatic stress disorder, seasonal affective disorder, social anxiety disorder, post-partum depression, serotonin syndrome, substance abuse and drug dependence, drug abuse relapse, Tourette's syndrome, tardive dyskinesia, drowsiness, excessive daytime sleepiness, cachexia, inattention, sexual dysfunction (e.g., erectile dysfunction or post-SSRI sexual dysfunction), migraine, systemic lupus erythematosus (SLE), hyperglycemia, atherosclerosis, dislipidemia, obesity, diabetes, sepsis, post-ischemic tubular necrosis, renal failure, hyponatremia, resistant edema, narcolepsy, hypertension, congestive heart failure, postoperative ocular hypotonia, sleep disorders, and pain. In some embodiments, L 1 is O or S. In some further embodiments, L 1 is S. In some embodiments, L 1 is O. In some embodiments, L 1 is NH. In some embodiments, L 1 is C(═O), CH(OH), or CH(OCH 3 ). In some further embodiments, L 1 is C(═O) or CH(OH). In some embodiments, T 1 is H, F, Cl, methyl, or C 1 fluoroalkyl; and each of T 2 , T 3 , and T 4 is independently selected from the group consisting of H, halogen, —CN, C 1-4 alkyl, C 1-4 haloalkyl, C 3-4 cycloalkyl, C 3-4 halocycloalkyl, cyclopropylmethyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some further embodiments, each of T 2 , T 3 , and T 4 is independently selected from the group consisting of H, halogen, —CN, methoxy, C 1 fluoroalkoxy, methyl, and C 1 fluoroalkyl, In some embodiments, T 1 is H, F, Cl, methyl, or C 1 fluoroalkyl. In some embodiments, T 1 is H and T 4 is H. In some embodiments, each of T 2 and T 3 is independently H, CN, F, Cl, Br, methyl, methoxy, C 1 fluoroalkoxy, or C 1 fluoroalkyl. In some embodiments, X 1 is O. In some embodiments, X 1 is O; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is N. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N, and X 4 is C-T 4 . In some embodiments, X 1 is S. In some embodiments, X 1 is S; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is N. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N, and X 4 is C-T 4 . In some embodiments, X 1 is NH. In some embodiments, X 1 is NH; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is C-T 4 . In some embodiments, X 1 is NH; X 2 is C-T 2 ; and X 3 is N. In some embodiments, X 4 is N; and X 1 is O or S. In some further embodiments, 0 or 1 of X 2 and X 3 is N. In some embodiments, X 4 is N; and X 1 is O. In some further embodiments, 0 or 1 of X 2 and X 3 is N. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-a: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-b: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-c: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-d: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-e: or a pharmaceutically acceptable salt thereof. The embodiments described herein in the first aspect of the invention, unless specified otherwisely, include the methods for use of a compound of Formula I, I-a, I-b, I-c, I-d, or I-e, or a pharmaceutically acceptable salt thereof. In some embodiments, each of R 1 and R 2 is independently H or halogen. In some further embodiments, each of R 1 and R 2 is H. In some embodiments, each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In some embodiments, R 3 is H and R 4 is H, halogen, —CN, methyl, or C 1 haloalkyl. In some embodiments, R 3 is H and R 4 is methyl. In some embodiments, Q 1 is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl, each optionally substituted with one R 9 and 1, 2, 3, or 4 R 10 . In some embodiments, Q 1 is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl, each substituted with one R 9 and further optionally substituted with 1, 2, 3, or 4 R 10 . In some embodiment: R 9 is halogen(e.g. Cl), C 1-4 alkyl, C 1-4 haloalkyl, —CN, —SF 5 , —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkoxy, or C 3-7 cycloalkyl, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —SF 5 , —NO 2 , Oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 6-10 aryl, a 4- to 10-membered heterocycloalkyl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —S(═O) 2 N(R 5 )(R 6 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , —SR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 6-10 aryl, 4- to 10-membered heterocycloalkyl, 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of halogen, OH, —CN, —NO 2 , C 1-4 alkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, —N(R 5 )(R 6 ), —S—(C 1-4 alkyl), —S(═O) 2 —(C 1-4 alkyl), C 6-10 aryloxy, [(C 6-10 aryl)-C 1-4 alkyloxy-optionally substituted with 1 or 2 C 1-4 alkyl], oxo, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)O—C 1-4 alkyl, —C(═O)NH 2 , —NHC(═O)H, —NHC(═O)—(C 1-4 alkyl), C 3-7 cycloalkyl, a 5- or 6-membered heteroaryl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; or R 9 and an adjacent R 10 together with the two ring atoms on Q 1 to which they are attached form a fused benzene ring or a fused 5- or 6-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 independently selected R 10a . In some embodiment, R 9 is halogen (e.g. Cl), C 1-4 alkyl, C 1-4 haloalkyl, —CN, —SF 5 , —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkoxy, or C 3-7 cycloalkyl, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some further embodiments, R 9 is C 1-4 alkyl, C 1-4 haloalkyl, —CN, —SF 5 , —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkoxy, or C 3-7 cycloalkyl, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some embodiments: Q 1 is a moiety of ring Q 1a is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl; represents a single bond or double bond; each of Z 1 and Z 2 is independently C or N; R 9 is halogen (e.g. Cl), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, —CN, —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, or C 3-7 cycloalkoxy, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —NO 2 , oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 6-10 aryl, a 4- to 10-membered heterocycloalkyl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 2-4 alkenyl-, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —S(═O) 2 N(R 5 )(R 6 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 6-10 aryl, 4- to 10-membered heterocycloalkyl, 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 2-4 alkenyl- is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of halogen, OH, —CN, —NO 2 , C 1-4 alkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, —N(R 5 )(R 6 ), —S—(C 1-4 alkyl), —S(═O) 2 —(C 1-4 alkyl), C 6-10 aryloxy, (C 6-10 aryl)-C 1-4 alkyloxy-optionally substituted with 1 or 2 C 1-4 alkyl, oxo, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)O—C 1-4 alkyl, —C(═O)NH 2 , —NHC(═O)H, —NHC(═O)—(C 1-4 alkyl), C 3-7 cycloalkyl, a 5- or 6-membered heteroaryl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; or R 9 and the adjacent R 10 together with the two ring atoms on ring Q 1a to which they are attached form a fused benzene ring or a fused 5- or 6-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 independently selected R R10a ; each R 10a is independently selected from the group consisting of halogen, —OH, —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, C 1-4 haloalkyl, and C 1-4 haloalkoxy; and m is 0, 1, 2, 3, or 4. In some embodiments, Q 1 is a moiety of Moiety M 1 and Z 1 is C. In some embodiments, Q 1 or ring Q 1a is an optionally substituted N-containing 6-membered heteroaryl. In some embodiments, Q 1 or ring Q 1a is an optionally substituted pyridinyl, pyrimidinyl, pyridazinyl, or pyrazinyl. In some further embodiments, Q 1 or ring Q 1a is an optionally substituted pyrimidinyl, pyridazinyl, or pyrazinyl. In some embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of OH, halogen (e.g., Cl), CN, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, and C 3-7 cycloalkyl. In some further embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of CN, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, and C 3-7 cycloalkyl. In still further embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1 or 2 substituents each independently selected from the group consisting of CN, C 1-4 alkyl, and C 1-4 haloalkyl. In some embodiments, Moiety M 1 is selected from the group consisting of quinolinyl, isoquinolinyl, 1H-imidazo[4,5-c]pyridinyl, imidazo[1,2-a]pyridinyl, 1H-pyrrolo[3,2-c]pyridinyl, imidazo[1,2-a]pyrazinyl, imidazo[2,1-c][1,2,4]triazinyl, imidazo[1,5-a]pyrazinyl, imidazo[1,2-a]pyrimidinyl, 1H-indazolyl, 9H-purinyl, imidazo[1,2-a]pyrimidinyl, [1,2,4]triazolo[1,5-a]pyrimidinyl, isoxazolo[5,4-c]pyridazinyl, isoxazolo[3,4-c]pyridazinyl, and [1,2,4]triazolo[4,3-b]pyridazinyl, each optionally substituted with 1, 2, or 3 R 10 and further optionally substituted with 1 or 2 R 10a ; or wherein Moiety M 1 is selected from the group consisting of pyrimidinyl, pyrazinyl, pyridinyl, pyridazinyl, 1H-pyrazolyl, 1H-pyrrolyl, 4H-pyrazolyl, 1H-imidazolyl, 1H-imidazolyl, 3-oxo-2H-pyridazinyl, 1H-2-oxo-pyrimidinyl, 1H-2-oxo-pyridinyl, 2,4(1H,3H)-dioxo-pyrimidinyl, and 1H-2-oxo-pyrazinyl, each substituted with R 9 and further optionally substituted with 1, 2, or 3 R 10 . In some embodiments: Moiety M 1 is R 10a is C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, or C 3-7 cycloalkyl; t1 is 0 or 1; and t is 0 or 1. In some embodiments, Moiety M 1 is e″). In some embodiments, Moiety M 1 is In some embodiments: Moiety M 1 is and R 11 is H, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, or C 3-7 cycloalkyl. In some embodiments, R 9 is halogen (e.g., Cl), C 3-6 cycloalkyl (e.g., cyclopropyl), C 1-4 alkyl, or —CN. In some further embodiments, R 9 is halogen (e.g., Cl), C 1-4 alkyl, or —CN. In some embodiments, R 9 is C 1-4 alkyl or —CN. In some further embodiments, R 9 is C 1-4 alkyl. In some yet further embodiments, R 9 is methyl. In some embodiments, each R 10 is independently selected from the group consisting of halogen (e.g., Cl), C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, —CN, and —N(R 5 )(R 6 ), wherein each of R 5 and R 6 independently is H or selected from the group consisting of C 1-4 alkyl, C 1-4 haloalkyl, and C 3-7 cycloalkyl; or R 5 and R 6 together with the N atom to which they are attached form a 4- to 7-membered heterocycloalkyl or a 5-membered heteroaryl, each optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CN, C 1-4 alkyl, C 1-4 alkoxy, C 3-6 cycloalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy. In some further embodiments, each R 10 is independently halogen (e.g., Cl), C 1-4 alkyl or CN. In yet further embodiments, each R 10 is independently C 1-4 alkyl or CN. In still yet further embodiments, each R 10 is C 1-4 alkyl (e.g., methyl). In further embodiments, each R 10 is C 1-4 alkyl methyl. In some embodiments, each of R 9 and R 10 is independently halogen (e.g., Cl), C 3-6 cycloalkyl (e.g., cyclopropyl), C 1-4 alkyl, or —CN. In some further embodiments, each of R 9 and R 10 is independently halogen (e.g., Cl), C 1-4 alkyl, or —CN. In some embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In some further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; X 4 is N; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is N, X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; X 4 is N; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M-m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is N, X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. The first aspect of the invention includes any subset of any embodiment described herein. The first aspect of the invention includes combinations of two or more embodiments described herein, or any subset thereof. The first aspect of the invention further provides the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subset thereof) for use in treating a D1-mediated (or D1-associated) disorder described herein. The first aspect of the invention further provides use of the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subset thereof) for treating a D1-mediated (or D1-associated) disorder described herein. The first aspect of the invention further provides use of the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subset thereof) in manufacturing a medicament for use in treating a D1-mediated (or D1-associated) disorder described herein. The term “therapeutically effective amount” as used herein refers to that amount of the compound (including a pharmaceutically acceptable salt thereof) being administered which will relieve to some extent one or more of the symptoms of the disorder being treated. In reference to the treatment of a D1-mediated disorder (e.g., schizophrenia), a therapeutically effective amount refers to that amount which has the effect of relieving to some extent (or, for example, eliminating) one or more symptoms associated with a D1-mediated disorder (e.g., schizophrenia, or cognitive and negative symptoms in schizophrenia, or cognitive impairment associated with schizophrenia). The term “treating”, as used herein, unless otherwise indicated, means reversing, alleviating, inhibiting the progress of, or preventing the disorder or condition to which such term applies, or one or more symptoms of such disorder or condition. The term “treatment”, as used herein, unless otherwise indicated, refers to the act of treating as “treating” is defined herein. The term “treating” also includes adjuvant and neo-adjuvant treatment of a subject. The compound of Formula I or its salt used in the method for treating a D1-mediated (or D1-associated) disorder of present invention is a D1R modulator (e.g., a D1 agoninst for example, a D1 partial agonist). The amount of the compound of Formula I or a pharmaceutically acceptable amount used in the method of the present invention is effective in modulating (e.g., agonizing or partially agonizing) D1R. The present invention further provides a method for modulating (such as agonizing or partially agonizing) an activity of D1R (either in vitro or in vivo), comprising contacting (including incubating) the D1R with a compound of Formula I or a pharmaceutically acceptable salt thereof (such as one selected from Examples 1-23 herein) described herein. In a second aspect, the present invention provides a compound of Formula I: or a pharmaceutically acceptable salt thereof, wherein: L 1 is O, S, NR N , C(═O), or CH(OH); Q 1 is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl, each optionally substituted with one R 9 and further optionally substituted with 1, 2, 3, or 4 R 10 ; X 1 is O, S, or NH; X 2 is N or C-T 2 ; X 3 is N or C-T 3 ; provided that when X 1 is O or S, then at least one of X 2 and X 2 is not N; X 4 is N or C-T 4 ; T 1 is H, F, Cl, methyl, or C 1 fluoroalkyl; each of T 2 , T 3 , and T 4 is independently selected from the group consisting of H, halogen, —CN, C 1-4 alkyl, C 1-4 haloalkyl, C 3-4 cycloalkyl, C 3-4 halocycloalkyl, cyclopropylmethyl, C 1-4 alkoxy, C 1-4 haloalkoxy; R N is H, C 1-4 alkyl, C 3-4 cycloalkyl, or —C 1-2 alkyl-C 3-4 cycloalkyl, each of R 1 and R 2 is independently selected from the group consisting of H, halogen, —CN, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-6 cycloalkyl, —C(═O)OH, and C(═O)—O—(C 1-4 alkyl), wherein each of said C 1-6 alkyl and C 3-6 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from halo, —OH, —CN, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each of R 3 and R 4 is independently selected from the group consisting of H, halogen, —OH, —NO 2 , —CN, —SF 5 , C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 haloalkoxy, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, a 4- to 10-membered heterocycloalkyl, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , —OC(═O)R 8 , —N(R 7 )(S(═O) 2 R 8 ), —S(═O) 2 —N(R 5 )(R 6 ), —SR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, and heterocycloalkyl is optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CN, —OH, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, C 3-6 cycloalkyl, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —C(═O)—OR 8 , —C(═O)H, —C(═O)R 8 , —C(═O)N(R 5 )(R 6 ), —N(R 7 )(S(═O) 2 R 8 ), —S(═O) 2 —N(R 5 )(R 6 ), —SR 8 , and —OR 8 ; or R 1 and R 3 together with the two carbon atoms to which they are attached form a fused N-containing 5- or 6-membered heteroaryl, a fused N-containing 5- or 6-membered heterocycloalkyl, a fused 5- or 6-membered cycloalkyl, or a fused benzene ring, each optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halo, —CN, —OH, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, and C 1-3 haloalkoxy; R 5 is H, C 1-4 alkyl, C 1-4 haloalkyl, or C 3-7 cycloalkyl; R 6 is H or selected from the group consisting of C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, a 4- to 10-membered heterocycloalkyl, C 6-10 aryl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl-, wherein each of the selections from the group is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of —OH, —CN, C 1-4 alkyl, C 3-7 cycloalkyl, C 1-4 hydroxylalkyl, —S—C 1-4 alkyl, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)—O—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , C 1-4 haloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; or R 5 and R 6 together with the N atom to which they are attached form a 4- to 10-membered heterocycloalkyl or a 5- to 10-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —OH, oxo, —C(═O)H, —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; R 7 is selected from the group consisting of H, C 1-4 alkyl, and C 3-7 cycloalkyl; R 8 is selected from the group consisting of C 1-6 alkyl, C 3-7 cycloalkyl, a 4- to 14-membered heterocycloalkyl, C 6-10 aryl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl-, wherein each of the selections from the group is optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CF 3 , —CN, —OH, oxo, —S—C 1-4 alkyl, C 1-4 alkyl, C 1-4 haloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; R 9 is halogen, C 1-4 alkyl, C 1-4 haloalkyl, —CN, —SF 5 , —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkoxy, or C 3-7 cycloalkyl, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —SF 5 , —NO 2 , Oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 6-10 aryl, a 4- to 10-membered heterocycloalkyl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —S(═O) 2 N(R 5 )(R 6 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , —SR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 6-10 aryl, 4- to 10-membered heterocycloalkyl, 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of halogen, OH, —CN, —NO 2 , C 1-4 alkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, —N(R 5 )(R 6 ), —S—(C 1-4 alkyl), —S(═O) 2 —(C 1-4 alkyl), C 6-10 aryloxy, [(C 6-10 aryl)-C 1-4 alkyloxy-optionally substituted with 1 or 2 C 1-4 alkyl], oxo, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)O—C 1-4 alkyl, —C(═O)NH 2 , —NHC(═O)H, —NHC(═O)—(C 1-4 alkyl), C 3-7 cycloalkyl, a 5- or 6-membered heteroaryl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; or R 9 and an adjacent R 10 together with the two ring atoms on Q 1 to which they are attached form a fused benzene ring or a fused 5- or 6-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 independently selected R 10a ; and each R 10a is independently selected from the group consisting of halogen, —OH, —N(R 5 )(R 6 ), —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, —SF 5 , C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy, with the proviso that (1) when X 4 is N then X 1 is O; (2) when X 1 is NH then X 3 is other than N; (3) when X 2 is C-T 2 , X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than S or O; (4) when L 1 is O or NR N , X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than NH; (5) when X 1 is NH or O, and at least one of X 3 and X 4 is N, then Q 1 is not an optionally substituted monocyclic 5-membered ring; and (6) when X 4 is N and X 1 is O, then L 1 is other than NR N . In some embodiments, when X 3 is C-T 3 and X 4 is C-T 4 , then X 1 is other than NH. In some embodiments, when Q 1 is an optionally substituted monocylic ring, then a ring-forming carbon atom of Q 1 is directly linked to the benzene ring of Formula I that is substituted by R 1 , R 2 , R 3 , and R 4 . In some embodiments, when a ring-forming nitrogen atom of Q 1 is directly linked to the benzene ring of Formula I that is substituted by R 1 , R 2 , R 3 , and R 4 , then Q 1 is an optionally substituted bicyclic ring (e.g., an optionally substituted bicyclic heteroaryl). In some embodiments, Q 1 is other than an optionally substituted monocyclic 5-membered ring. In some embodiments, L 1 is other than NR N . In some embodiments, each of the ring-forming atoms of Q 1 is a nitrogen or carbon atom. In some further embodiment, when Q 1 is an optionally substituted monocylic ring, then a ring-forming carbon atom of Q 1 is directly linked to the benzene ring that is substituted by R 1 , R 2 , R 3 , and R 4 . In some embodiments, L 1 is other than NR N . In some embodiments: (1) when X 4 is N then X 1 is O; (2) when X 1 is NH then X 3 is other than N; (3) when X 2 is C-T 2 , X 3 is C-T 3 , and X 4 is C-T 4 , then X 1 is other than S or O; (4) when X 3 is C-T 3 and X 4 is C-T 4 , then X 1 is other than NH; (5) Q 1 is other than an optionally substituted monocyclic 5-membered ring; (6) each of the ring-forming atoms of Q 1 is a nitrogen or carbon atom; (7) when Q 1 is an optionally substituted monocylic ring, then a ring-forming carbon atom of Q 1 is directly linked to the benzene ring that is substituted by R 1 , R 2 , R 3 , and R 4 ; and (8) L 1 is other than NR N . In some embodiments, L 1 is O or S. In some further embodiments, L 1 is S. In some embodiments, L 1 is O. In some embodiments, L 1 is NH. In some embodiments, L 1 is C(═O) or CH(OH). In some embodiments, each of T 2 , T 3 , and T 4 is independently selected from the group consisting of H, halogen, —CN, methoxy, C 1 fluoroalkoxy, methyl, and C 1 fluoroalkyl. In some embodiments, T 1 is H and T 4 is H. In some embodiments, each of T 2 and T 3 is independently H, CN, F, Cl, Br, methoxy, C 1 fluoroalkoxy, methyl, or C 1 fluoroalkyl. In some embodiments, T 1 is H; each of T 2 and T 3 is independently H, F, Cl, methoxy, C 1 fluoroalkoxy, methyl, or C 1 fluoroalkyl; and T 4 is H. In some embodiments, T 2 is H and T 3 is H. In some embodiments, X 1 is O. In some embodiments, X 1 is O; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is N. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N, and X 4 is C-T 4 . In some embodiments, X 1 is S. In some embodiments, X 1 is S; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is N. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N, and X 4 is C-T 4 . In some embodiments, X 1 is NH. In some embodiments, X 1 is NH; and 0 or 1 of X 2 and X 3 is N. In some further embodiments, X 4 is C-T 4 . In some embodiments, X 1 is NH; X 2 is C-T 2 ; and X 3 is N. In some embodiments, X 4 is N; and X 1 is O or S. In some further embodiments, 0 or 1 of X 2 and X 3 is N. In some embodiments, X 4 is N; and X 1 is O. In some further embodiments, 0 or 1 of X 2 and X 3 is N. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-a: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-b: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-c: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-d: or a pharmaceutically acceptable salt thereof. In some embodiments, the compound of Formula I or a pharmaceutically acceptable salt thereof is a compound of Formula I-e: or a pharmaceutically acceptable salt thereof. The embodiments described herein in the second aspect of the invention, unless specified otherwisely, include a compound of Formula I, I-a, I-b, I-c, I-d, or I-e, or a pharmaceutically acceptable salt thereof. In some embodiments, each of R 1 and R 2 is independently H or halogen. In some further embodiments, each of R 1 and R 2 is H. In some embodiments, each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In some embodiments, R 3 is H and R 4 is H, halogen, —CN, methyl, or C 1 haloalkyl. In some embodiments, R 3 is H and R 4 is methyl. In some embodiments, Q 1 is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl, each substituted with one R 9 and further optionally substituted with 1, 2, 3, or 4 R 10 . In some embodiments: Q 1 is a moiety of ring Q 1a is an N-containing 5- to 6-membered heteroaryl or an N-containing 5- to 6-membered heterocycloalkyl; represents a single bond or double bond; each of Z 1 and Z 2 is independently C or N; R 9 is halogen (e.g. Cl), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, —CN, —N(R 5 )(R 6 ), C 1-6 alkoxy, C 1-6 haloalkoxy, or C 3-7 cycloalkoxy, wherein each of the C 1-4 alkyl and C 3-7 cycloalkyl is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy; each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —NO 2 , oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 6-10 aryl, a 4- to 10-membered heterocycloalkyl, a 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 2-4 alkenyl-, —N(R 5 )(R 6 ), —N(R 7 )(C(═O)R 8 ), —S(═O) 2 N(R 5 )(R 6 ), —C(═O)—N(R 5 )(R 6 ), —C(═O)—R 8 , —C(═O)—OR 8 , and —OR 8 , wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 6-10 aryl, 4- to 10-membered heterocycloalkyl, 5- to 10-membered heteroaryl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, (4- to 10-membered heterocycloalkyl)-C 1-4 alkyl-, (C 6-10 aryl)-C 1-4 alkyl-, (5- to 10-membered heteroaryl)-C 1-4 alkyl-, and (5- to 10-membered heteroaryl)-C 2-4 alkenyl- is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of halogen, OH, —CN, —NO 2 , C 1-4 alkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, —N(R 5 )(R 6 ), —S—(C 1-4 alkyl), —S(═O) 2 —(C 1-4 alkyl), C 6-10 aryloxy, (C 6-10 aryl)-C 1-4 alkyloxy-optionally substituted with 1 or 2 C 1-4 alkyl, oxo, —C(═O)H, —C(═O)—C 1-4 alkyl, —C(═O)O—C 1-4 alkyl, —C(═O)NH 2 , —NHC(═O)H, —NHC(═O)—(C 1-4 alkyl), C 3-7 cycloalkyl, a 5- or 6-membered heteroaryl, C 1-4 haloalkyl, and C 1-4 haloalkoxy; or R 9 and the adjacent R 10 together with the two ring atoms on ring Q 1a to which they are attached form a fused benzene ring or a fused 5- or 6-membered heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 independently selected R 10a ; each R 10a is independently selected from the group consisting of halogen, —OH, —C(═O)OH, —C(═O)—C 1-4 alkyl, —C(═O)—NH 2 , —C(═O)—N(C 1-4 alkyl) 2 , —CN, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 hydroxylalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, C 1-4 haloalkyl, and C 1-4 haloalkoxy; and m is 0, 1, 2, 3, or 4. In some embodiment, each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —SF 5 , —NO 2 , Oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, and (C 3-7 cycloalkyl)-C 1-4 alkyl-, wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, and (C 3-7 cycloalkyl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some embodiments, Z 1 is C. In some embodiments, Q 1 or ring Q 1a is an optionally substituted N-containing 6-membered heteroaryl. In some embodiments, Q 1 or ring Q 1a is an optionally substituted pyridinyl, pyrimidinyl, pyridazinyl, or pyrazinyl. In some further embodiments, Q 1 or ring Q 1a is an optionally substituted pyrimidinyl, pyridazinyl, or pyrazinyl. In some embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of OH, CN, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, and C 3-7 cycloalkyl. In some further embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1, 2, 3, or 4 substituents each independently selected from the group consisting of CN, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, and C 3-7 cycloalkyl. In still further embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1 or 2 substituents each independently selected from the group consisting of CN, C 1-4 alkyl, and C 1-4 haloalkyl. In yet still further embodiments, Q 1 or ring Q 1a is pyrimidinyl, pyridazinyl, or pyrazinyl, each of which is optionally substituted with 1 or 2 substituents each independently selected from the group consisting of CN and C 1-4 alkyl. In some embodiments, Moiety M 1 is selected from the group consisting of quinolinyl, isoquinolinyl, 1H-imidazo[4,5-c]pyridinyl, imidazo[1,2-a]pyridinyl, 1H-pyrrolo[3,2-c]pyridinyl, imidazo[1,2-a]pyrazinyl, imidazo[2,1-c][1,2,4]triazinyl, imidazo[1,5-a]pyrazinyl, imidazo[1,2-a]pyrimidinyl, 1H-indazolyl, 9H-purinyl, imidazo[1,2-a]pyrimidinyl, [1,2,4]triazolo[1,5-a]pyrimidinyl, isoxazolo[5,4-c]pyridazinyl, isoxazolo[3,4-c]pyridazinyl, and [1,2,4]triazolo[4,3-b]pyridazinyl, each optionally substituted with 1, 2, or 3 R 10 and further optionally substituted with 1 or 2 R 10a ; or wherein Moiety M 1 is selected from the group consisting of pyrimidinyl, pyrazinyl, pyridinyl, pyridazinyl, 1H-pyrazolyl, 1H-pyrrolyl, 4H-pyrazolyl, 1H-imidazolyl, 1H-imidazolyl, 3-oxo-2H-pyridazinyl, 1H-2-oxo-pyrimidinyl, 1H-2-oxo-pyridinyl, 2,4(1H,3H)-dioxo-pyrimidinyl, and 1H-2-oxo-pyrazinyl, each substituted with R 9 and further optionally substituted with 1, 2, or 3 R 10 . In some embodiments: Moiety M 1 is R 10a is C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, or C 3-7 cycloalkyl; t1 is 0 or 1; and t is 0 or 1. In some embodiments, Moiety M 1 is In some embodiments, Moiety M 1 is In some embodiments: Moiety M 1 is and R 11 is H, C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, or C 3-7 cycloalkyl. In some embodiments, R 9 is halogen (e.g., Cl), C 3-6 cycloalkyl (e.g., cyclopropyl), C 1-4 alkyl, or —CN. In some further embodiments, R 9 is halogen (e.g., Cl), C 1-4 alkyl, or —CN. In some embodiments, R 9 is C 1-4 alkyl or —CN. In some further embodiments, R 9 is C 1-4 alkyl. In some yet further embodiments, R 9 is methyl. In some embodiments, each R 10 is independently selected from the group consisting of halogen, —OH, —CN, —SF 5 , —NO 2 , Oxo, thiono, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, and (C 3-7 cycloalkyl)-C 1-4 alkyl-, wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, and (C 3-7 cycloalkyl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, —N(R 5 )(R 6 ), C 1-4 alkyl, C 1-4 haloalkyl, C 3-7 cycloalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some embodiments, each R 10 is independently selected from the group consisting of —CN, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 hydroxylalkyl, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, (C 3-7 cycloalkyl)-C 1-4 alkyl-, and —N(R 5 )(R 6 ), wherein each of said C 1-6 alkyl, C 3-7 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, and (C 3-7 cycloalkyl)-C 1-4 alkyl- is optionally substituted with 1, 2, 3, 4, or 5 substituents each independently selected from the group consisting of halogen, C 1-4 alkoxy, and C 1-4 haloalkoxy. In some further embodiments, each R 10 is independently selected from the group consisting of —CN, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 hydroxylalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, and C 3-4 cycloalkyl, and —N(R 5 )(R 6 ). In some embodiments, each R 10 is independently selected from the group consisting of C 1-4 alkyl, C 1-4 haloalkyl, (C 1-2 alkoxy)-C 1-4 alkyl-, —CN, and —N(R 5 )(R 6 ), wherein each of R 5 and R 6 independently is H or selected from the group consisting of C 1-4 alkyl, C 1-4 haloalkyl, and C 3-7 cycloalkyl; or R 5 and R 6 together with the N atom to which they are attached form a 4- to 7-membered heterocycloalkyl or a 5-membered heteroaryl, each optionally substituted with 1, 2, or 3 substituents each independently selected from the group consisting of halogen, —CN, C 1-4 alkyl, C 1-4 alkoxy, C 3-6 cycloalkyl, C 1-4 haloalkyl, and C 1-4 haloalkoxy. In some further embodiments, each R 10 is independently C 1-4 alkyl or CN. In yet further embodiments, each R 10 is independently C 1-4 alkyl. In still yet further embodiments, each R 10 is methyl. In some embodiments, each of R 9 and R 10 is independently halogen (e.g., Cl), C 3-6 cycloalkyl (e.g., cyclopropyl), C 1-4 alkyl, or —CN. In some further embodiments, each of R 9 and R 10 is independently halogen (e.g., Cl), C 1-4 alkyl, or —CN. In some embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In some further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; X 4 is N; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is N, X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M-m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is O; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; X 4 is N; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 0 or 1 of X 2 and X 3 is N (e.g., neither of X 2 and X 3 is N); X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; 1 of X 2 and X 3 is N (e.g., X 2 is N and X 3 is C-T 3 ); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is N, X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is S; X 2 is C-T 2 , X 3 is C-T 3 ; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is as described in one of the embodiments provided herein (e.g., M 1 -g, M 1 -k, M 1 -m, or M 1 -n). In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; 0 or 1 of X 2 and X 3 is N (e.g., X 2 is C-T 2 and X 3 is N); X 4 is C-T 4 ; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, X 1 is NH; X 2 is C-T 2 , X 3 is N; X 4 is N; Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, L 1 is O or S. In yet further embodiments, L 1 is O. In still further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet still further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-a or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-a or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-a or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-a or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-b or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-b or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-b or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-b or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-c or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-c or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-c or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-c or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-d or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-d or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-d or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-d or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-e or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -g. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-e or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -k. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-e or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -m. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the compound of Formula I or a salt thereof is a compound of Formula I-e or a salt thereof; and Q 1 is M 1 ; and M 1 is M 1 -n. In some further embodiments, each of R 1 and R 2 is independently H or halogen; and each of R 3 and R 4 is independently H, halogen, —CN, methyl, C 1 haloalkyl, methoxy, or C 1 haloalkoxy. In yet further embodiments, each of R 1 and R 2 is H; R 3 is H; and R 4 is methyl. In some still further embodiments, each of R 9 and R 10 is independently C 1-4 alkyl or CN. In yet still further embodiments, each of R 9 and R 10 is independently methyl or CN. In some embodiments, the invention also provides one or more of the compounds described in Examples 1-23 in the Examples section of the subject application, pharmaceutically acceptable salts of the compounds; or the N-oxides of the compound or salt. In some embodiments, the present invention provides a compound selected from the group consisting of: 4-[4-(4,6-dimethylpyrimidin-5-yl)-3-methylphenoxy]furo[2,3-d]pyrimidine; 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one; (−)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one; (+)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one; 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one; (+)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one; (−)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one; 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1,5-dimethylpyrimidine-2,4(1H,3H)-dione; 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-4,6-dimethylpyridazin-3(2H)-one; 5-ethyl-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1-methylpyrimidine-2,4(1H,3H)-dione; 1-ethyl-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-5-methylpyrimidine-2,4(1H,3H)-dione; and 1-cyclopropyl-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-5-methylpyrimidine-2,4(1H,3H)-dione, or a pharmaceutically acceptable salt thereof. The second aspect of the invention includes any subset of any embodiment described herein. The second aspect of the invention includes combinations of two or more embodiments described hereinabove, or any subset thereof. The second aspect of the invention further provides the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subcombination thereof) for use in treating a D1-mediated (or D1-associated) disorder described herein. The second aspect of the invention further provides use of the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subcombination thereof) for treating a D1-mediated (or D1-associated) disorder described herein. The second aspect of the invention further provides use of the compound of Formula I or a pharmaceutically acceptable salt thereof (including all embodiments and combinations of two or more embodiments described herein or any subcombination thereof) in manufacturing a medicament for use in treating a D1-mediated (or D1-associated) disorder described herein. The compound of Formula I or its salt of the second aspect of present invention is a D1R modulator (e.g., a D1R agoninst for example, a D1R partial agonist). Thus, the second aspect of present invention further provides a method for modulating (such as agonizing or partially agonizing) an activity of D1R (either in vitro or in vivo), comprising contacting (including incubating) the D1R with a compound of Formula I or a pharmaceutically acceptable salt thereof (such as one selected from Examples 1-23 herein) described herein. As used herein, the term “n-membered” where n is an integer typically describes the number of ring-forming atoms in a moiety where the number of ring-forming atoms is n. For example, pyridine is an example of a 6-membered heteroaryl ring and thiophene is an example of a 5-membered heteroaryl group. At various places in the present specification, substituents of compounds of the invention are disclosed in groups or in ranges. It is specifically intended that the invention include each and every individual subcombination of the members of such groups and ranges. For example, the term “C 1-6 alkyl” is specifically intended to include C 1 alkyl (methyl), C 2 alkyl (ethyl), C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl. For another example, the term “a 5- to 10-membered heteroaryl group” is specifically intended to include any 5-, 6-, 7-, 8-, 9- or 10-membered heteroaryl group. As used herein, the term “alkyl” is defined to include saturated aliphatic hydrocarbons including straight chains and branched chains. In some embodiments, the alkyl group has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. For example, the term “C 1-6 alkyl,” as well as the alkyl moieties of other groups referred to herein (e.g., C 1-6 alkoxy) refers to linear or branched radicals of 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl). For yet another example, the term “C 1-4 alkyl” refers to linear or branched aliphatic hydrocarbon chains of 1 to 4 carbon atoms; the term “C 1-3 alkyl” refers to linear or branched aliphatic hydrocarbon chains of 1 to 3 carbon atoms; the term “C 1-2 alkyl” refers to linear or branched aliphatic hydrocarbon chains of 1 to 2 carbon atoms; and the term “C 1 alkyl” refers to methyl. An alkyl group optionally can be substituted by one or more (e.g. 1 to 5) suitable substituents. As used herein, the term “alkenyl” refers to aliphatic hydrocarbons having at least one carbon-carbon double bond, including straight chains and branched chains having at least one carbon-carbon double bond. In some embodiments, the alkenyl group has 2 to 20 carbon atoms, 2 to 10 carbon atoms, 2 to 6 carbon atoms, 3 to 6 carbon atoms, or 2 to 4 carbon atoms. For example, as used herein, the term “C 2-6 alkenyl” means straight or branched chain unsaturated radicals (having at least one carbon-carbon double bond) of 2 to 6 carbon atoms, including, but not limited to, ethenyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and the like. An alkenyl group optionally can be substituted by one or more (e.g. 1 to 5) suitable substituents. When the compounds of Formula I contain an alkenyl group, the alkenyl group may exist as the pure E form, the pure Z form, or any mixture thereof. As used herein, the term “alkynyl” refers to aliphatic hydrocarbons having at least one carbon-carbon triple bond, including straight chains and branched chains having at least one carbon-carbon triple bond. In some embodiments, the alkynyl group has 2 to 20, 2 to 10, 2 to 6, or 3 to 6 carbon atoms. For example, as used herein, the term “C 2-6 alkynyl” refers to straight or branched hydrocarbon chain alkynyl radicals as defined above, having 2 to 6 carbon atoms. An alkynyl group optionally can be substituted by one or more (e.g. 1 to 5) suitable substituents. As used herein, the term “cycloalkyl” refers to saturated or unsaturated, non-aromatic, monocyclic or polycyclic (such as bicyclic) hydrocarbon rings (e.g., monocyclics such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or bicyclics including spiro, fused, or bridged systems (such as bicyclo[1.1.1]pentanyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1]octanyl or bicyclo[5.2.0]nonanyl, decahydronaphthalenyl, etc.). The cycloalkyl group has 3 to 15 carbon atoms. In some embodiments the cycloalkyl may optionally contain one, two or more non-cumulative non-aromatic double or triple bonds and/or one to three oxo groups. In some embodiments, the bicycloalkyl group has 6 to 14 carbon atoms. For example, the term “C 3-14 cycloalkyl” refers to saturated or unsaturated, non-aromatic, monocyclic or polycyclic (such as bicyclic) hydrocarbon rings of 3 to 14 ring-forming carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[1.1.1]pentanyl, or cyclodecanyl); and the term “C 3-7 cycloalkyl” refers to saturated or unsaturated, non-aromatic, monocyclic or polycyclic (such as bicyclic) hydrocarbon rings of 3 to 7 ring-forming carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[1.1.1]pentan-1-yl, or bicyclo[1.1.1]pentan-2-yl). For another example, the term “C 3-6 cycloalkyl” refers to saturated or unsaturated, non-aromatic, monocyclic or polycyclic (such as bicyclic) hydrocarbon rings of 3 to 6 ring-forming carbon atoms. For yet another example, the term “C 3-4 cycloalkyl” refers to cyclopropyl or cyclobutyl. Also included in the definition of cycloalkyl are moieties that have one or more aromatic rings (including aryl and heteroaryl) fused to the cycloalkyl ring, for example, benzo or thienyl derivatives of cyclopentane, cyclopentene, cyclohexane, and the like (e.g., 2,3-dihydro-1H-indene-1-yl, or 1H-inden-2(3H)-one-1-yl). The cycloalkyl group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used herein, the term “aryl” refers to all-carbon monocyclic or fused-ring polycyclic aromatic groups having a conjugated pi-electron system. The aryl group has 6 or 10 carbon atoms in the ring(s). Most commonly, the aryl group has 6 carbon atoms in the ring. For example, as used herein, the term “C 6-10 aryl” means aromatic radicals containing from 6 to 10 carbon atoms such as phenyl or naphthyl. The aryl group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used herein, the term “heteroaryl” refers to monocyclic or fused-ring polycyclic aromatic heterocyclic groups with one or more heteroatom ring members (ring-forming atoms) each independently selected from O, S and N in at least one ring. The heteroaryl group has 5 to 14 ring-forming atoms, including 1 to 13 carbon atoms, and 1 to 8 heteroatoms selected from O, S, and N. In some embodiments, the heteroaryl group has 5 to 10 ring-forming atoms including one to four heteroatoms. The heteroaryl group can also contain one to three oxo or thiono (i.e. ═S) groups. In some embodiments, the heteroaryl group has 5 to 8 ring-forming atoms including one, two or three heteroatoms. For example, the term “5-membered heteroaryl” refers to a monocyclic heteroaryl group as defined above with 5 ring-forming atoms in the monocyclic heteroaryl ring; the term “6-membered heteroaryl” refers to a monocyclic heteroaryl group as defined above with 6 ring-forming atoms in the monocyclic heteroaryl ring; and the term “5- or 6-membered heteroaryl” refers to a monocyclic heteroaryl group as defined above with 5 or 6 ring-forming atoms in the monocyclic heteroaryl ring. For another example, term “5- or 10-membered heteroaryl” refers to a monocyclic or bicyclic heteroaryl group as defined above with 5, 6, 7, 8, 9 or 10 ring-forming atoms in the monocyclic or bicyclic heteroaryl ring. A heteroaryl group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. Examples of monocyclic heteroaryls include those with 5 ring-forming atoms including one to three heteroatoms or those with 6 ring-forming atoms including one, two or three nitrogen heteroatoms. Examples of fused bicyclic heteroaryls include two fused 5- and/or 6-membered monocyclic rings including one to four heteroatoms. Examples of heteroaryl groups include pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g., 1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl, 1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl, 1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl (e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl, benzofuryl, indolyl, 1H-imidazo[4,5-c]pyridinyl, imidazo[1,2-a]pyridinyl, 1H-pyrrolo[3,2-c]pyridinyl, imidazo[1,2-a]pyrazinyl, imidazo[2,1-c][1,2,4]triazinyl, imidazo[1,5-a]pyrazinyl, imidazo[1,2-a]pyrimidinyl, 1H-indazolyl, 9H-purinyl, imidazo[1,2-a]pyrimidinyl, [1,2,4]triazolo[1,5-a]pyrimidinyl, [1,2,4]triazolo[4,3-b]pyridazinyl, isoxazolo[5,4-c]pyridazinyl, isoxazolo[3,4-c]pyridazinyl, pyridone, pyrimidone, pyrazinone, pyrimidinone, 1H-imidazol-2(3H)-one, 1H-pyrrole-2,5-dione, 3-oxo-2H-pyridazinyl, 1H-2-oxo-pyrimidinyl, 1H-2-oxo-pyridinyl, 2,4(1H,3H)-dioxo-pyrimidinyl, 1H-2-oxo-pyrazinyl, and the like. The heteroaryl group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used herein, the term “heterocycloalkyl” refers to a monocyclic or polycyclic [including 2 or more rings that are fused together, including spiro, fused, or bridged systems, for example, a bicyclic ring system], saturated or unsaturated, non-aromatic 4- to 15-membered ring system (such as a 4- to 14-membered ring system, 4- to 12-membered ring system, 5- to 10-membered ring system, 4- to 7-membered ring system, 4- to 6-membered ring system, or 5- to 6-membered ring system), including 1 to 14 ring-forming carbon atoms and 1 to 10 ring-forming heteroatoms each independently selected from O, S and N. The heterocycloalkyl group can also optionally contain one or more oxo or thiono (i.e. ═S) groups. For example, the term “4- to 12-membered heterocycloalkyl” refers to a monocyclic or polycyclic, saturated or unsaturated, non-aromatic 4- to 12-membered ring system that comprises one or more ring-forming heteroatoms each independently selected from O, S and N; and the term “4- to 10-membered heterocycloalkyl” refers to a monocyclic or polycyclic, saturated or unsaturated, non-aromatic 4- to 10-membered ring system that comprises one or more ring-forming heteroatoms each independently selected from O, S and N. For another example, the term “4- to 6-membered heterocycloalkyl” refers to a monocyclic or polycyclic, saturated or unsaturated, non-aromatic 4- to 6-membered ring system that comprises one or more ring-forming heteroatoms each independently selected from O, S and N; and the term “5- to 6-membered heterocycloalkyl” refers to a monocyclic or polycyclic, saturated or unsaturated, non-aromatic 5- to 6-membered ring system that comprises one or more ring-forming heteroatoms each independently selected from O, S and N. Also included in the definition of heterocycloalkyl are moieties that have one or more aromatic rings (including aryl and heteroaryl) fused to the nonaromatic heterocycloalkyl ring, for example pyridinyl, pyrimidinyl, thiophenyl, pyrazolyl, phthalimidyl, naphthalimidyl, and benzo derivatives of the nonaromatic heterocycloalkyl rings. The heterocycloalkyl group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. Examples of such heterocycloalkyl rings include azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, thiomorpholinyl, tetrahydrothiazinyl, tetrahydrothiadiazinyl, morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl, quinuclidinyl, chromanyl, isochromanyl, benzoxazinyl, 7-azabicyclo[2.2.1]heptan-1-yl, 7-azabicyclo[2.2.1]heptan-2-yl, 7-azabicyclo[2.2.1]heptan-7-yl, 2-azabicyclo[2.2.1]heptan-3-on-2-yl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl and the like. Further examples of heterocycloalkyl rings include tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, piperazin-1-yl, piperazin-2-yl, 1,3-oxazolidin-3-yl, 1,4-oxazepan-1-yl, isothiazolidinyl, 1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,2-tetrahydrothiazin-2-yl, 1,3-thiazinan-3-yl, 1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-4-yl, oxazolidinonyl, 2-oxo-piperidinyl (e.g., 2-oxo-piperidin-1-yl), and the like. Some examples of aromatic-fused heterocycloalkyl groups include indolinyl, isoindolinyl, isoindolin-1-one-3-yl, 5,7-dihydro-6H-pyrrolo[3,4-b]pyridin-6-yl, 6,7-dihydro-5H-pyrrolo[3,4-d]pyrimidin-6-yl, 4,5,6,7-tetrahydrothieno[2,3-c]pyridine-5-yl, 5,6-dihydrothieno[2,3-c]pyridin-7(4H)-one-5-yl, 1,4,5,6-tetrahydropyrrolo[3,4-c]pyrazol-5-yl, and 3,4-dihydroisoquinolin-1(2H)-one-3-yl groups. The heterocycloalkyl group is optionally substituted by 1 or more (e.g., 1 to 5) suitable substituents. Examples of heterocycloalkyl groups include 5- or 6-membered monocyclic rings and 9- or 10-membered fused bicyclic rings. As used herein, the term “halo” or “halogen” group is defined to include fluorine, chlorine, bromine or iodine. As used herein, the term “haloalkyl” refers to an alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by a halogen atom). For example, the term “C 1-6 haloalkyl” refers to a C 1-6 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by a halogen atom). For another example, the term “C 1-4 haloalkyl” refers to a C 1-4 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by a halogen atom); the term “C 1-3 haloalkyl” refers to a C 1-3 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by a halogen atom); and the term “C 1-2 haloalkyl” refers to a C 1-2 alkyl group (i.e. methyl or ethyl) having one or more halogen substituents (up to perhaloalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by a halogen atom). For yet another example, the term “C 1 haloalkyl” refers to a methyl group having one, two, or three halogen substituents. Examples of haloalkyl groups include CF 3 , C 2 F 5 , CHF 2 , CH 2 F, CH 2 CF 3 , CH 2 Cl and the like. As used herein, the term “halocycloalkyl” refers to a cycloalkyl group having one or more halogen substituents (up to perhalocycloalkyl, i.e., every hydrogen atom of the cycloalkyl group has been replaced by a halogen atom). For example, the term “C 3-4 halocycloalkyl” refers to a cyclopropyl or cyclobutyl group having one or more halogen substituents. An example of halocycloalkyl is 2-fluorocyclopropan-1-yl. As used herein, the term “alkoxy” or “alkyloxy” refers to an —O-alkyl group. For example, the term “C 1-6 alkoxy” or “C 1-6 alkyloxy” refers to an —O—(C 1-6 alkyl) group; and the term “C 1-4 alkoxy” or “C 1-4 alkyloxy” refers to an —O—(C 1-4 alkyl) group; For another example, the term “C 1-2 alkoxy” or “C 1-2 alkyloxy” refers to an —O—(C 1-2 alkyl) group. Examples of alkoxy include methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), tert-butoxy, and the like. The alkoxy or alkyloxy group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used here, the term “haloalkoxy” refers to an —O-haloalkyl group. For example, the term “C 1-6 haloalkoxy” refers to an —O—(C 1-6 haloalkyl) group. For another example, the term “C 1-4 haloalkoxy” refers to an —O—(C 1-4 haloalkyl) group; and the term “C 1-2 haloalkoxy” refers to an —O—(C 1-2 haloalkyl) group. For yet another example, the term “C 1 haloalkoxy” refers to a methoxy group having one, two, or three halogen substituents. An example of haloalkoxy is —OCF 3 or —OCHF 2 . As used herein, the term “cycloalkoxy” or “cycloalkyloxy” refers to an —O— cycloalkyl group. For example, the term “C 3-7 cycloalkoxy” or “C 3-7 cycloalkyloxy” refers to an —O—(C 3-7 cycloalkyl) group. For another example, the term “C 3-6 cycloalkoxy” or “C 3-6 cycloalkyloxy” refers to an —O—(C 3-6 cycloalkyl) group. Examples of cycloalkoxy include C 3-6 cycloalkoxy (e.g., cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexanoxy, and the like). The cycloalkoxy or cycloalkyloxy group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used here, the term “C 6-10 aryloxy” refers to an —O—(C 6-10 aryl) group. An example of a C 6-10 aryloxy group is —O-phenyl [i.e., phenoxy]. The C 6-10 aryloxy y group optionally can be substituted by 1 or more (e.g., 1 to 5) suitable substituents. As used herein, the term “fluoroalkyl” refers to an alkyl group having one or more fluorine substituents (up to perfluoroalkyl, i.e., every hydrogen atom of the alkyl group has been replaced by fluorine). For example, the term “C 1-2 fluoroalkyl” refers to a C 1-2 alkyl group having one or more fluorine substituents (up to perfluoroalkyl, i.e., every hydrogen atom of the C 1-2 alkyl group has been replaced by fluorine). For another example, the term “C 1 fluoroalkyl” refers to a C 1 alkyl group (i.e., methyl) having 1, 2, or 3 fluorine substituents). Examples of fluoroalkyl groups include CF 3 , C 2 F 5 , CH 2 CF 3 , CHF 2 , CH 2 F, and the like. As used here, the term “fluoroalkoxy” refers to an —O-fluoroalkyl group. For example, the term “C 1-2 fluoroalkoxy” refers to an —O—C 1-2 fluoroalkyl group. For another example, the term “C 1 fluoroalkoxy” refers to a methoxy group having one, two, or three fluorine substituents. An example of C 1 fluoroalkoxy is —OCF 3 or —OCHF 2 . As used herein, the term “hydroxylalkyl” or “hydroxyalkyl” refers to an alkyl group having one or more (e.g., 1, 2, or 3) OH substituents. The term “C 1-6 hydroxylalkyl” or “C 1-6 hydroxyalkyl” refers to a C 1-6 alkyl group having one or more (e.g., 1, 2, or 3) OH substituents. The term “C 1-4 hydroxylalkyl” or “C 1-4 hydroxyalkyl” refers to a C 1-4 alkyl group having one or more (e.g., 1, 2, or 3) OH substituents; the term “C 1-3 hydroxylalkyl” or “C 1-3 hydroxyalkyl” refers to a C 1-3 alkyl group having one or more (e.g., 1, 2, or 3) OH substituents; and the term “C 1-2 hydroxylalkyl” or “C 1-2 hydroxyalkyl” refers to a C 1-2 alkyl group having one or more (e.g., 1, 2, or 3) OH substituents. An example of hydroxylalkyl is —CH 2 OH or —CH 2 CH 2 OH. As used herein, the term “oxo” refers to ═O. When an oxo is substituted on a carbon atom, they together form a carbonyl moiety [—C(═O)—]. When an oxo is substituted on a sulfur atom, they together form a sulfinyl moiety [—S(═O)—]; when two oxo groups are substituted on a sulfur atom, they together form a sulfonyl moiety [—S(═O) 2 —]. As used herein, the term “thiono” refers to ═S. When an thiono is substituted on a carbon atom, they together form moiety of [—C(═S)—]. As used herein, the term “optionally substituted” means that substitution is optional and therefore includes both unsubstituted and substituted atoms and moieties. A “substituted” atom or moiety indicates that any hydrogen on the designated atom or moiety can be replaced with a selection from the indicated substituent group (up to that every hydrogen atom on the designated atom or moiety is replaced with a selection from the indicated substituent group), provided that the normal valency of the designated atom or moiety is not exceeded, and that the substitution results in a stable compound. For example, if a methyl group (i.e., CH 3 ) is optionally substituted, then up to 3 hydrogen atoms on the carbon atom can be replaced with substituent groups. As used herein, the term “optionally substituted C 1-4 alkyl” refers to C 1-4 alkyl optionally substituted by one or more (e.g. 1 to 5) substituents each independently selected from the group consisting of —OH, halogen, —CN, —NH 2 , —NH(C 1-4 alkyl), —N(C 1-4 alkyl) 2 , C 1-4 alkoxy, and C 1-4 haloalkoxy. As used herein, the term “optionally substituted C 1-2 alkyl” refers to C 1-2 alkyl optionally substituted by one or more (e.g. 1 to 5) substituents each independently selected from the group consisting of —OH, halogen, —CN, —NH 2 , —NH(C 1-4 alkyl), —N(C 1-4 alkyl) 2 , C 1-4 alkoxy, and C 1-4 haloalkoxy. As used herein, the term “optionally substituted C 3-4 cycloalkyl” refers to C 3-4 cycloalkyl optionally substituted by one or more (e.g. 1 to 5) substituents each independently selected from the group consisting of —OH, halogen, —CN, —NH 2 , —NH(C 1-4 alkyl), —N(C 1-4 alkyl) 2 , C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. As used herein, the term “optionally substituted cyclopropylmethyl” refers to cyclopropylmethyl optionally substituted by one or more (e.g. 1 to 5) substituents each independently selected from the group consisting of —OH, halogen, —CN, —NH 2 , —NH(C 1-4 alkyl), —N(C 1-4 alkyl) 2 , C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 hydroxylalkyl, C 1-4 alkoxy, and C 1-4 haloalkoxy. As used herein, the term “optionally substituted C 1-4 alkoxy” refers to C 1-4 alkoxy optionally substituted by one or more (e.g. 1 to 5) substituents each independently selected from the group consisting of —OH, halogen, —CN, —NH 2 , —NH(C 1-4 alkyl), —N(C 1-4 alkyl) 2 , C 1-4 alkoxy, and C 1-4 haloalkoxy. As used herein, unless specified, the point of attachment of a substituent can be from any suitable position of the substituent. For example, piperidinyl can be piperidin-1-yl (attached through the N atom of the piperidinyl), piperidin-2-yl (attached through the C atom at the 2-position of the piperidinyl), piperidin-3-yl (attached through the C atom at the 3-position of the piperidinyl), or piperidin-4-yl (attached through the C atom at the 4-position of the piperidinyl). For another example, pyridinyl (or pyridyl) can be 2-pyridinyl (or pyridin-2-yl), 3-pyridinyl (or pyridin-3-yl), or 4-pyridinyl (or pyridin-4-yl). When a bond to a substituent is shown to cross a bond connecting two atoms in a ring, then such substituent may be bonded to any of the ring-forming atoms in that ring that are substitutable (i.e., bonded to one or more hydrogen atoms), unless otherwise specified or otherwise implicit from the context. For example, as shown in Formula a-101 below, R 10 may be bonded to either of the two ring carbon atoms each of which bears a hydrogen atom (but not shown). For another example, as shown in Formula a-102 below, R 10 may be bonded to either of the two ring carbon atoms on the pyrazine ring each of which bears a hydrogen atom (but not shown); and R 10a may be bonded to either of the two ring carbon atoms on the imidazole ring each of which bears a hydrogen atom (but not shown). When a substituted or optionally substituted moiety is described without indicating the atom via which such moiety is bonded to a substituent, then the substituent may be bonded via any appropriate atom in such moiety. For example in a substituted arylalkyl, a substituent on the arylalkyl [e.g., (C 6-10 aryl)-C 1-4 alkyl-] can be bonded to any carbon atom on the alkyl part or on the aryl part of the arylalkyl. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds. As noted above, the compounds of Formula I may exist in the form of pharmaceutically acceptable salts such as acid addition salts and/or base addition salts of the compounds of Formula I. The phrase “pharmaceutically acceptable salt(s)”, as used herein, unless otherwise indicated, includes acid addition or base salts which may be present in the compounds of Formula I. Pharmaceutically acceptable salts of the compounds of Formula I include the acid addition and base salts thereof. Suitable acid addition salts are formed from acids which form non-toxic salts. Examples include the acetate, adipate, aspartate, benzoate, besylate, bicarbonate/carbonate, bisulfate/sulfate, borate, camphorsulfonate, citrate, cyclamate, edisylate, esylate, formate, fumarate, gluceptate, gluconate, glucuronate, hexafluorophosphate, hibenzate, hydrochloride/chloride, hydrobromide/bromide, hydroiodide/iodide, isethionate, lactate, malate, maleate, malonate, mesylate, methylsulfate, naphthylate, 2-napsylate, nicotinate, nitrate, orotate, oxalate, palmitate, pamoate, phosphate/hydrogen phosphate/dihydrogen phosphate, pyroglutamate, saccharate, stearate, succinate, tannate, tartrate, tosylate, trifluoroacetate and xinofoate salts. Suitable base salts are formed from bases which form non-toxic salts. Examples include the aluminium, arginine, benzathine, calcium, choline, diethylamine, diolamine, glycine, lysine, magnesium, meglumine, olamine, potassium, sodium, tromethamine and zinc salts. Hemisalts of acids and bases may also be formed, for example, hemisulfate and hemicalcium salts. For a review on suitable salts, see “Handbook of Pharmaceutical Salts: Properties, Selection, and Use” by Stahl and Wermuth (Wiley-VCH, 2002). Methods for making pharmaceutically acceptable salts of compounds of Formula I are known to one of skill in the art. As used herein the terms “Formula I”, “Formula I or pharmaceutically acceptable salts thereof”, “pharmaceutically acceptable salts of the compound or the salt [of Formula I]” are defined to include all forms of the compound of Formula I, including hydrates, solvates, isomers (including for example rotational stereoisomers), crystalline and non-crystalline forms, isomorphs, polymorphs, metabolites, and prodrugs thereof. As it is known to the person skilled in the art, amine compounds (i.e., those comprising one or more nitrogen atoms), for example tertiary amines, can form N-oxides (also known as amine oxides or amine N-oxides). An N-oxide has the formula of (R 100 R 200 R 300 )N + —O − wherein the parent amine (R 100 R 200 R 300 )N can be for example, a tertiary amine (for example, each of R 100 , R 200 , R 300 is independently alkyl, arylalkyl, aryl, heteroaryl, or the like), a heterocyclic or heteroaromatic amine [for example, (R 100 R 200 R 300 )N together forms 1-alkylpiperidine, 1-alkylpyrrolidine, 1-benzylpyrrolidine, or pyridine]. For instance, an imine nitrogen, especially heterocyclic or heteroaromatic imine nitrogen, or pyridine-type nitrogen atom [such as a nitrogen atom in pyridine, pyridazine, or pyrazine], can be N-oxidized to form the N-oxide comprising the group Thus, a compound according to the present invention comprising one or more nitrogen atoms (e.g., an imine nitrogen atom) may be capable of forming an N-oxide thereof (e.g., mono-N-oxides, bis-N-oxides or multi-N-oxides, or mixtures thereof depending on the number of nitrogen atoms suitable to form stable N-oxides). As used herein, the term “N-oxide(s)” refer to all possible, and in particular all stable, N-oxide forms of the amine compounds (e.g., compounds comprising one or more imine nitrogen atoms) described herein, such as mono-N-oxides (including different isomers when more than one nitrogen atom of an amine compound can form a mono-N-oxide) or multi-N-oxides (e.g., bis-N-oxides), or mixtures thereof in any ratio. Compounds of Formula I and their salts described herein further include N-oxides thereof. Compounds of Formula I (including salts thereof) may exist in a continuum of solid states ranging from fully amorphous to fully crystalline. The term ‘amorphous’ refers to a state in which the material lacks long-range order at the molecular level and, depending upon temperature, may exhibit the physical properties of a solid or a liquid. Typically such materials do not give distinctive X-ray diffraction patterns and, while exhibiting the properties of a solid, are more formally described as a liquid. Upon heating, a change from apparent solid to a material with liquid properties occurs, which is characterised by a change of state, typically second order (‘glass transition’). The term ‘crystalline’ refers to a solid phase in which the material has a regular ordered internal structure at the molecular level and gives a distinctive X-ray diffraction pattern with defined peaks. Such materials when heated sufficiently will also exhibit the properties of a liquid, but the change from solid to liquid is characterized by a phase change, typically first order (‘melting point’). Compounds of Formula I (including salts thereof) may exist in unsolvated and solvated forms. When the solvent or water is tightly bound, the complex will have a well-defined stoichiometry independent of humidity. When, however, the solvent or water is weakly bound, as in channel solvates and hygroscopic compounds, the water/solvent content will be dependent on humidity and drying conditions. In such cases, non-stoichiometry will be the norm. The compounds of Formula I (including salts thereof) may exist as clathrates or other complexes (e.g., co-crystals). Included within the scope of the invention are complexes such as clathrates, drug-host inclusion complexes wherein the drug and host are present in stoichiometric or non-stoichiometric amounts. Also included are complexes of the compounds of Formula I containing two or more organic and/or inorganic components, which may be in stoichiometric or non-stoichiometric amounts. The resulting complexes may be ionized, partially ionized, or non-ionized. Co-crystals are typically defined as crystalline complexes of neutral molecular constituents that are bound together through non-covalent interactions, but could also be a complex of a neutral molecule with a salt. Co-crystals may be prepared by melt crystallization, by recrystallization from solvents, or by physically grinding the components together; see O. Almarsson and M. J. Zaworotko, Chem. Commun. 2004, 17, 1889-1896. For a general review of multi-component complexes, see J. K. Haleblian, J. Pharm. Sci. 1975, 64, 1269-1288. The compounds of the invention (including salts thereof) may also exist in a mesomorphic state (mesophase or liquid crystal) when subjected to suitable conditions. The mesomorphic state is intermediate between the true crystalline state and the true liquid state (either melt or solution). Mesomorphism arising as the result of a change in temperature is described as ‘thermotropic’ and that resulting from the addition of a second component, such as water or another solvent, is described as ‘lyotropic’. Compounds that have the potential to form lyotropic mesophases are described as ‘amphiphilic’ and consist of molecules which possess an ionic (such as —COO − Na + , —COO − K + , or —SO 3 —Na + ) or non-ionic (such as —N − N + (CH 3 ) 3 ) polar head group. For more information, see Crystals and the Polarizing Microscope by N. H. Hartshorne and A. Stuart, 4 th Edition (Edward Arnold, 1970). The invention also relates to prodrugs of the compounds of Formula I. Thus certain derivatives of compounds of Formula I which may have little or no pharmacological activity themselves can, when administered into or onto the body, be converted into compounds of Formula I having the desired activity, for example, by hydrolytic cleavage. Such derivatives are referred to as “prodrugs”. Further information on the use of prodrugs may be found in Pro-drugs as Novel Delivery Systems, Vol. 14, ACS Symposium Series (T. Higuchi and W. Stella) and Bioreversible Carriers in Drug Design, Pergamon Press, 1987 (Ed. E. B. Roche, American Pharmaceutical Association). Prodrugs in accordance with the invention can, for example, be produced by replacing appropriate functionalities present in the compounds of Formula I with certain moieties known to those skilled in the art as ‘pro-moieties’ as described, for example, in Design of Prodrugs by H. Bundgaard (Elsevier, 1985), or in Prodrugs: Challenges and Reward, 2007 edition, edited by Valentino Stella, Ronald Borchardt, Michael Hageman, Reza Oliyai, Hans Maag, Jefferson Tilley, pages 134-175 (Springer, 2007). Moreover, certain compounds of Formula I may themselves act as prodrugs of other compounds of Formula I. Also included within the scope of the invention are metabolites of compounds of Formula I, that is, compounds formed in vivo upon administration of the drug. The compounds of Formula I (including salts thereof) include all stereoisomers and tautomers. Stereoisomers of Formula I include cis and trans isomers, optical isomers such as R and S enantiomers, diastereomers, geometric isomers, rotational isomers, atropisomers, and conformational isomers of the compounds of Formula I, including compounds exhibiting more than one type of isomerism; and mixtures thereof (such as racemates and diastereomeric pairs). Also included are acid addition or base addition salts wherein the counterion is optically active, for example, D-lactate or L-lysine, or racemic, for example, DL-tartrate or DL-arginine. In some embodiments, the compounds of Formula I (including salts thereof) may have asymmetric carbon atoms. The carbon-carbon bonds of the compounds of Formula I may be depicted herein using a solid line (—), a solid wedge ( ), or a dotted wedge ( ). The use of a solid line to depict bonds to asymmetric carbon atoms is meant to indicate that all possible stereoisomers (e.g., specific enantiomers, racemic mixtures, etc.) at that carbon atom are included. The use of either a solid or dotted wedge to depict bonds to asymmetric carbon atoms is meant to indicate that only the stereoisomer shown is meant to be included. It is possible that compounds of Formula I may contain more than one asymmetric carbon atom. In those compounds, the use of a solid line to depict bonds to asymmetric carbon atoms is meant to indicate that all possible stereoisomers are meant to be included. For example, unless stated otherwise, it is intended that the compounds of Formula I can exist as enantiomers and diastereomers or as racemates and mixtures thereof. The use of a solid line to depict bonds to one or more asymmetric carbon atoms in a compound of Formula I and the use of a solid or dotted wedge to depict bonds to other asymmetric carbon atoms in the same compound is meant to indicate that a mixture of diastereomers is present. In some embodiments, the compounds of Formula I (including salts thereof) may exist in and/or be isolated as atropisomers (e.g., one or more atropenantiomers). Those skilled in the art would recognize that atropisomerism may exist in a compound that has two or more aromatic rings (for example, two aromatic rings linked through a single bond). See e.g., Freedman, T. B. et al., Absolute Configuration Determination of Chiral Molecules in the Solution State Using Vibrational Circular Dichroism. Chirality 2003, 15, 743-758; and Bringmann, G. et al., Atroposelective Synthesis of Axially Chiral Biaryl Compounds. Angew. Chem., Int. Ed. 2005, 44, 5384-5427. When any racemate crystallizes, crystals of different types are possible. One type is the racemic compound (true racemate) wherein one homogeneous form of crystal is produced containing both enantiomers in equimolar amounts. Another type is a racemic mixture or conglomerate wherein two forms of crystal are produced in equal or different molar amounts each comprising a single enantiomer. The compounds of Formula I (including salts thereof) may exhibit the phenomena of tautomerism and structural isomerism. For example, the compounds of Formula I may exist in several tautomeric forms, including the enol and imine form, the amide and imidic acid form, and the keto and enamine form and geometric isomers and mixtures thereof. All such tautomeric forms are included within the scope of the compounds of Formula I. Tautomers may exist as mixtures of a tautomeric set in solution. In solid form, usually one tautomer predominates. Even though one tautomer may be described, the present invention includes all tautomers of the compounds of Formula I. For example, when one of the following two tautomers of the invention is disclosed in the experimental section herein, those skilled in the art would readily recognize that the invention also includes the other. For another example, when one of the following three tautomers of the invention is disclosed in the experimental section herein, those skilled in the art would readily recognize that the invention also includes other tautomers such as the other two shown below. The present invention includes all pharmaceutically acceptable isotopically-labelled compounds of Formula I (including salts thereof) wherein one or more atoms are replaced by atoms having the same atomic number, but an atomic mass or mass number different from the atomic mass or mass number which predominates in nature. Examples of isotopes suitable for inclusion in the compounds of the invention (including salts thereof) include isotopes of hydrogen, such as 2 H and 3 H, carbon, such as 11 C, 13 C and 14 C, chlorine, such as 36 Cl, fluorine, such as 18 F, iodine, such as 123 I and 125 I, nitrogen, such as 13 N and 15 N, oxygen, such as 15 O, 17 O and 18 O, phosphorus, such as 32 P, and sulphur, such as 35 S. Certain isotopically-labelled compounds of Formula I, for example, those incorporating a radioactive isotope, are useful in drug and/or substrate tissue distribution studies. The radioactive isotopes tritium, i.e., 3 H, and carbon-14, i.e., 14 C, are particularly useful for this purpose in view of their ease of incorporation and ready means of detection. Substitution with heavier isotopes such as deuterium, i.e., 2 H, may afford certain therapeutic advantages resulting from greater metabolic stability, for example, increased in vivo half-life or reduced dosage requirements, and hence may be preferred in some circumstances. Substitution with positron-emitting isotopes, such as 11 C, 18 F, 15 O and 13 N, can be useful in Positron Emission Topography (PET) studies for examining substrate receptor occupancy. Isotopically-labeled compounds of Formula I (including salts thereof) can generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described in the accompanying Examples and Preparations using an appropriate isotopically-labeled reagent in place of the non-labeled reagent previously employed. The present invention also provides compositions (e.g., pharmaceutical compositions) comprising a novel compound of Formula I (including a pharmaceutically acceptable salt thereof) in the second aspect of the invention. Accordingly, in one embodiment, the invention provides a pharmaceutical composition comprising (a therapeutically effective amount of) a novel compound of Formula I (or a pharmaceutically acceptable salt thereof) and optionally comprising a pharmaceutically acceptable carrier. In one further embodiment, the invention provides a pharmaceutical composition comprising (a therapeutically effective amount of) a compound of Formula I (or a pharmaceutically acceptable salt thereof), optionally comprising a pharmaceutically acceptable carrier and, optionally, at least one additional medicinal or pharmaceutical agent (such as an antipsychotic agent or anti-schizophrenia agent described below). In one embodiment, the additional medicinal or pharmaceutical agent is an anti-schizophrenia agent as described below. The pharmaceutically acceptable carrier may comprise any conventional pharmaceutical carrier or excipient. Suitable pharmaceutical carriers include inert diluents or fillers, water and various organic solvents (such as hydrates and solvates). The pharmaceutical compositions may, if desired, contain additional ingredients such as flavorings, binders, excipients and the like. Thus for oral administration, tablets containing various excipients, such as citric acid, may be employed together with various disintegrants such as starch, alginic acid and certain complex silicates and with binding agents such as sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often useful for tableting purposes. Solid compositions of a similar type may also be employed in soft and hard filled gelatin capsules. Non-limiting examples of materials, therefore, include lactose or milk sugar and high molecular weight polyethylene glycols. When aqueous suspensions or elixirs are desired for oral administration, the active compound therein may be combined with various sweetening or flavoring agents, coloring matters or dyes and, if desired, emulsifying agents or suspending agents, together with diluents such as water, ethanol, propylene glycol, glycerin, or combinations thereof. The pharmaceutical composition may, for example, be in a form suitable for oral administration as a tablet, capsule, pill, powder, sustained release formulation, solution or suspension, for parenteral injection as a sterile solution, suspension or emulsion, for topical administration as an ointment or cream or for rectal administration as a suppository. Exemplary parenteral administration forms include solutions or suspensions of active compounds in sterile aqueous solutions, for example, aqueous propylene glycol or dextrose solutions. Such dosage forms may be suitably buffered, if desired. The pharmaceutical composition may be in unit dosage forms suitable for single administration of precise dosages. One of ordinary skill in the art would appreciate that the composition may be formulated in sub-therapeutic dosage such that multiple doses are envisioned. In one embodiment the composition comprises a therapeutically effective amount of a compound of Formula I (or a pharmaceutically acceptable salt thereof) and a pharmaceutically acceptable carrier. Compounds of Formula I (including pharmaceutically acceptable salts thereof) are D1R modulators. In some embodiments, a compound of Formula I is a D1R agonist [i.e., binding (having affinity for) and activating D1R receptors]. In some embodiments, using dopamine as a reference full D1R agonist, a compound of Formula I is a super agonist (i.e., a compound that is capable of producing a greater maximal response than the endogenous D1R agonist, dopamine, for a D1R receptor, and thus exhibiting an efficacy of more than about 100%, for example 120%). In some embodiments, using dopamine as a reference full agonist, a compound of Formula I is a full D1R agonist (i.e., having an efficacy of about 100%, for example, 90%-100%, compared to that of dopamine). In some embodiments, using dopamine as a reference full D1R agonist, a compound of Formula I is a partial agonist [i.e., a compound having only partial efficacy (i.e., less than 100%, for example 10%-80% or 50%-70%) at a D1 receptor relative to the full agonist, dopamine, although it binds and activates a D1 receptor]. A D1R agonist (including superagonist, full agonist, and partial agonist) can agonize or partially agonize an activity of D1R. In some embodiments, the EC 50 of a compound of Formula I with respect to D1R is less than about 10 μM, 5 μM, 2 μM, 1 μM, 500 nM, 200 nM, 100 nM, 50, 40, 30, 20, 10, 5, 2, or 1 nM. As used herein, when referencing to a compound, the term “D1R modulator” or “D1R agonist” (including a super D1R agonist, a full D1R agonist, or a partial D1R agonist) refers to a compound that is a D1-like receptor modulator or a D1-like receptor agonist respectively (i.e., not necessarily selective between/among subtypes of D1-like receptors). See Lewis, JPET 286:345-353, 1998. D1Rs include, for example, D1 and D5 in humans and D1A and D1B in rodents. Administration of the compounds of Formula I may be effected by any method that enables delivery of the compounds to the site of action. These methods include, for example, enteral routes (e.g., oral routes, buccal routes, sublabial routes, sublingual routes), oral routes, intranasal routes, inhaled routes, intraduodenal routes, parenteral injection (including intravenous, subcutaneous, intramuscular, intravascular or infusion),intrathecal routes, epidural routes, intracerebral routes, intracerbroventricular routes, topical, and rectal administration. In one embodiment of the present invention, the compounds of Formula I may be administered/effected by oral routes. Dosage regimens may be adjusted to provide the optimum desired response. For example, a single bolus may be administered, several divided doses may be administered over time or the dose may be proportionally reduced or increased as indicated by the exigencies of the therapeutic situation. It may be advantageous to formulate parenteral compositions in dosage unit form for ease of administration and uniformity of dosage. Dosage unit form, as used herein, refers to physically discrete units suited as unitary dosages for the mammalian subjects to be treated; each unit containing a predetermined quantity of active compound calculated to produce the desired therapeutic effect in association with the required pharmaceutical carrier. The specifications for the dosage unit forms of the invention are dictated by a variety of factors such as the unique characteristics of the therapeutic agent and the particular therapeutic or prophylactic effect to be achieved. In one embodiment of the present invention, the compounds of Formula I may be used to treat humans. It is to be noted that dosage values may vary with the type and severity of the condition to be alleviated, and may include single or multiple doses. It is to be further understood that for any particular subject, specific dosage regimens should be adjusted over time according to the individual need and the professional judgment of the person administering or supervising the administration of the compositions, and that dosage ranges set forth herein are exemplary only and are not intended to limit the scope or practice of the claimed composition. For example, doses may be adjusted based on pharmacokinetic or pharmacodynamic parameters, which may include clinical effects such as toxic effects and/or laboratory values. Thus, the present invention encompasses intra-patient dose-escalation as determined by the skilled artisan. Determining appropriate dosages and regimens for administration of the chemotherapeutic agent is well-known in the relevant art and would be understood to be encompassed by the skilled artisan once provided the teachings disclosed herein. The amount of the compound of Formula I or a pharmaceutically acceptable salt thereof administered will be dependent on the subject being treated, the severity of the disorder or condition, the rate of administration, the disposition of the compound and the discretion of the prescribing physician. Generally, an effective dosage is in the range of about 0.0001 to about 50 mg per kg body weight per day, for example about 0.01 to about 10 mg/kg/day, in single or divided doses. For a 70 kg human, this would amount to about 0.007 mg to about 3500 mg/day, for example about 0.7 mg to about 700 mg/day. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several small doses for administration throughout the day. As used herein, the term “combination therapy” refers to the administration of a compound of Formula I or a pharmaceutically acceptable salt thereof together with an at least one additional pharmaceutical or medicinal agent (e.g., an anti-schizophrenia agent), either sequentially or simultaneously. The present invention includes the use of a combination of a compound of Formula I (or a pharmaceutically acceptable salt thereof) and one or more additional pharmaceutically active agent(s). If a combination of active agents is administered, then they may be administered sequentially or simultaneously, in separate dosage forms or combined in a single dosage form. Accordingly, the present invention also includes pharmaceutical compositions comprising an amount of: (a) a first agent comprising a compound of Formula I (including an N-oxide thereof or a pharmaceutically acceptable salt of the compound or the N-oxide); (b) a second pharmaceutically active agent; and (c) a pharmaceutically acceptable carrier, vehicle or diluent. Various pharmaceutically active agents may be selected for use in conjunction with the compounds of Formula I (including or pharmaceutically acceptable salts thereof), depending on the disease, disorder, or condition to be treated. Pharmaceutically active agents that may be used in combination with the compositions of the present invention include, without limitation: (i) acetylcholinesterase inhibitors such as donepezil hydrochloride (ARICEPT, MEMAC); or Adenosine A 2A receptor antagonists such as Preladenant (SCH 420814) or SCH 412348; (ii) amyloid-β (or fragments thereof), such as Aβ 1-15 conjugated to pan HLA DR-binding epitope (PADRE) and ACC-001 (Elan/Wyeth); (iii) antibodies to amyloid-β (or fragments thereof), such as bapineuzumab (also known as AAB-001) and AAB-002 (Wyeth/Elan); (iv) amyloid-lowering or -inhibiting agents (including those that reduce amyloid production, accumulation and fibrillization) such as colostrinin and bisnorcymserine (also known as BNC); (v) alpha-adrenergic receptor agonists such as clonidine (CATAPRES); (vi) beta-adrenergic receptor blocking agents (beta blockers) such as carteolol; (vii) anticholinergics such as amitriptyline (ELAVIL, ENDEP); (viii) anticonvulsants such as carbamazepine (TEGRETOL, CARBATROL); (ix) antipsychotics, such as lurasidone (also known as SM-13496; Dainippon Sumitomo); (x) calcium channel blockers such as nilvadipine (ESCOR, NIVADIL); (xi) catechol O-methyltransferase (COMT) inhibitors such as tolcapone (TASMAR); (xii) central nervous system stimulants such as caffeine; (xiii) corticosteroids such as prednisone (STERAPRED, DELTASONE); (xiv) dopamine receptor agonists such as apomorphine (APOKYN); (xv) dopamine receptor antagonists such as tetrabenazine (NITOMAN, XENAZINE, dopamine D2 antagonist such as Quetiapine); (xvi) dopamine reuptake inhibitors such as nomifensine maleate (MERITAL); (xvii) gamma-aminobutyric acid (GABA) receptor agonists such as baclofen (LIORESAL, KEMSTRO); (xviii) histamine 3 (H 3 ) antagonists such as ciproxifan; (xix) immunomodulators such as glatiramer acetate (also known as copolymer-1; COPAXONE); (xx) immunosuppressants such as methotrexate (TREXALL, RHEUMATREX); (xxi) interferons, including interferon beta-1a (AVONEX, REBIF) and interferon beta-1b (BETASERON, BETAFERON); (xxii) levodopa (or its methyl or ethyl ester), alone or in combination with a DOPA decarboxylase inhibitor (e.g., carbidopa (SINEMET, CARBILEV, PARCOPA)); (xxiii) N-methyl-D-aspartate (NMDA) receptor antagonists such as memantine (NAMENDA, AXURA, EBIXA); (xxiv) monoamine oxidase (MAO) inhibitors such as selegiline (EMSAM); (xxv) muscarinic receptor (particularly M1 subtype) agonists such as bethanechol chloride (DUVOID, URECHOLINE); (xxvi) neuroprotective drugs such as 2,3,4,9-tetrahydro-1H-carbazol-3-one oxime; (xxvii) nicotinic receptor agonists such as epibatidine; (xxviii) norepinephrine (noradrenaline) reuptake inhibitors such as atomoxetine (STRATTERA); (xxix) phosphodiesterase (PDE) inhibitors, for example,PDE9 inhibitors such as BAY 73-6691 (Bayer AG) and PDE 10 (e.g. PDE10A) inhibitors such as papaverine; (xxx) other PDE inhibitors including (a) PDE1 inhibitors (e.g., vinpocetine), (b) PDE2 inhibitors (e.g., erythro-9-(2-hydroxy-3-nonyl)adenine (EHNA)), (c) PDE4 inhibitors (e.g., rolipram), and (d) PDE5 inhibitors (e.g., sildenafil (VIAGRA, REVATIO)); (xxxi) quinolines such as quinine (including its hydrochloride, dihydrochloride, sulfate, bisulfate and gluconate salts); (xxxii) β-secretase inhibitors such as WY-25105; (xxxiii) γ-secretase inhibitors such as LY-411575 (Lilly); (xxxiv) serotonin (5-hydroxytryptamine) 1A (5-HT 1A ) receptor antagonists such as spiperone; (xxxv) serotonin (5-hydroxytryptamine) 4 (5-HT 4 ) receptor agonists such as PRX-03140 (Epix); (xxxvi) serotonin (5-hydroxytryptamine) 6 (5-HT 6 ) receptor antagonists such as mianserin (TORVOL, BOLVIDON, NORVAL); (xxxvii) serotonin (5-HT) reuptake inhibitors such as alaproclate, citalopram (CELEXA, CIPRAMIL); (xxxviii) trophic factors, such as nerve growth factor (NGF), basic fibroblast growth factor (bFGF; ERSOFERMIN), neurotrophin-3 (NT-3), cardiotrophin-1, brain-derived neurotrophic factor (BDNF), neublastin, meteorin, and glial-derived neurotrophic factor (GDNF), and agents that stimulate production of trophic factors, such as propentofylline; and the like. The compound of Formula I (including a pharmaceutically acceptable salt thereof) is optionally used in combination with another active agent. Such an active agent may be, for example, an atypical antipsychotic or an anti-Parkinson's disease agent or an anti-Alzheimer's agent. Accordingly, another embodiment of the invention provides methods of treating a D1-mediated disorder (e.g., a neurological and psychiatric disorder associated with D1), comprising administering to a mammal an effective amount of a compound of Formula I (including an N-oxide thereof or a pharmaceutically acceptable salt of the compound or the N-oxide) and further comprising administering another active agent. As used herein, the term “another active agent” refers to any therapeutic agent, other than the compound of Formula I (including or a pharmaceutically acceptable salt thereof) that is useful for the treatment of a subject disorder. Examples of additional therapeutic agents include antidepressants, antipsychotics (such as anti-schizophrenia), anti-pain, anti-Parkinson's disease agents, anti-LID (levodopa-induced dyskinesia), anti-Alzheimer's and anti-anxiety agents. Examples of particular classes of antidepressants that can be used in combination with the compounds of the invention include norepinephrine reuptake inhibitors, selective serotonin reuptake inhibitors (SSRIs), NK-1 receptor antagonists, monoamine oxidase inhibitors (MAOIs), reversible inhibitors of monoamine oxidase (RIMAs), serotonin and noradrenaline reuptake inhibitors (SNRIs), corticotropin releasing factor (CRF) antagonists, α-adrenoreceptor antagonists, and atypical antidepressants. Suitable norepinephrine reuptake inhibitors include tertiary amine tricyclics and secondary amine tricyclics. Examples of suitable tertiary amine tricyclics and secondary amine tricyclics include amitriptyline, clomipramine, doxepin, imipramine, trimipramine, dothiepin, butriptyline, iprindole, lofepramine, nortriptyline, protriptyline, amoxapine, desipramine and maprotiline. Examples of suitable selective serotonin reuptake inhibitors include fluoxetine, fluvoxamine, paroxetine, and sertraline. Examples of monoamine oxidase inhibitors include isocarboxazid, phenelzine, and tranylcyclopramine. Examples of suitable reversible inhibitors of monoamine oxidase include moclobemide. Examples of suitable serotonin and noradrenaline reuptake inhibitors of use in the present invention include venlafaxine. Examples of suitable atypical anti-depressants include bupropion, lithium, nefazodone, trazodone and viloxazine. Examples of anti-Alzheimer's agents include Dimebon, NMDA receptor antagonists such as memantine; and cholinesterase inhibitors such as donepezil and galantamine. Examples of suitable classes of anti-anxiety agents that can be used in combination with the compounds of the invention include benzodiazepines and serotonin 1A (5-HT1A) agonists or antagonists, especially 5-HT1A partial agonists, and corticotropin releasing factor (CRF) antagonists. Suitable benzodiazepines include alprazolam, chlordiazepoxide, clonazepam, chlorazepate, diazepam, halazepam, lorazepam, oxazepam, and prazepam. Suitable 5-HT1A receptor agonists or antagonists include buspirone, flesinoxan, gepirone, and ipsapirone. Suitable atypical antipsychotics include paliperidone, bifeprunox, ziprasidone, risperidone, aripiprazole, olanzapine, and quetiapine. Suitable nicotine acetylcholine agonists include ispronicline, varenicline and MEM 3454. Anti-pain agents include pregabalin, gabapentin, clonidine, neostigmine, baclofen, midazolam, ketamine and ziconotide. Examples of suitable anti-Parkinson's disease agents include L-DOPA (or its methyl or ethyl ester), a DOPA decarboxylase inhibitor (e.g., carbidopa (SINEMET, CARBILEV, PARCOPA), an Adenosine A 2A receptor antagonist [e.g., Preladenant (SCH 420814) or SCH 412348], benserazide (MADOPAR), α-methyldopa, monofluoromethyldopa, difluoromethyldopa, brocresine, or m-hydroxybenzylhydrazine), a dopamine agonist [such as apomorphine (APOKYN), bromocriptine (PARLODEL), cabergoline (DOSTINEX), dihydrexidine, dihydroergocryptine, fenoldopam (CORLOPAM), lisuride (DOPERGIN), pergolide (PERMAX), piribedil (TRIVASTAL, TRASTAL), pramipexole (MIRAPEX), quinpirole, ropinirole (REQUIP), rotigotine (NEUPRO), SKF-82958 (GlaxoSmithKline), and sarizotan], a monoamine oxidase (MAO) inhibitor [such as selegiline (EMSAM), selegiline hydrochloride (L-deprenyl, ELDEPRYL, ZELAPAR), dimethylselegilene, brofaromine, phenelzine (NARDIL), tranylcypromine (PARNATE), moclobemide (AURORIX, MANERIX), befloxatone, safinamide, isocarboxazid (MARPLAN), nialamide (NIAMID), rasagiline (AZILECT), iproniazide (MARSILID, IPROZID, IPRONID), CHF-3381 (Chiesi Farmaceutici), iproclozide, toloxatone (HUMORYL, PERENUM), bifemelane, desoxypeganine, harmine (also known as telepathine or banasterine), harmaline, linezolid (ZYVOX, ZYVOXID), and pargyline (EUDATIN, SUPIRDYL)], a catechol O-methyltransferase (COMT) inhibitor [such as tolcapone (TASMAR), entacapone (COMTAN), and tropolone], an N-methyl-D-aspartate (NMDA) receptor antagonist [such as amantadine (SYMMETREL)], anticholinergics [such as amitriptyline (ELAVIL, ENDEP), butriptyline, benztropine mesylate (COGENTIN), trihexyphenidyl (ARTANE), diphenhydramine (BENADRYL), orphenadrine (NORFLEX), hyoscyamine, atropine (ATROPEN), scopolamine (TRANSDERM-SCOP), scopolamine methylbromide (PARMINE), dicycloverine (BENTYL, BYCLOMINE, DIBENT, DILOMINE, tolterodine (DETROL), oxybutynin (DITROPAN, LYRINEL XL, OXYTROL), penthienate bromide, propantheline (PRO-BANTHINE), cyclizine, imipramine hydrochloride (TOFRANIL), imipramine maleate (SURMONTIL), lofepramine, desipramine (NORPRAMIN), doxepin (SINEQUAN, ZONALON), trimipramine (SURMONTIL), and glycopyrrolate (ROBINUL)], or a combination thereof. Examples of anti-schizophrenia agents include ziprasidone, risperidone, olanzapine, quetiapine, aripiprazole, asenapine, blonanserin, or iloperidone. Some additional “another active agent” examples include rivastigmine (Exelon), Clozapine, Levodopa, Rotigotine, Aricept, Methylphenidate, memantine. milnacipran, guanfacine, bupropion, and atomoxetine. As noted above, the compounds of Formula I (including pharmaceutically acceptable salts thereof) may be used in combination with one or more additional anti-schizophrenia agents which are described herein. When a combination therapy is used, the one or more additional anti-schizophrenia agents may be administered sequentially or simultaneously with the compound of the invention. In one embodiment, the additional anti-schizophrenia agent is administered to a mammal (e.g., a human) prior to administration of the compound of the invention. In another embodiment, the additional anti-schizophrenia agent is administered to the mammal after administration of the compound of the invention. In another embodiment, the additional anti-schizophrenia agent is administered to the mammal (e.g., a human) simultaneously with the administration of the compound of the invention (or an N-oxide thereof or a pharmaceutically acceptable salt of the foregoing). The invention also provides a pharmaceutical composition for the treatment of schizophrenia in a mammal, including a human, which comprises an amount of a compound of Formula I (or a pharmaceutically acceptable salt thereof), as defined above (including hydrates, solvates and polymorphs of said compound or pharmaceutically acceptable salts thereof), in combination with one or more (for example one to three) anti-schizophrenia agents such as ziprasidone, risperidone, olanzapine, quetiapine, aripiprazole, asenapine, blonanserin, or iloperidone, wherein the amounts of the active agent and the combination when taken as a whole are therapeutically effective for treating schizophrenia. The invention also provides a pharmaceutical composition for the treatment of Parkinson's disease in a mammal (including cognition impairment associated with PD), including a human, which comprises an amount of a compound of Formula I (or a pharmaceutically acceptable salt thereof), as defined above (including hydrates, solvates and polymorphs of said compound or pharmaceutically acceptable salts thereof), in combination with one or more (for example one to three) anti-Parkinson's disease agents such as L-DOPA, wherein the amounts of the active agent and the combination when taken as a whole are therapeutically effective for treating Parkinson's disease. It will be understood that the compounds of Formula I depicted above are not limited to a particular stereoisomer (e.g. enantiomer or atropisomer) shown, but also include all stereoisomers and mixtures thereof. DETAILED DESCRIPTION OF THE INVENTION Compounds of the invention, including N-oxides and salts of the compounds or N-oxides, can be prepared using known organic synthesis techniques and can be synthesized according to any of numerous possible synthetic routes. The reactions for preparing compounds of the invention can be carried out in suitable solvents, which can be readily selected by one of skill in the art of organic synthesis. Suitable solvents can be substantially non-reactive with the starting materials (reactants), the intermediates, or products at the temperatures at which the reactions are carried out, e.g., temperatures that can range from the solvent's freezing temperature to the solvent's boiling temperature. A given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the particular reaction step, suitable solvents for a particular reaction step can be selected by the skilled artisan. Preparation of compounds of the invention can involve the protection and deprotection of various chemical groups. The need for protection and deprotection, and the selection of appropriate protecting groups, can be readily determined by one skilled in the art. The chemistry of protecting groups can be found, for example, in T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3 rd Ed., Wiley & Sons, Inc., New York (1999), which is incorporated herein by reference in its entirety. Reactions can be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy (e.g., 1 H or 13 C), infrared spectroscopy, spectrophotometry (e.g., UV-visible), mass spectrometry, or by chromatographic methods such as high-performance liquid chromatography (HPLC) or thin layer chromatography (TLC). Compounds of Formula I and intermediates thereof may be prepared according to the following reaction schemes and accompanying discussion. Unless otherwise indicated, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , L 1 , X 1 , X 2 , X 3 , X 4 , Q 1 , and structural Formula I in the reaction schemes and discussion that follow are as defined above. In general, the compounds of this invention may be made by processes which include processes analogous to those known in the chemical arts, particularly in light of the description contained herein. Certain processes for the manufacture of the compounds of this invention and intermediates thereof are provided as further features of the invention and are illustrated by the following reaction schemes. Other processes are described in the experimental section. The schemes and examples provided herein (including the corresponding description) are for illustration only, and not intended to limit the scope of the present invention. Scheme 1 refers to preparation of compounds of Formula I. Referring to Scheme 1, compounds of Formula 1-1 [where Lg 1 is a suitable leaving group such as halo (e.g., F, Cl or Br)] and 1-2 [wherein Z 1 can be, e.g., halogen (e.g., Br or I) or trifluoromethanesulfonate (triflate)] are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 1-3 can be prepared by coupling a compound of Formula 1-1 with a compound of Formula 1-2 under suitable conditions. The coupling can be accomplished, for example, by heating a mixture of a compound of Formula 1-1 with a compound of Formula 1-2 in the presence of a base, such as Cs 2 CO 3 , in an appropriate solvent, such as dimethyl sulfoxide (DMSO). Alternatively, a metal-catalyzed (such as using a palladium or copper catalyst) coupling may be employed to accomplish the aforesaid coupling. In this variant of the coupling, a mixture of a compound of Formula 1-1 and a compound of Formula 1-2 can be heated in the presence of a base (such as Cs 2 CO 3 ), a metal catalyst [such as a palladium catalyst, e.g., Pd(OAc) 2 ], and a ligand [such as 1,1′-binaphthalene-2,2′-diylbis(diphenylphosphane) (BINAP)] in an appropriate solvent, such as 1,4-dioxane. A compound of Formula 1-3 can subsequently be reacted with a compound of Formula Q 1 -Z 2 [wherein Z 2 can be Br; B(OH) 2 ; B(OR) 2 wherein each R is independently H or C 1-6 alkyl, or wherein the two (OR) groups, together with the B atom to which they are attached, form a 5- to 10-membered heterocycloalkyl optionally substituted with one or more C 1-6 alkyl; a trialkyltin moiety; or the like] by a metal-catalyzed (such as using a palladium catalyst) coupling reaction to obtain a compound of Formula I. Compounds of Formula Q 1 -Z 2 are commercially available or can be made by methods described herein or by methods analogous to those described in the chemical art. Alternatively, a compound of Formula 1-3 can be converted to a compound of Formula 1-4 (wherein Z 2 is defined as above). For example, a compound of Formula 1-3 (wherein Z 1 is halogen such as Br or I) can be converted to a compound of Formula 1-4 [wherein Z 2 is B(OH) 2 ; B(OR) 2 wherein each R is independently H or C 1-6 alkyl, or wherein the two (OR) groups, together with the B atom to which they are attached, form a 5- to 10-membered heterocycloalkyl or heteroaryl optionally substituted with one or more C 1-6 alkyl] by methods described herein or other methods well known to those skilled in the art. In this example, this reaction can be accomplished, for example, by reacting a compound of Formula 1-3 (wherein Z 1 is halogen such as Br) with 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane, a suitable base (such as potassium acetate), and a palladium catalyst {such as [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)} in a suitable solvent such as 1,4-dioxane. In another example, a compound of Formula 1-3 (wherein Z 1 is halogen such as Br) can be converted to a compound of Formula 1-4 (wherein Z 2 is a trialkyltin moiety) by alternate methods described herein or other methods well known to those skilled in the art. In this example, this reaction can be accomplished, for example, by reacting a compound of Formula 1-3 (wherein Z 1 is halogen such as Br) with a hexaalkyldistannane (such as hexamethyldistannane) in the presence of a palladium catalyst [such as tetrakis(triphenylphosphine)palladium(0)] in a suitable solvent such as 1,4-dioxane. A compound of Formula 1-4 can then be reacted with a compound of Formula Q 1 -Z 1 (wherein Z 1 is defined as above) by a metal-catalyzed (such as using a palladium catalyst) coupling reaction to obtain a compound of Formula I. Compounds of Formula Q 1 -Z 1 are commercially available or can be made by methods described herein or by methods analogous to those described in the chemical art. The type of reaction employed depends on the selection of Z 1 and Z 2 . For example, when Z 1 is halogen or triflate and the Q 1 -Z 2 reagent is a boronic acid or boronic ester, a Suzuki reaction may be used [A. Suzuki, J. Organomet. Chem. 1999, 576, 147-168; N. Miyaura and A. Suzuki, Chem. Rev. 1995, 95, 2457-2483; A. F. Littke et al., J. Am. Chem. Soc. 2000, 122, 4020-4028]. In some specific embodiments, an aromatic iodide, bromide, or triflate of Formula 1-3 is combined with an aryl or heteroaryl boronic acid or boronic ester of Formula Q 1 -Z 2 and a suitable base, such as potassium phosphate, in a suitable organic solvent such as tetrahydrofuran (THF). A palladium catalyst is added, such as S-Phos precatalyst {also known as chloro(2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl)[2-(2-aminoethylphenyl)]palladium(II)-tert-butyl methyl ether adduct}, and the reaction mixture is heated. Alternatively, when Z 1 is halogen or triflate and Z 2 is trialkyltin, a Stille coupling may be employed [V. Farina et al., Organic Reactions 1997, 50, 1-652]. More specifically, a compound of Formula 1-3 (wherein Z 1 is Br, I, or triflate) may be combined with a compound of Formula Q 1 -Z 2 (wherein the Q 1 -Z 2 compound is a Q 1 -stannane compound) in the presence of a palladium catalyst, such as dichlorobis(triphenylphosphine)palladium(II), in a suitable organic solvent such as toluene, and the reaction may be heated. Where Z 1 is Br, I, or triflate and Z 2 is Br or I, a Negishi coupling may be used [E. Erdik, Tetrahedron 1992, 48, 9577-9648]. More specifically, a compound of Formula 1-3 (wherein Z 1 is Br, I, or triflate) may be transmetallated by treatment with 1 to 1.1 equivalents of an alkyllithium reagent followed by a solution of 1.2 to 1.4 equivalents of zinc chloride in an appropriate solvent such as THF at a temperature ranging from −80° C. to −65° C. After warming to a temperature between 10° C. and 30° C., the reaction mixture may be treated with a compound of Formula Q 1 -Z 2 (wherein Z 2 is Br or I), and heated at 50° C. to 70° C. with addition of a catalyst such as tetrakis(triphenylphosphine)palladium(0). The reaction may be carried out for times ranging from 1 to 24 hours to yield the compound of Formula I. Scheme 2 also refers to preparation of compounds of Formula I. Referring to Scheme 2, compounds of Formula I may be prepared utilizing analogous chemical transformations to those described in Scheme 1, but with a different ordering of steps. Compounds of Formula 2-1 [wherein Pg 1 is a suitable protecting group such as Boc or Cbz when L 1 is NH or methyl, benzyl, tetrahydropyranyl (THP), or tert-butyldimethyl (TBS) when L 1 is O] are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 2-1 can be converted to a compound of Formula 2-2 either directly or after conversion to a compound of Formula 2-3 using methods analogous to those described in Scheme 1. A compound of Formula 2-2 may then be deprotected, using appropriate conditions depending on the selection of the Pg 1 group, to obtain a compound of Formula 2-4, which in turn can be coupled with a compound of Formula 1-1 in Scheme 1 to afford a compound of Formula I. The coupling conditions employed may be analogous to those described for the preparation of a compound of Formula 1-3 in Scheme 1. Scheme 3 refers to a preparation of a compound of Formula 3-6 wherein A 1 is a moiety of Formula A 1a or a Pg 1 . Referring to Scheme 3, compounds of Formula 3-1 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 3-3 can be prepared by reacting compound of Formula 3-1 with acylated enol of Formula 3-2 in the presence of a suitable palladium catalyst such as palladium(II) acetate, tributylmethoxystannane and a suitable phosphine ligand (such as tri-o-tolylphosphine). The resulting aryl ketone of Formula 3-3 can be converted to the diketone of Formula 3-4 upon treatment with a suitable oxidizing agent such as selenium dioxide. Diketones of Formula 3-4 can be reacted with glycinamide or a salt thereof (such as an acetic acid salt) in the presence of a base such as sodium hydroxide to obtain pyrazinones of Formula 3-5. Alkylation of the pyrazinone nitrogen to obtain a compound of Formula 3-6 can be achieved by treatment of a compound of Formula 3-5 with a base [such as lithium diisopropylamide (LDA), lithium bis(trimethylsilyl)amide (LHMDS), and the like] and a compound of the formula R 11 —Z 3 [wherein Z 3 is an acceptable leaving group such as Cl, Br, I, methanesulfonate (mesylate), and the like and wherein R 11 is for example C 1-3 alkyl (e.g., methyl)]. Suitable reaction solvents typically can be selected from polar aprotic solvents such as N,N-dimethylformamide (DMF), 1,4-dioxane, or THF. Alternatively, a compound of Formula 3-6 may be prepared as in Scheme 4 wherein L 1 is O, NH, N(C 1-4 alkyl) and N(C 3-6 cycloalkyl). Referring to Scheme 4, compounds of Formula 4-1 and 4-2 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 4-3 can be prepared by coupling a compound of Formula 4-1 with a compound of Formula 4-2. The aforesaid coupling may be accomplished by reacting a compound of Formula 4-1 with a compound of Formula 4-2 in the presence of a suitable base (such as potassium carbonate), a suitable catalyst [such as tetrakis(triphenylphosphine)palladium(0)], and a suitable solvent (such as ethanol). A compound of Formula 4-3 can be reacted with maleic anhydride and hydrogen peroxide in a solvent (such as dichloromethane) to provide a compound of Formula 4-4, which may contain a mixture of N-oxide regioisomers. A compound of Formula 4-5 can be prepared from a compound of Formula 4-4 by heating with acetic anydride; the initial product can be saponified using a base (such as NaOH) in a suitable polar solvent (such as water or methanol). A compound of Formula 3-6 can be prepared from a compound of Formula 4-5 by reaction with a suitable base (such as LDA, LHMDS and the like), lithium bromide, and a compound of the formula R 11 —Z 3 (wherein Z 3 is an acceptable leaving group such as Cl, Br, I, mesylate, and the like). Suitable reaction solvents typically can be selected from polar aprotic solvents (such as DMF, 1,4-dioxane, or THF). Scheme 5 refers to a preparation of a compound of Formula 5-4 wherein L 1 is O, NH, carbonyl, N(C 1-4 alkyl) and N(C 3-6 cycloalkyl) and A 1 is a moiety of Formula A 1a , or a Pg 2 (such as a benzyl group). Referring to Scheme 5, compounds of Formula 4-1 and 5-1 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 5-2 can be prepared by coupling a compound of Formula 4-1 with an enol trifluoromethanesulfonate of Formula 5-1. The aforesaid coupling may be accomplished by reacting a compound of Formula 4-1 with a trifluoromethanesulfonate of Formula 5-1 in the presence of a suitable base (such as potassium carbonate or sodium carbonate), a suitable catalyst [such as palladium(II) acetate], optionally a suitable ligand (such as tricyclohexylphosphine), and optionally a suitable phase-transfer catalyst such as tetrabutylammonium chloride. Suitable reaction solvents typically can be selected from polar aprotic solvents such as 1,4-dioxane or THF. A compound of Formula 5-2 can be reacted with 1 to 5 equivalents of a suitable base [such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)] under an oxygen atmosphere to obtain a compound of Formula 5-3. Suitable reaction solvents typically can be selected from polar aprotic solvents such as DMF, 1,4-dioxane, or THF. A compound of Formula 5-4 can be obtained by reacting a compound of Formula 5-3 with hydrazine in a suitable solvent such as 1-butanol. Scheme 6 refers to a preparation of a compound of Formula 6-5. Referring to Scheme 6, a compound of Formula 6-1 can be prepared as described in Scheme 5, wherein Pg 2 is a suitable protecting group (such as benzyl). A compound of Formula 6-1 can be converted to a suitably protected compound of Formula 6-2 using methods described herein or other methods well known to those skilled in the art, wherein Pg 3 is a suitable protecting group (such as THP) that can be removed under orthogonal reaction conditions to Pg 2 . A compound of Formula 6-3 can be prepared by selective removal of Pg 2 under suitable deprotection conditions depending on the selection of Pg 2 . For example, when Pg 2 is a benzyl group, it can be removed by treatment with palladium (10% on carbon) under hydrogenation condition in a suitable solvent, such as methanol and ethyl acetate. Using the aforementioned reaction conditions described in Scheme 1, a compound of Formula 6-3 can be coupled with a reagent of Formula 1-1 to yield a compound of Formula 6-4. A compound of Formula 6-5 can be obtained by removing Pg 3 under suitable deprotection conditions depending on the selection of Pg 3 . For example, when Pg 3 is THP, it can be removed under acidic conditions, such as hydrogen chloride in a suitable solvent, such as dichloromethane. Scheme 7 refers to a preparation of a compound of Formula 7-6 [wherein R 9 is, for example, C 1-3 alkyl (e.g., methyl); R 11 is, for example, H or C 1-3 alkyl (e.g., methyl); and Pg 4 is a suitable protecting group [e.g., 2-(trimethylsilyl)ethoxymethyl (SEM), tert-butoxycarbonyl (Boc), or benzyloxymethyl acetal (BOM)]. Referring to Scheme 7, compounds of Formula 7-1 and 7-2 are commercially available or can be prepared by methods described herein or other methods well known to those skilled in the art. A compound of Formula 7-3 can be prepared by coupling a compound of Formula 7-1 with a compound of Formula 7-2, in the presence of a suitable base (such as potassium carbonate) and a suitable catalyst {such as [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II)}. A compound of Formula 7-4 can be prepared by selective removal of Pg 2 under suitable de-protection conditions depending on the selection of Pg 2 . For example, when Pg 2 is a benzyl group, it can be removed by treatment with palladium (10% on carbon) under hydrogenation condition in a suitable solvent, such as methanol and ethyl acetate. Using the aforementioned reaction conditions described in Scheme 1, a compound of Formula 7-4 can be coupled with a reagent of Formula 1-1 to yield a compound of Formula 7-5. Alternatively, a compound of Formula 7-5 can be prepared from intermediate 1-4, following the coupling conditions described in Scheme 1. A compound of Formula 7-6 can then be obtained from a compound of Formula 7-5 by removing Pg 4 under suitable deprotection conditions that are known to those skilled in the art. Scheme 8 refers to preparation of compounds of Formula 8-5 and 8-6. Referring to Scheme 8, compounds of Formula 8-1 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 8-1 can be converted to a compound of Formula 8-2 either directly or after conversion to a compound of Formula 8-3 using methods analogous to those described in Scheme 1. The nitro group of a compound of Formula 8-2 can then be converted to an amine via hydrogenation in the presence of a suitable catalyst, such as palladium (10% on carbon), to yield a compound of Formula 8-4. A compound of Formula 8-4 can then be coupled with a compound of Formula 1-1 in Scheme 1 to afford a compound of Formula 8-5. The coupling conditions employed may be analogous to those described for the preparation of a compound of Formula 1-3 in Scheme 1. A compound of Formula 8-6 can be prepared via N-alkylation of a compound of formula 8-5 using a reagent of Y—Z 3 , wherein Y is C 1-4 alkyl, or C 3-6 cycloalkyl, and Z 3 is an acceptable leaving group such as Cl, Br, I, mesylate, and the like. Scheme 9 refers to preparation of compounds of Formula 9-4. Referring to Scheme 9, a compound of Formula 9-1 can be prepared via triflation of a compound of Formula 2-4 (Scheme 2) using a suitable reagent such as trifluoromethanesulfonic anhydride in the presence of a suitable base such as triethylamine. A compound of Formula 9-1 can be converted to a compound of Formula 9-2 by coupling with potassium thioacetate, in the presence of a suitable metal catalyst, such as tris(dibenzylideneacetone)dipalladium(0), and a suitable ligand, such as (R)-(−)-1-[(S P )-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-tert-butylphosphine, in a suitable solvent, such as toluene. A compound of Formula 9-2 can then be hydrolyzed to obtain a compound of Formula 9-3, which in turn can be coupled with a compound of Formula 1-1 in Scheme 1 to afford a compound of Formula 9-4. The coupling conditions employed may be analogous to those described for the preparation of a compound of Formula 1-3 in Scheme 1. Scheme 10 refers to a preparation of a compound of Formula 10-3 [wherein A 1 is either Pg 2 as defined above or a moiety of Formula A 1a ], which can be used in Scheme 2 as intermediate/starting material for the preparation of compounds of Formula I. Referring to Scheme 3, compounds of Formula 10-1 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. A compound of Formula 10-1 can be reacted with 4-chloro-3-nitropyridine and the initial product can be subsequently reduced to obtain a compound of Formula 10-2. Examples of suitable reaction conditions for the coupling of a compound of Formula 10-1 with 4-chloro-3-nitropyridine include mixing the two reactants with a suitable base, such as triethylamine, in a suitable reaction solvent such as ethanol. The subsequent reduction of the nitro group to afford a compound of Formula 10-2 can be achieved by, for example, hydrogenation in the presence of a catalyst such as palladium on carbon in a suitable solvent such as methanol. Suitable hydrogen pressures for the aforesaid reaction are typically between 1 atm and 4 atm. A compound of Formula 10-2 can then be heated with acetic anhydride and triethyl orthoformate to obtain a compound of Formula 10-3. Scheme 11 refers to a preparation of a compound of Formula 11-2 [wherein R 10 is H or C 1-3 alkyl, for example methyl], which is an example of a compound of Formula I. Referring to Scheme 11, a compound of Formula 11-1 can be prepared by methods described in Scheme 1. A compound of Formula 11-1 can be reacted with chloroacetaldehyde to obtain a compound of Formula 11-2 typically at an elevated temperature for about 1 hour to 24 hours. Scheme 12 refers to a preparation of a compound of Formula 12-4. Referring to Scheme 12, compounds of Formula 12-1 are commercially available or can be made by methods described herein or other methods well known to those skilled in the art. The free NH of a compound of Formula 12-1 can be protected by a suitable amine protecting group Pg 5 such as 2-(trimethylsilyl)ethoxymethyl (SEM) to give a mixture of regioisomers of Formula 12-2A and 12-2B. The mixture can be coupled with intermediate 2-4 under the conditions described in Scheme 1 to give a mixture of compounds of Formula 12-3A and 12-3B, which upon deprotection under suitable reaction conditions depending on the choice of Pg 5 yield a compound of Formula 12-4. Additional starting materials and intermediates useful for making the compounds of the present invention can be obtained from chemical vendors such as Sigma-Aldrich or can be made according to methods described in the chemical art. Those skilled in the art can recognize that in all of the Schemes described herein, if there are functional (reactive) groups present on a part of the compound structure such as a substituent group, for example R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , L 1 , X 1 , X 2 , X 3 , X 4 , and Q 1 , etc., further modification can be made if appropriate and/or desired, using methods well known to those skilled in the art. For example, a —CN group can be hydrolyzed to afford an amide group; a carboxylic acid can be converted to an amide; a carboxylic acid can be converted to an ester, which in turn can be reduced to an alcohol, which in turn can be further modified. For another example, an OH group can be converted into a better leaving group such as a methanesulfonate, which in turn is suitable for nucleophilic substitution, such as by a cyanide ion (CN − ). For another example, an —S— can be oxidized to —S(═O)— and/or —S(═O) 2 —. For yet another example, an unsaturated bond such as C═C or C≡C can be reduced to a saturated bond by hydrogenation. In some embodiments, a primary amine or a secondary amine moiety (present on a substituent group such as R 3 , R 4 , R 9 , R 10 , etc.) can be converted to an amide, sulfonamide, urea, or thiourea moiety by reacting it with an appropriate reagent such as an acid chloride, a sulfonyl chloride, an isocyanate, or a thioisocyanate compound. One skilled in the art will recognize further such modifications. Thus, a compound of Formula I having a substituent that contains a functional group can be converted to another compound of Formula I having a different substituent group. Similarly, those skilled in the art can also recognize that in all of the schemes described herein, if there are functional (reactive) groups present on a substituent group such as R 3 , R 4 , R 9 , R 10 , etc., these functional groups can be protected/deprotected in the course of the synthetic scheme described here, if appropriate and/or desired. For example, an OH group can be protected by a benzyl, methyl, or acetyl group, which can be deprotected and converted back to the OH group in a later stage of the synthetic process. For another example, an NH 2 group can be protected by a benzyloxycarbonyl (Cbz) or Boc group; conversion back to the NH 2 group can be carried out at a later stage of the synthetic process via deprotection. As used herein, the term “reacting” (or “reaction” or “reacted”) refers to the bringing together of designated chemical reactants such that a chemical transformation takes place generating a compound different from any initially introduced into the system. Reactions can take place in the presence or absence of solvent. Compounds of Formula I may exist as stereoisomers, such as atropisomers, racemates, enantiomers, or diastereomers. Conventional techniques for the preparation/isolation of individual enantiomers include chiral synthesis from a suitable optically pure precursor or resolution of the racemate using, for example, chiral high-performance liquid chromatography (HPLC). Alternatively, the racemate (or a racemic precursor) may be reacted with a suitable optically active compound, for example, an alcohol, or, in the case where the compound contains an acidic or basic moiety, an acid or base such as tartaric acid or 1-phenylethylamine. The resulting diastereomeric mixture may be separated by chromatography and/or fractional crystallization and one or both of the diastereoisomers converted to the corresponding pure enantiomer(s) by means well known to one skilled in the art. Chiral compounds of Formula I (and chiral precursors thereof) may be obtained in enantiomerically enriched form using chromatography, typically HPLC, on an asymmetric resin with a mobile phase consisting of a hydrocarbon, typically heptane or hexane, containing from 0% to 50% 2-propanol, typically from 2% to 20%, and from 0% to 5% of an alkylamine, typically 0.1% diethylamine. Concentration of the eluate affords the enriched mixture. Stereoisomeric conglomerates may be separated by conventional techniques known to those skilled in the art. See, e.g., Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen (Wiley, New York, 1994), the disclosure of which is incorporated herein by reference in its entirety. Suitable stereoselective techniques are well known to those of ordinary skill in the art. Where a compound of Formula I contains an alkenyl or alkenylene (alkylidene) group, geometric cis/trans (or Z/E) isomers are possible. Cis/trans isomers may be separated by conventional techniques well known to those skilled in the art, for example, chromatography and fractional crystallization. Salts of the present invention can be prepared according to methods known to those of skill in the art. The compounds of Formula I that are basic in nature are capable of forming a wide variety of salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate the compound of the present invention from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent and subsequently convert the latter free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the basic compounds of this invention can be prepared by treating the basic compound with a substantially equivalent amount of the selected mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent, such as methanol or ethanol. Upon evaporation of the solvent, the desired solid salt is obtained. The desired acid salt can also be precipitated from a solution of the free base in an organic solvent by adding an appropriate mineral or organic acid to the solution. If the inventive compound is a base, the desired pharmaceutically acceptable salt may be prepared by any suitable method available in the art, for example, treatment of the free base with an inorganic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like, or with an organic acid, such as acetic acid, maleic acid, succinic acid, mandelic acid, fumaric acid, malonic acid, pyruvic acid, oxalic acid, glycolic acid, salicylic acid, isonicotinic acid, lactic acid, pantothenic acid, bitartric acid, ascorbic acid, 2,5-dihydroxybenzoic acid, gluconic acid, saccharic acid, formic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and pamoic [i.e., 4,4′-methanediyl bis(3-hydroxynaphthalene-2-carboxylic acid)] acid, a pyranosidyl acid, such as glucuronic acid or galacturonic acid, an alpha-hydroxy acid, such as citric acid or tartaric acid, an amino acid, such as aspartic acid or glutamic acid, an aromatic acid, such as benzoic acid or cinnamic acid, a sulfonic acid, such as ethanesulfonic acid, or the like. Those compounds of Formula I that are acidic in nature are capable of forming base salts with various pharmacologically acceptable cations. Examples of such salts include the alkali metal or alkaline earth metal salts, and particularly the sodium and potassium salts. These salts are all prepared by conventional techniques. The chemical bases which are used as reagents to prepare the pharmaceutically acceptable base salts of this invention are those which form non-toxic base salts with the acidic compounds of Formula I. These salts may be prepared by any suitable method, for example, treatment of the free acid with an inorganic or organic base, such as an amine (primary, secondary or tertiary), an alkali metal hydroxide or alkaline earth metal hydroxide, or the like. These salts can also be prepared by treating the corresponding acidic compounds with an aqueous solution containing the desired pharmacologically acceptable cations, and then evaporating the resulting solution to dryness, for example under reduced pressure. Alternatively, they may also be prepared by mixing lower alkanolic solutions of the acidic compounds and the desired alkali metal alkoxide together, and then evaporating the resulting solution to dryness in the same manner as before. In either case, stoichiometric quantities of reagents are, for example, employed in order to ensure completeness of reaction and maximum yields of the desired final product. Pharmaceutically acceptable salts of compounds of Formula I (including compounds of Formula Ia or Ib) may be prepared by one or more of three methods: (i) by reacting the compound of Formula I with the desired acid or base; (ii) by removing an acid- or base-labile protecting group from a suitable precursor of the compound of Formula I or by ring-opening a suitable cyclic precursor, for example, a lactone or lactam, using the desired acid or base; or (iii) by converting one salt of the compound of Formula I to another by reaction with an appropriate acid or base or by means of a suitable ion exchange column. All three reactions are typically carried out in solution. The resulting salt may precipitate out and be collected by filtration or may be recovered by evaporation of the solvent. The degree of ionization in the resulting salt may vary from completely ionized to almost non-ionized. Polymorphs can be prepared according to techniques well-known to those skilled in the art, for example, by crystallization. When any racemate crystallizes, crystals of two different types are possible. The first type is the racemic compound (true racemate) referred to above wherein one homogeneous form of crystal is produced containing both enantiomers in equimolar amounts. The second type is the racemic mixture or conglomerate wherein two forms of crystal are produced in equimolar amounts each comprising a single enantiomer. While both of the crystal forms present in a racemic mixture may have almost identical physical properties, they may have different physical properties compared to the true racemate. Racemic mixtures may be separated by conventional techniques known to those skilled in the art—see, for example, Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen (Wiley, New York, 1994). The invention also includes isotopically labeled compounds of Formula I wherein one or more atoms is replaced by an atom having the same atomic number, but an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Isotopically labeled compounds of Formula I (or pharmaceutically acceptable salts thereof or N-oxides thereof) can generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described herein, using an appropriate isotopically labeled reagent in place of the non-labeled reagent otherwise employed. Prodrugs in accordance with the invention can, for example, be produced by replacing appropriate functionalities present in the compounds of Formula I with certain moieties known to those skilled in the art as ‘pro-moieties’ as described, for example, in Design of Prodrugs by H. Bundgaard (Elsevier, 1985). The compounds of Formula I should be assessed for their biopharmaceutical properties, such as solubility and solution stability (across pH), permeability, etc., in order to select the most appropriate dosage form and route of administration for treatment of the proposed indication. Compounds of the invention intended for pharmaceutical use may be administered as crystalline or amorphous products. They may be obtained, for example, as solid plugs, powders, or films by methods such as precipitation, crystallization, freeze drying, spray drying, or evaporative drying. Microwave or radio frequency drying may be used for this purpose. They may be administered alone or in combination with one or more other compounds of the invention or in combination with one or more other drugs (or as any combination thereof). Generally, they will be administered as a formulation in association with one or more pharmaceutically acceptable excipients. The term “excipient” is used herein to describe any ingredient other than the compound(s) of the invention. The choice of excipient will to a large extent depend on factors such as the particular mode of administration, the effect of the excipient on solubility and stability, and the nature of the dosage form. Pharmaceutical compositions suitable for the delivery of compounds of the present invention (or pharmaceutically acceptable salts thereof) and methods for their preparation will be readily apparent to those skilled in the art. Such compositions and methods for their preparation may be found, for example, in Remington's Pharmaceutical Sciences, 19th Edition (Mack Publishing Company, 1995). The compounds of the invention (including pharmaceutically acceptable salts thereof and N-oxides thereof) may be administered orally. Oral administration may involve swallowing, so that the compound enters the gastrointestinal tract, and/or buccal, lingual, or sublingual administration by which the compound enters the blood stream directly from the mouth. Formulations suitable for oral administration include solid, semi-solid and liquid systems such as tablets; soft or hard capsules containing multi- or nano-particulates, liquids, or powders; lozenges (including liquid-filled); chews; gels; fast dispersing dosage forms; films; ovules; sprays; and buccal/mucoadhesive patches. Liquid formulations include suspensions, solutions, syrups and elixirs. Such formulations may be employed as fillers in soft or hard capsules (made, for example, from gelatin or hydroxypropyl methyl cellulose) and typically comprise a carrier, for example, water, ethanol, polyethylene glycol, propylene glycol, methyl cellulose, or a suitable oil, and one or more emulsifying agents and/or suspending agents. Liquid formulations may also be prepared by the reconstitution of a solid, for example, from a sachet. The compounds of the invention may also be used in fast-dissolving, fast-disintegrating dosage forms such as those described by Liang and Chen, Expert Opinion in Therapeutic Patents 2001, 11, 981-986. For tablet dosage forms, depending on dose, the drug may make up from 1 weight % to 80 weight % of the dosage form, more typically from 5 weight % to 60 weight % of the dosage form. In addition to the drug, tablets generally contain a disintegrant. Examples of disintegrants include sodium starch glycolate, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, croscarmellose sodium, crospovidone, polyvinylpyrrolidone, methyl cellulose, microcrystalline cellulose, lower alkyl-substituted hydroxypropyl cellulose, starch, pregelatinized starch and sodium alginate. Generally, the disintegrant will comprise from 1 weight % to 25 weight %, for example, from 5 weight % to 20 weight % of the dosage form. Binders are generally used to impart cohesive qualities to a tablet formulation. Suitable binders include microcrystalline cellulose, gelatin, sugars, polyethylene glycol, natural and synthetic gums, polyvinylpyrrolidone, pregelatinized starch, hydroxypropyl cellulose and hydroxypropyl methylcellulose. Tablets may also contain diluents, such as lactose (monohydrate, spray-dried monohydrate, anhydrous and the like), mannitol, xylitol, dextrose, sucrose, sorbitol, microcrystalline cellulose, starch and dibasic calcium phosphate dihydrate. Tablets may also optionally comprise surface active agents, such as sodium lauryl sulfate and polysorbate 80, and glidants such as silicon dioxide and talc. When present, surface active agents may comprise from 0.2 weight % to 5 weight % of the tablet, and glidants may comprise from 0.2 weight % to 1 weight % of the tablet. Tablets also generally contain lubricants such as magnesium stearate, calcium stearate, zinc stearate, sodium stearyl fumarate, and mixtures of magnesium stearate with sodium lauryl sulfate. Lubricants generally comprise from 0.25 weight % to 10 weight %, for example, from 0.5 weight % to 3 weight % of the tablet. Other possible ingredients include anti-oxidants, colorants, flavoring agents, preservatives and taste-masking agents. Exemplary tablets contain up to about 80% drug, from about 10 weight % to about 90 weight % binder, from about 0 weight % to about 85 weight % diluent, from about 2 weight % to about 10 weight % disintegrant, and from about 0.25 weight % to about 10 weight % lubricant. Tablet blends may be compressed directly or by roller to form tablets. Tablet blends or portions of blends may alternatively be wet-, dry-, or melt-granulated, melt-congealed, or extruded before tabletting. The final formulation may comprise one or more layers and may be coated or uncoated; it may even be encapsulated. The formulation of tablets is discussed in Pharmaceutical Dosage Forms: Tablets , Vol. 1, by H. Lieberman and L. Lachman (Marcel Dekker, New York, 1980). Consumable oral films for human or veterinary use are typically pliable water-soluble or water-swellable thin film dosage forms which may be rapidly dissolving or mucoadhesive and typically comprise a compound of Formula I, a film-forming polymer, a binder, a solvent, a humectant, a plasticizer, a stabilizer or emulsifier, a viscosity-modifying agent and a solvent. Some components of the formulation may perform more than one function. The compound of Formula I (or pharmaceutically acceptable salts thereof or N-oxides thereof) may be water-soluble or insoluble. A water-soluble compound typically comprises from 1 weight % to 80 weight %, more typically from 20 weight % to 50 weight %, of the solutes. Less soluble compounds may comprise a smaller proportion of the composition, typically up to 30 weight % of the solutes. Alternatively, the compound of Formula I may be in the form of multiparticulate beads. The film-forming polymer may be selected from natural polysaccharides, proteins, or synthetic hydrocolloids and is typically present in the range 0.01 to 99 weight %, more typically in the range 30 to 80 weight %. Other possible ingredients include anti-oxidants, colorants, flavorings and flavor enhancers, preservatives, salivary stimulating agents, cooling agents, co-solvents (including oils), emollients, bulking agents, anti-foaming agents, surfactants and taste-masking agents. Films in accordance with the invention are typically prepared by evaporative drying of thin aqueous films coated onto a peelable backing support or paper. This may be done in a drying oven or tunnel, typically a combined coater dryer, or by freeze-drying or vacuuming. Solid formulations for oral administration may be formulated to be immediate and/or modified release. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted and programmed release. Suitable modified release formulations for the purposes of the invention are described in U.S. Pat. No. 6,106,864. Details of other suitable release technologies such as high energy dispersions and osmotic and coated particles are to be found in Verma et al., Pharmaceutical Technology On - line, 25(2), 1-14 (2001). The use of chewing gum to achieve controlled release is described in WO 00/35298. The compounds of the invention (including pharmaceutically acceptable salts thereof) may also be administered directly into the blood stream, into muscle, or into an internal organ. Suitable means for parenteral administration include intravenous, intraarterial, intraperitoneal, intrathecal, intraventricular, intraurethral, intrasternal, intracranial, intramuscular, intrasynovial and subcutaneous. Suitable devices for parenteral administration include needle (including microneedle) injectors, needle-free injectors and infusion techniques. Parenteral formulations are typically aqueous solutions which may contain excipients such as salts, carbohydrates and buffering agents (for example to a pH of from 3 to 9), but, for some applications, they may be more suitably formulated as a sterile non-aqueous solution or as a dried form to be used in conjunction with a suitable vehicle such as sterile, pyrogen-free water. The preparation of parenteral formulations under sterile conditions, for example, by lyophilization, may readily be accomplished using standard pharmaceutical techniques well known to those skilled in the art. The solubility of compounds of Formula I (including pharmaceutically acceptable salts thereof) used in the preparation of parenteral solutions may be increased by the use of appropriate formulation techniques, such as the incorporation of solubility-enhancing agents. Formulations for parenteral administration may be formulated to be immediate and/or modified release. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted and programmed release. Thus compounds of the invention may be formulated as a suspension or as a solid, semi-solid, or thixotropic liquid for administration as an implanted depot providing modified release of the active compound. Examples of such formulations include drug-coated stents and semi-solids and suspensions comprising drug-loaded poly(DL-lactic-coglycolic acid) (PLGA) microspheres. The compounds of the invention (including pharmaceutically acceptable salts thereof) may also be administered topically, (intra)dermally, or transdermally to the skin or mucosa. Typical formulations for this purpose include gels, hydrogels, lotions, solutions, creams, ointments, dusting powders, dressings, foams, films, skin patches, wafers, implants, sponges, fibers, bandages and microemulsions. Liposomes may also be used. Typical carriers include alcohol, water, mineral oil, liquid petrolatum, white petrolatum, glycerin, polyethylene glycol and propylene glycol. Penetration enhancers may be incorporated. See e.g., Finnin and Morgan, J. Pharm. Sci. 1999, 88, 955-958. Other means of topical administration include delivery by electroporation, iontophoresis, phonophoresis, sonophoresis and microneedle or needle-free (e.g., Powderject™, Bioject™, etc.) injection. Formulations for topical administration may be formulated to be immediate and/or modified release. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted and programmed release. The compounds of the invention (including pharmaceutically acceptable salts thereof) can also be administered intranasally or by inhalation, typically in the form of a dry powder (either alone; as a mixture, for example, in a dry blend with lactose; or as a mixed component particle, for example, mixed with phospholipids, such as phosphatidylcholine) from a dry powder inhaler, as an aerosol spray from a pressurized container, pump, spray, atomizer (for example an atomizer using electrohydrodynamics to produce a fine mist), or nebulizer, with or without the use of a suitable propellant, such as 1,1,1,2-tetrafluoroethane or 1,1,1,2,3,3,3-heptafluoropropane, or as nasal drops. For intranasal use, the powder may comprise a bioadhesive agent, for example, chitosan or cyclodextrin. The pressurized container, pump, spray, atomizer, or nebulizer contains a solution or suspension of the compound(s) of the invention comprising, for example, ethanol, aqueous ethanol, or a suitable alternative agent for dispersing, solubilizing, or extending release of the active, a propellant(s) as solvent and an optional surfactant, such as sorbitan trioleate, oleic acid, or an oligolactic acid. Prior to use in a dry powder or suspension formulation, the drug product is micronized to a size suitable for delivery by inhalation (typically less than 5 microns). This may be achieved by any appropriate comminuting method, such as spiral jet milling, fluid bed jet milling, supercritical fluid processing to form nanoparticles, high pressure homogenization, or spray drying. Capsules (made, for example, from gelatin or hydroxypropyl methyl cellulose), blisters and cartridges for use in an inhaler or insufflator may be formulated to contain a powder mix of the compound of the invention, a suitable powder base such as lactose or starch and a performance modifier such as L-leucine, mannitol, or magnesium stearate. The lactose may be anhydrous or in the form of the monohydrate. Other suitable excipients include dextran, glucose, maltose, sorbitol, xylitol, fructose, sucrose and trehalose. A suitable solution formulation for use in an atomizer using electrohydrodynamics to produce a fine mist may contain from 1 μg to 20 mg of the compound of the invention per actuation and the actuation volume may vary from 1 μL to 100 μL. A typical formulation may comprise a compound of Formula I or a pharmaceutically acceptable salt thereof, propylene glycol, sterile water, ethanol and sodium chloride. Alternative solvents which may be used instead of propylene glycol include glycerol and polyethylene glycol. Suitable flavors, such as menthol and levomenthol, or sweeteners, such as saccharin or saccharin sodium, may be added to those formulations of the invention intended for inhaled/intranasal administration. Formulations for inhaled/intranasal administration may be formulated to be immediate and/or modified release using, for example, PGLA. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted and programmed release. In the case of dry powder inhalers and aerosols, the dosage unit is determined by means of a valve which delivers a metered amount. Units in accordance with the invention are typically arranged to administer a metered dose or “puff” containing from 0.01 to 100 mg of the compound of Formula I. The overall daily dose will typically be in the range 1 μg to 200 mg, which may be administered in a single dose or, more usually, as divided doses throughout the day. The compounds of the invention may be administered rectally or vaginally, for example, in the form of a suppository, pessary, or enema. Cocoa butter is a traditional suppository base, but various alternatives may be used as appropriate. Formulations for rectal/vaginal administration may be formulated to be immediate and/or modified release. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted and programmed release. The compounds of the invention (including pharmaceutically acceptable salts thereof) may also be administered directly to the eye or ear, typically in the form of drops of a micronized suspension or solution in isotonic, pH-adjusted, sterile saline. Other formulations suitable for ocular and aural administration include ointments, gels, biodegradable (e.g., absorbable gel sponges, collagen) and non-biodegradable (e.g., silicone) implants, wafers, lenses and particulate or vesicular systems, such as niosomes or liposomes. A polymer such as crossed-linked polyacrylic acid, polyvinylalcohol, hyaluronic acid, a cellulosic polymer, for example, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, or methyl cellulose, or a heteropolysaccharide polymer, for example, gelan gum, may be incorporated together with a preservative, such as benzalkonium chloride. Such formulations may also be delivered by iontophoresis. Formulations for ocular/aural administration may be formulated to be immediate and/or modified release. Modified release formulations include delayed-, sustained-, pulsed-, controlled-, targeted, or programmed release. The compounds of the invention (including pharmaceutically acceptable salts thereof) may be combined with soluble macromolecular entities, such as cyclodextrin and suitable derivatives thereof or polyethylene glycol-containing polymers, in order to improve their solubility, dissolution rate, taste-masking, bioavailability and/or stability for use in any of the aforementioned modes of administration. Drug-cyclodextrin complexes, for example, are found to be generally useful for most dosage forms and administration routes. Both inclusion and non-inclusion complexes may be used. As an alternative to direct complexation with the drug, the cyclodextrin may be used as an auxiliary additive, i.e., as a carrier, diluent, or solubilizer. Most commonly used for these purposes are alpha-, beta- and gamma-cyclodextrins, examples of which may be found in International Patent Applications Nos. WO 91/11172, WO 94/02518 and WO 98/55148. Since the present invention has an aspect that relates to the treatment of the disease/conditions described herein with a combination of active ingredients which may be administered separately, the invention also relates to combining separate pharmaceutical compositions in kit form. The kit comprises two separate pharmaceutical compositions: a compound of Formula I a prodrug thereof or a salt of such compound or prodrug and a second compound as described above. The kit comprises means for containing the separate compositions such as a container, a divided bottle or a divided foil packet. Typically the kit comprises directions for the administration of the separate components. The kit form is particularly advantageous when the separate components are for example administered in different dosage forms (e.g., oral and parenteral), are administered at different dosage intervals, or when titration of the individual components of the combination is desired by the prescribing physician. An example of such a kit is a so-called blister pack. Blister packs are well known in the packaging industry and are being widely used for the packaging of pharmaceutical unit dosage forms (tablets, capsules, and the like). Blister packs generally consist of a sheet of relatively stiff material covered with a foil of a transparent plastic material. During the packaging process recesses are formed in the plastic foil. The recesses have the size and shape of the tablets or capsules to be packed. Next, the tablets or capsules are placed in the recesses and the sheet of relatively stiff material is sealed against the plastic foil at the face of the foil which is opposite from the direction in which the recesses were formed. As a result, the tablets or capsules are sealed in the recesses between the plastic foil and the sheet. In some embodiments, the strength of the sheet is such that the tablets or capsules can be removed from the blister pack by manually applying pressure on the recesses whereby an opening is formed in the sheet at the place of the recess. The tablet or capsule can then be removed via said opening. It may be desirable to provide a memory aid on the kit, e.g., in the form of numbers next to the tablets or capsules whereby the numbers correspond with the days of the regimen which the tablets or capsules so specified should be ingested. Another example of such a memory aid is a calendar printed on the card, e.g., as follows “First Week, Monday, Tuesday, etc. . . . Second Week, Monday, Tuesday, . . . ” etc. Other variations of memory aids will be readily apparent. A “daily dose” can be a single tablet or capsule or several pills or capsules to be taken on a given day. Also, a daily dose of Formula I compound can consist of one tablet or capsule while a daily dose of the second compound can consist of several tablets or capsules and vice versa. The memory aid should reflect this. In another specific embodiment of the invention, a dispenser designed to dispense the daily doses one at a time in the order of their intended use is provided. For example, the dispenser is equipped with a memory aid, so as to further facilitate compliance with the regimen. An example of such a memory aid is a mechanical counter which indicates the number of daily doses that has been dispensed. Another example of such a memory aid is a battery-powered micro-chip memory coupled with a liquid crystal readout, or audible reminder signal which, for example, reads out the date that the last daily dose has been taken and/or reminds one when the next dose is to be taken. The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters that can be changed or modified to yield essentially the same results. Additional compounds within the scope of this invention may be prepared using the methods illustrated in these Examples, either alone or in combination with techniques generally known in the art. In the following Examples and Preparations, “DMSO” means dimethyl sulfoxide, “N” where referring to concentration means Normal, “M” means molar, “mL” means milliliter, “mmol” means millimoles, “μmol” means micromoles, “eq.” means equivalent, “° C.” means degrees Celsius, “MHz” means megahertz, “HPLC” means high-performance liquid chromatography. EXAMPLES The following illustrate the synthesis of various compounds of the present invention. Additional compounds within the scope of this invention may be prepared using the methods illustrated in these Examples, either alone or in combination with techniques generally known in the art. Experiments were generally carried out under inert atmosphere (nitrogen or argon), particularly in cases where oxygen- or moisture-sensitive reagents or intermediates were employed. Commercial solvents and reagents were generally used without further purification. Anhydrous solvents were employed where appropriate, generally AcroSeal® products from Acros Organics or DriSolv® products from EMD Chemicals. In other cases, commercial solvents were passed through columns packed with 4 Å molecular sieves, until the following QC standards for water were attained: a) <100 ppm for dichloromethane, toluene, N,N-dimethylformamide and tetrahydrofuran; b)<180 ppm for methanol, ethanol, 1,4-dioxane and diisopropylamine. For very sensitive reactions, solvents were further treated with metallic sodium, calcium hydride or molecular sieves, and distilled just prior to use. Products were generally dried under vacuum before being carried on to further reactions or submitted for biological testing. Mass spectrometry data is reported from either liquid chromatography-mass spectrometry (LCMS), atmospheric pressure chemical ionization (APCI) or gas chromatography-mass spectrometry (GCMS) instrumentation. Chemical shifts for nuclear magnetic resonance (NMR) data are expressed in parts per million (ppm, δ) referenced to residual peaks from the deuterated solvents employed. In some examples, chiral separations were carried out to separate enantiomers or atropisomers (or atropenantiomers) of certain compounds of the invention (in some examples, the separated atropisomers are designated as ENT-1 and ENT-2, according to their order of elution). In some examples, the optical rotation of an enantiomer or atropisomer was measured using a polarimeter. According to its observed rotation data (or its specific rotation data), an enantiomer or atropisomer (or atropenantiomer) with a clockwise rotation was designated as the (+)-enantiomer or (+)-atropisomer [or the (+) atropenantiomer] and an enantiomer or atropisomer (or atropenantiomer) with a counter-clockwise rotation was designated as the (−)-enantiomer or (−)-atropisomer [or the (−) atropenantiomer]. Reactions proceeding through detectable intermediates were generally followed by LCMS, and allowed to proceed to full conversion prior to addition of subsequent reagents. For syntheses referencing procedures in other Examples or Methods, reaction conditions (reaction time and temperature) may vary. In general, reactions were followed by thin layer chromatography or mass spectrometry, and subjected to work-up when appropriate. Purifications may vary between experiments: in general, solvents and the solvent ratios used for eluents/gradients were chosen to provide appropriate R f s or retention times. Example 1 4-[4-(4,6-Dimethylpyrimidin-5-yl)-3-methylphenoxy]furo[2,3-d]pyrimidine (1) Step 1. Synthesis of 2-aminofuran-3-carbonitrile (C1) 1,4-Dioxane-2,5-diol (hydroxyacetaldehyde dimer, 5 g, 40 mmol) was dissolved in water (5 mL), treated with aqueous hydrochloric acid (0.1 M, 15 mL), and allowed to stir for 18 hours. Malononitrile (4.72 mL, 74.9 mmol) was added drop-wise, followed by the addition of diethylamine (7.72 mL, 74.9 mmol) drop-wise. The reaction mixture was stirred at room temperature for 3 hours and was then quenched with saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate, and the combined organic layers were dried over magnesium sulfate. After removal of solvent in vacuo, the residue was purified by silica gel chromatography (Gradient: 20% to 40% ethyl acetate in heptane) to provide the product as a yellow solid. Yield: 3.22 g, 28 mmol, 70%. LCMS m/z 108.8 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 6.72 (d, J=2.1 Hz, 1H), 6.29 (d, J=2.3 Hz, 1H), 4.72 (br s, 2H). Step 2. Synthesis of furo[2,3-d]pyrimidin-4-amine (C2) Compound C1 (100 mg, 0.925 mmol) was dissolved in formamide (2 mL) and the reaction mixture was heated at 120° C. overnight. The reaction mixture was cooled to room temperature and partitioned between water and ethyl acetate. The aqueous layer was extracted with ethyl acetate and dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo to afford the product as a yellow solid. Yield: 21 mg, 0.16 mmol, 17%. LCMS m/z 135.9 [M+H] + . 1 H NMR (400 MHz, CD 3 OD) δ 8.13 (s, 1H), 7.61 (d, J=2.5 Hz, 1H), 6.89 (d, J=2.5 Hz, 1H). Step 3. Synthesis of 4-chlorofuro[2,3-d]pyrimidine (C3) A mixture of C2 (660 mg, 4.88 mmol), tert-butyl nitrite (12.1 mL, 97.7 mmol), and trimethylsilyl chloride (3.12 mL, 24.4 mmol) in acetonitrile (20 mL) was stirred at 50° C. for 1 hour. The reaction was cooled to room temperature and quenched with aqueous sodium hydroxide solution (2 M, 30 mL). The aqueous layer was extracted with ethyl acetate (3×50 mL), and the combined organic layers were dried over sodium sulfate. The solvent was removed in vacuo and the residue was purified via chromatography on silica gel (Gradient: 0% to 30% ethyl acetate in heptane) to provide the product as a volatile white solid. Yield: 168 mg, 1.09 mmol, 22%. LCMS m/z 154.8 [M+H]+. 1 H NMR (400 MHz, CDCl 3 ) δ 8.77 (s, 1H), 7.76 (d, J=0.8 Hz, 1H), 7.25 (d, J=0.8 Hz, 1H). Step 4. Synthesis of 5-(4-methoxy-2-methylphenyl)-4,6-dimethylpyrimidine (C4) [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II)-dichloromethane complex (5 g, 6 mmol) was added to a degassed mixture of 2-(4-methoxy-2-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (30 g, 120 mmol), 5-bromo-4,6-dimethylpyrimidine (22.5 g, 120 mmol), and potassium phosphate (76.3 g, 359 mmol) in 1,4-dioxane (300 mL) and water (150 mL). The reaction mixture was heated at reflux for 4 hours, whereupon it was filtered and concentrated in vacuo. Purification via silica gel chromatography (Gradient: ethyl acetate in petroleum ether) provided the product as a brown solid. Yield: 25 g, 110 mmol, 92%. LCMS m/z 229.3 [M+H] + . 1 H NMR (300 MHz, CDCl 3 ) δ 8.95 (s, 1H), 6.94 (d, J=8.2 Hz, 1H), 6.87-6.89 (m, 1H), 6.84 (dd, J=8.3, 2.5 Hz, 1H), 3.86 (s, 3H), 2.21 (s, 6H), 1.99 (s, 3H). Step 5. Synthesis of 4-(4,6-dimethylpyrimidin-5-yl)-3-methylphenol (C5) Boron tribromide (3.8 mL, 40 mmol) was added drop-wise to a solution of C4 (3.0 g, 13 mmol) in dichloromethane (150 mL) at −70° C. The reaction mixture was stirred at room temperature for 16 hours, then adjusted to pH 8 with saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted with dichloromethane (3×200 mL), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. Silica gel chromatography (Gradient: 60% to 90% ethyl acetate in petroleum ether) afforded the product as a yellow solid. Yield: 1.2 g, 5.6 mmol, 43%. LCMS m/z 215.0 [M+H + ]. 1 H NMR (400 MHz, CDCl 3 ) δ 8.98 (s, 1H), 6.89 (d, J=8.0 Hz, 1H), 6.86 (d, J=2.3 Hz, 1H), 6.80 (dd, J=8.3, 2.5 Hz, 1H), 2.24 (s, 6H), 1.96 (s, 3H). Step 6. Synthesis of 4-[4-(4,6-dimethylpyrimidin-5-yl)-3-methylphenoxy]furo[2,3-d]pyrimidine (1) To a stirred solution of C3 (33 mg, 0.21 mmol) in dimethyl sulfoxide (1 mL) was added C5 (45 mg, 0.21 mmol) and cesium carbonate (205 mg, 0.63 mmol). The 5 reaction mixture was stirred at 120° C. for 3 hours, then was cooled to room temperature. The reaction mixture was partitioned between ethyl acetate and water, and the aqueous layer was extracted twice with ethyl acetate. The organic layers were combined and dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified via silica gel chromatography (Gradient: 0% to 40% [80:20:1 dichloromethane/methanol/concentrated ammonium hydroxide] in dichloromethane) to provide the product as a pale yellow solid. Yield: 30 mg, 0.09 mmol, 43%. LCMS m/z 333.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.96 (s, 1H), 8.55 (s, 1H), 7.76 (d, J=2.3 Hz, 1H), 7.19 (m, 1H), 7.10 (m, 1H), 6.79 (d, J=2.5 Hz, 1H), 2.24 (s, 6H), 2.03 (s, 3H), 1.51 (s, 3H). Example 2 4-[3-Methyl-4-(6-methylimidazo[1,2-a]pyrazin-5-yl) phenoxy]-1H-imidazo[4,5-c]pyridine (2) Step 1. Synthesis of 4-chloro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-imidazo[4,5-c]pyridine (C6) and 4-chloro-3-{[2-(trimethylsilyl)ethoxy]methyl}-3H-imidazo[4,5-c]pyridine (C7) To a solution of 4-chloro-1H-imidazo[4,5-c]pyridine (4.64 g, 30.2 mmol) in tetrahydrofuran (200 mL) was added sodium hydride (1.57 g, 39.3 mmol) at 0° C. The reaction mixture was stirred for 45 minutes at 0° C., whereupon 2-(trimethylsilyl)ethoxymethyl chloride (6.55 g, 39.3 mmol) was added. Stirring was continued for 2 hours at 0° C., at which time the reaction mixture was quenched with saturated aqueous ammonium chloride solution and then extracted with dichloromethane (3×50 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give a residue, which was purified by silica gel chromatography to afford a mixture of C6 and C7. Yield: 7.0 g, 24 mmol, 80%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.25 (t, J=5.1 Hz, 2H), 8.18 (s, 1H), 8.12 (s, 1H), 7.71 (d, J=5.6 Hz, 1H), 7.48 (d, J=5.6 Hz, 1H), 5.89 (s, 2H), 5.59 (s, 2H), 3.65 (t, J=8.0 Hz, 2H), 3.55 (t, J=8.0 Hz, 2H), 0.97 (m, 4H), 0.01 (s, 9H), 0.00 (s, 9H). Step 2. Synthesis of (4-bromo-3-methylphenoxy)[tri(propan-2-yl)]silane (C8) To a solution of 4-bromo-3-methylphenol (70 g, 0.374 mol) and 1H-imidazole (51.52 g, 0.748 mol) in N,N-dimethylformamide (420 mL) was added tri(propan-2-yl)silyl chloride (88 mL, 0.41 mol) drop-wise. The reaction mixture was stirred at room temperature overnight, then poured into water (1.5 L) and extracted with heptane (1.2 L). The organic layer was washed with water (1 L) and with saturated aqueous sodium chloride solution (400 mL), and dried over magnesium sulfate. The solvent was removed in vacuo to provide the product as a yellow oil. Yield: 137 g, 0.37 mmol, 100% yield. 1 H NMR (400 MHz, CDCl 3 ) δ 7.32 (d, J=8.7 Hz, 1H), 6.76 (d, J=2.7 Hz, 1H), 6.64 (dd, J=8.5, 2.7 Hz, 1H), 2.32 (s, 3H), 1.22 (m, 3H), 1.09 (d, J=8.0 Hz, 18H). Step 3. Synthesis of [3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy][tri(propan-2-yl)]silane (C9) To a degassed solution of C8 (137 g, 0.374 mol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (190 g, 0.748 mol) and potassium acetate (147 g, 1.49 mol) in 1,4-dioxane (1.3 L) was added [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (12.2 g, 15 mmol), and the reaction mixture was heated at reflux overnight. The reaction mixture was filtered through diatomaceous earth, washing with ethyl acetate, and concentrated in vacuo. Silica gel chromatography (Gradient: 0% to 3% ethyl acetate in heptane) afforded the product as a yellow oil. Yield: 131 g, 0.34 mmol, 90%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.62 (d, J=7.8 Hz, 1H), 6.65 (m, 2H), 2.47 (s, 3H), 1.31 (s, 12H), 1.27 (m, 1H), 1.08 (d, J=8.0 Hz, 18H). Step 4. Synthesis of 3-methyl-4-(6-methylimidazo[1,2-a]pyrazin-5-yl) phenol (C10) Water (17 μL, 0.94 mmol) was added to a suspension of 5-bromo-6-methylimidazo[1,2-a]pyrazine (see A. R. Harris et al., Tetrahedron 2011, 67, 9063-9066) (100 mg, 0.472 mmol), C9 (368 mg, 0.943 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (35 mg, 47 μmol) and potassium carbonate (130 mg, 0.943 mmol) in degassed 1,2-dimethoxyethane (2 mL). The reaction mixture was heated at reflux for 24 hours, then filtered through neutral diatomaceous earth, washing with acetone (20 mL). The solvent was removed in vacuo and the residue was purified by silica gel chromatography (Gradient: 0% to 10% methanol in ethyl acetate) to afford the product as a pale pink solid. Yield: 114 mg, 0.47 mmol, quantitative yield. 1 H NMR (400 MHz, CD 3 OD) δ 8.94 (s, 1H), 7.72 (d, J=1.4 Hz, 1H), 7.23 (s, 1H), 7.13 (d, J=8.2 Hz, 1H), 6.89 (d, J=2.7 Hz, 1H), 6.83 (dd, J=8.2, 2.3 Hz, 1H), 2.29 (s, 3H), 1.94 (s, 3H). Step 5. Synthesis of 4-[3-methyl-4-(6-methylimidazo[1,2-a]pyrazin-5-yl)phenoxy]-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-imidazo[4,5-c]pyridine (C11) and 4-[3-methyl-4-(6-methylimidazo[1,2-a]pyrazin-5-yl)phenoxy]-3-{[2-(trimethylsilyl)ethoxy]methyl}-3H-imidazo[4,5-c]pyridine (C12) To a solution of a mixture of C6 and C7 (100 mg, 0.35 mmol) in 1,4-dioxane (5 mL) were added C10 (84 mg, 0.35 mmol), 1,1′-binaphthalene-2,2′-diylbis(diphenylphosphane) (BINAP, 43.5 mg, 0.07 mmol), cesium carbonate (341 mg, 1.05 mmol), and palladium(II) acetate (7.84 mg, 35 μmol) at room temperature. The reaction mixture was degassed with nitrogen for 5 minutes and then heated to 120° C. for 4 hours. After cooling to room temperature, it was filtered through a pad of diatomaceous earth. The filtrate was concentrated in vacuo to provide the crude product (350 mg), which was used in the next step without further purification. Step 6. Synthesis of 4-[3-methyl-4-(6-methylimidazo[1,2-a]pyrazin-5-yl)phenoxy]-1H-imidazo[4,5-c]pyridine (2) To a mixture of C11 and C12 (from the previous step, 350 mg) was added trifluoroacetic acid (8 mL) at room temperature. The reaction mixture was stirred for 1 hour at 80° C. and was then concentrated in vacuo and purified by preparative HPLC to give the product. Yield: 46 mg, 0.13 mmol, 37% over two steps. LCMS m/z 357.0 [M+H] + . 1 H NMR (400 MHz, CD 3 OD) 9.03 (s, 1H), 8.39 (s, 1H), 7.93 (d, J=5.8 Hz, 1H), 7.81 (d, J=1.0 Hz, 1H), 7.54 (s, 1H), 7.45 (m, 2H), 7.39 (s, 1H), 7.31 (dd, J=8.0, 1.8 Hz, 1H), 2.40 (s, 3H), 2.09 (s, 3H). Examples 3, 4, and 5 6-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (3), (−)-6-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (4), and (+)-6-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (5) Step 1. Synthesis of 1-(4-methoxy-2-methylphenyl)propan-2-one (C13) This experiment was carried out four times. Tributyl(methoxy)stannane (400 g, 1.24 mol), 1-bromo-4-methoxy-2-methylbenzene (250 g, 1.24 mol), prop-1-en-2-yl acetate (187 g, 1.87 mol), palladium(II) acetate (7.5 g, 33 mmol) and tri-o-tolylphosphine (10 g, 33 mmol) were stirred together in toluene (2 L) at 100° C. for 18 hours. After it had cooled to room temperature, the reaction mixture was treated with aqueous potassium fluoride solution (4 M, 400 mL) and stirred for 2 hours at 40° C. The resulting mixture was diluted with toluene (500 mL) and filtered through diatomaceous earth; the filter pad was thoroughly washed with ethyl acetate (2×1.5 L). The organic phase from the combined filtrates was dried over sodium sulfate, filtered, and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 5% ethyl acetate in petroleum ether) provided the product as a yellow oil. Combined yield: 602 g, 3.38 mol, 68%. LCMS m/z 179.0 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 7.05 (d, J=8.3 Hz, 1H), 6.70-6.77 (m, 2H), 3.79 (s, 3H), 3.65 (s, 2H), 2.22 (s, 3H), 2.14 (s, 3H). Step 2. Synthesis of 1-(4-methoxy-2-methylphenyl)propane-1,2-dione (C14) Compound C13 (6.00 g, 33.7 mmol) and selenium dioxide (7.47 g, 67.3 mmol) were suspended in 1,4-dioxane (50 mL) and heated at 100° C. for 18 hours. The reaction mixture was cooled to room temperature and filtered through diatomaceous earth; the filtrate was concentrated in vacuo. Silica gel chromatography (Eluent: 10% ethyl acetate in heptane) afforded the product as a bright yellow oil. Yield: 2.55 g, 13.3 mmol, 39%. LCMS m/z 193.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 7.66 (d, J=8.6 Hz, 1H), 6.81 (br d, half of AB quartet, J=2.5 Hz, 1H), 6.78 (br dd, half of ABX pattern, J=8.7, 2.6 Hz, 1H), 3.87 (s, 3H), 2.60 (br s, 3H), 2.51 (s, 3H). Step 3. Synthesis of 6-(4-methoxy-2-methylphenyl)-5-methylpyrazin-2(1H)-one (C15) Compound C14 (4.0 g, 21 mmol) and glycinamide acetate (2.79 g, 20.8 mmol) were dissolved in methanol (40 mL) and cooled to −10° C. Aqueous sodium hydroxide solution (12 N, 3.5 mL, 42 mmol) was added, and the resulting mixture was slowly warmed to room temperature. After stirring for 3 days, the reaction mixture was concentrated in vacuo. The residue was diluted with water, and 1 M aqueous hydrochloric acid was added until the pH was approximately 7. The aqueous phase was extracted with ethyl acetate, and the combined organic extracts were washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting residue was slurried with 3:1 ethyl acetate/heptane, stirred for 5 minutes, filtered, and concentrated in vacuo. Silica gel chromatography (Eluent: ethyl acetate) provided the product as a tan solid that contained 15% of an undesired regioisomer; this material was used without further purification. Yield: 2.0 g. LCMS m/z 231.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.09 (s, 1H), 7.14 (d, J=8.2 Hz, 1H), 6.82-6.87 (m, 2H), 3.86 (s, 3H), 2.20 (s, 3H), 2.11 (s, 3H). Step 4. Synthesis of 6-(4-methoxy-2-methylphenyl)-1,5-dimethylpyrazin-2(1H)-one (C16) Compound C15 (from the previous step, 1.9 g) was dissolved in N,N-dimethylformamide (40 mL). Lithium bromide (0.86 g, 9.9 mmol) and sodium bis(trimethylsilyl)amide (95%, 1.91 g, 9.89 mmol) were added, and the resulting solution was stirred for 30 minutes. Methyl iodide (0.635 mL, 10.2 mmol) was added and stirring was continued at room temperature for 18 hours. The reaction mixture was then diluted with water and brought to a pH of approximately 7 by slow portion-wise addition of 1 M aqueous hydrochloric acid. The aqueous layer was extracted with ethyl acetate and the combined organic layers were washed several times with water, dried over magnesium sulfate, filtered, and concentrated. Silica gel chromatography (Gradient: 75% to 100% ethyl acetate in heptane) afforded the product as a viscous orange oil. Yield: 1.67 g, 6.84 mmol, 33% over two steps. LCMS m/z 245.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (s, 1H), 7.03 (br d, J=8 Hz, 1H), 6.85-6.90 (m, 2H), 3.86 (s, 3H), 3.18 (s, 3H), 2.08 (br s, 3H), 2.00 (s, 3H). Step 5. Synthesis of 6-(4-hydroxy-2-methylphenyl)-1,5-dimethylpyrazin-2(1H)-one (C17) To a −78° C. solution of C16 (1.8 g, 7.4 mmol) in dichloromethane (40 mL) was added a solution of boron tribromide in dichloromethane (1 M, 22 mL, 22 mmol). The cooling bath was removed after 30 minutes, and the reaction mixture was allowed to warm to room temperature and stir for 18 hours. The reaction was cooled to −78° C., and methanol (10 mL) was slowly added; the resulting mixture was gradually warmed to room temperature. After the solvent had been removed in vacuo, methanol (20 mL) was added, and the mixture was again concentrated under reduced pressure. The residue was diluted with ethyl acetate (300 mL) and water (200 mL), the aqueous layer was brought to pH 7 via portion-wise addition of saturated aqueous sodium carbonate solution, and the mixture was extracted with ethyl acetate (3×200 mL). The combined organic layers were washed with water and with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated in vacuo to afford the product as a light tan solid. Yield: 1.4 g, 6.0 mmol, 81%. LCMS m/z 231.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.21 (s, 1H), 6.98 (d, J=8.2 Hz, 1H), 6.87-6.89 (m, 1H), 6.85 (br dd, J=8.2, 2.5 Hz, 1H), 3.22 (s, 3H), 2.06 (br s, 3H), 2.03 (s, 3H). Step 6. Synthesis of 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (3), (−)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (4), and (+)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-1,5-dimethylpyrazin-2(1H)-one (5) To a stirred solution of C3 (60 mg, 0.39 mmol) in dimethyl sulfoxide (2 mL) was added C17 (121 mg, 0.39 mmol) and cesium carbonate (379 mg, 1.16 mmol). The reaction mixture was stirred at 120° C. for 3 hours, cooled to room temperature, and partitioned between ethyl acetate and water. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were washed sequentially with water and with saturated aqueous sodium chloride solution, then dried over sodium sulfate. The solvent was removed in vacuo and the residue was purified via silica gel chromatography (Gradient: 0% to 30% [80:20:1 dichloromethane/methanol/concentrated ammonium hydroxide] in dichloromethane) to provide product 3, a mixture of atropenantiomers, as a light yellow foam. Yield: 108 mg, 0.31 mmol, 80%. LCMS m/z 349.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.58 (s, 1H), 8.22 (s, 1H), 7.72 (d, J=2.5 Hz, 1H), 7.18-7.35 (m, 3H), 6.91 (d, J=2.4 Hz, 1H), 3.26 (s, 3H), 2.18 (s, 3H), 2.08 (s, 3H). Compound Example 3 was separated into its atropenantiomers via supercritical fluid chromatography Column: Chiral Technologies Chiralcel OJ-H, 5 μm; Eluent: 3:1 carbon dioxide/2-propanol). Example 4 [designated the (−)-atropenantiomer according to its observed rotation data] was the first-eluting isomer, followed by Example 5. Example 5 was designated the (+)-atropenantiomer according to its observed rotation data. 4: LCMS m/z 349.1 [M+H] + . 1 H NMR (400 MHz, CD 3 OD) δ 8.49 (s, 1H), 8.11 (s, 1H), 7.96 (d, J=2.5 Hz, 1H), 7.36-7.41 (m, 2H), 7.33 (br dd, half of ABX pattern, J=8, 2 Hz, 1H), 7.00 (d, J=2.5 Hz, 1H), 3.27 (s, 3H), 2.18 (s, 3H), 2.06 (s, 3H). 5: LCMS m/z 349.1 [M+H] + . 1 H NMR (400 MHz, CD 3 OD) δ 8.49 (s, 1H), 8.11 (s, 1H), 7.96 (d, J=2.5 Hz, 1H), 7.36-7.41 (m, 2H), 7.33 (br dd, half of ABX pattern, J=8, 2 Hz, 1H), 7.00 (d, J=2.5 Hz, 1H), 3.27 (s, 3H), 2.18 (s, 3H), 2.06 (s, 3H). Examples 6, 7, and 8 5-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (6), (+)-5-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (7), and (−)-5-[4-(Furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (8) Step 1. Synthesis of 4-hydroxy-3,5-dimethylfuran-2(5H)-one (C18) Methylation of ethyl 3-oxopentanoate according to the method of D. Kalaitzakis et al., Tetrahedron: Asymmetry 2007, 18, 2418-2426, afforded ethyl 2-methyl-3-oxopentanoate; subsequent treatment with 1 equivalent of bromine in chloroform provided ethyl 4-bromo-2-methyl-3-oxopentanoate. This crude material (139 g, 586 mmol) was slowly added to a 0° C. solution of potassium hydroxide (98.7 g, 1.76 mol) in water (700 mL). The internal reaction temperature rose to 30° C. during the addition. The reaction mixture was then subjected to vigorous stirring for 4 hours in an ice bath, at which point it was acidified via slow addition of concentrated hydrochloric acid. After extraction with ethyl acetate, the aqueous layer was saturated with solid sodium chloride and extracted three additional times with ethyl acetate. The combined organic layers were washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to afford a mixture of oil and solid (81.3 g). This material was suspended in chloroform (200 mL); the solids were removed via filtration and washed with chloroform (2×50 mL). The combined filtrates were concentrated in vacuo and treated with a 3:1 mixture of heptane and diethyl ether (300 mL). The mixture was vigorously swirled until some of the oil began to solidify, whereupon it was concentrated under reduced pressure to afford an oily solid (60.2 g). After addition of a 3:1 mixture of heptane and diethyl ether (300 mL) and vigorous stirring for 10 minutes, filtration afforded the product as an off-white solid. Yield: 28.0 g, 219 mmol, 37%. 1 H NMR (400 MHz, CDCl 3 ) δ 4.84 (br q, J=6.8 Hz, 1H), 1.74 (br s, 3H), 1.50 (d, J=6.8 Hz, 3H). Step 2. Synthesis of 2,4-dimethyl-5-oxo-2,5-dihydrofuran-3-yl trifluoromethanesulfonate (C19) Trifluoromethanesulfonic anhydride (23.7 mL, 140 mmol) was added portion-wise to a solution of C18 (15.0 g, 117 mmol) and N,N-diisopropylethylamine (99%, 24.8 mL, 140 mmol) in dichloromethane (500 mL) at −20° C., at a rate sufficient to maintain the internal reaction temperature below −10° C. The reaction mixture was allowed to warm gradually from −20° C. to 0° C. over 5 hours. It was then passed through a plug of silica gel, dried over magnesium sulfate, and concentrated in vacuo. The residue was suspended in diethyl ether and filtered; the filtrate was concentrated under reduced pressure. Purification using silica gel chromatography (Gradient: 0% to 17% ethyl acetate in heptane) afforded the product as a pale yellow oil. Yield: 21.06 g, 80.94 mmol, 69%. 1 H NMR (400 MHz, CDCl 3 ) δ 5.09-5.16 (m, 1H), 1.94-1.96 (m, 3H), 1.56 (d, J=6.6 Hz, 3H). Step 3. Synthesis of 2-[4-(benzyloxy)-2-methylphenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (C20) A mixture of benzyl 4-bromo-3-methylphenyl ether (19.0 g, 68.6 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (7.5 g, 10 mmol), potassium acetate (26.9 g, 274 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (20 g, 79 mmol) in 1,4-dioxane (500 mL) was heated at reflux for 2 hours. The reaction mixture was then filtered through diatomaceous earth, and the filtrate was concentrated in vacuo. Silica gel chromatography (Gradient: 0% to 1% ethyl acetate in petroleum ether) provided the product as a yellow gel. Yield: 15 g, 46 mmol, 67%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J=8.0 Hz, 1H), 7.30-7.46 (m, 5H), 6.76-6.82 (m, 2H), 5.08 (s, 2H), 2.53 (s, 3H), 1.34 (s, 12H). Step 4. Synthesis of 4-[4-(benzyloxy)-2-methylphenyl]-3,5-dimethylfuran-2(5H)-one (C21) Compound C19 (5.0 g, 19 mmol), C20 (7.48 g, 23.1 mmol), tetrakis(triphenylphosphine)palladium(0) (2.22 g, 1.92 mmol), and sodium carbonate (4.07 g, 38.4 mmol) were combined in 1,4-dioxane (100 mL) and water (5 mL), and heated at reflux for 2 hours. The reaction mixture was filtered and the filtrate was concentrated in vacuo. Silica gel chromatography (Eluents: 10:1, then 5:1 petroleum ether/ethyl acetate) provided the product as a white solid. Yield: 5.8 g, 19 mmol, 100%. NMR (400 MHz, CDCl 3 ) δ 7.33-7.49 (m, 5H), 6.98 (d, J=8.5 Hz, 1H), 6.94 (br d, J=2.5 Hz, 1H), 6.88 (br dd, J=8.3, 2.5 Hz, 1H), 5.20 (qq, J=6.7, 1.8 Hz, 1H), 5.09 (s, 2H), 2.21 (s, 3H), 1.78 (d, J=1.8 Hz, 3H), 1.31 (d, J=6.8 Hz, 3H). Step 5. Synthesis of 4-[4-(benzyloxy)-2-methylphenyl]-5-hydroxy-3,5-dimethylfuran-2(5H)-one (C22) A solution of C21 (5.4 g, 18 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (13.3 g, 87.4 mmol) in acetonitrile (100 mL) was cooled to −60° C. Oxygen was bubbled into the reaction mixture for 20 minutes at −60° C.; the solution was then stirred at 50° C. for 18 hours. The reaction mixture was concentrated in vacuo and purified via silica gel chromatography (Eluent: 5:1 petroleum ether/ethyl acetate) to provide the product as a colorless oil. Yield: 3.5 g, 11 mmol, 61%. 1 H NMR (400 MHz, CDCl 3 ), characteristic peaks: δ 7.33-7.49 (m, 5H), 6.92-6.96 (m, 1H), 6.88 (dd, J=8.5, 2.5 Hz, 1H), 5.09 (s, 2H), 2.20 (s, 3H), 1.73 (s, 3H). Step 6. Synthesis of 5-[4-(benzyloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (C23) A mixture of C22 (3.5 g, 11 mmol) and hydrazine hydrate (85% in water, 1.9 g, 32 mmol) in n-butanol (60 mL) was heated at reflux for 18 hours. After removal of volatiles under reduced pressure, the residue was stirred with ethyl acetate (20 mL) for 30 minutes, whereupon filtration provided the product as a white solid. Yield: 2.0 g, 6.2 mmol, 56%. 1 H NMR (400 MHz, CDCl 3 ) δ 10.93 (br s, 1H), 7.33-7.51 (m, 5H), 6.96 (s, 1H), 6.88-6.94 (m, 2H), 5.10 (s, 2H), 2.04 (s, 3H), 1.95 (s, 3H), 1.91 (s, 3H). Step 7. Synthesis of 5-[4-(benzyloxy)-2-methylphenyl]-4,6-dimethyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C24) A mixture of C23 (17.8 g, 55.6 mmol), 3,4-dihydro-2H-pyran (233 g, 2.77 mol) and p-toluenesulfonic acid monohydrate (2.1 g, 11 mmol) in tetrahydrofuran (800 mL) was heated at reflux for 18 hours. Triethylamine (10 mL, 72 mmol) was added, and the mixture was concentrated in vacuo. Silica gel chromatography (Gradient: 0% to 25% ethyl acetate in petroleum ether) afforded the product as a solid, presumed to be a mixture of diastereomeric atropisomers from its 1 H NMR spectrum. Yield: 20 g, 49 mmol, 88%. 1 H NMR (400 MHz, CDCl 3 ), characteristic peaks: δ 7.32-7.50 (m, 5H), 6.82-6.96 (m, 3H), 6.15 (br d, J=10.3 Hz, 1H), 5.08 (s, 2H), 4.14-4.23 (m, 1H), 3.76-3.85 (m, 1H), 2.28-2.41 (m, 1H), 2.01 and 2.04 (2 s, total 3H), 1.97 and 1.98 (2 s, total 3H), 1.89 and 1.89 (2 s, total 3H). Step 8. Synthesis of 5-(4-hydroxy-2-methylphenyl)-4,6-dimethyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C25) Palladium (10% on carbon, 1.16 g, 1.09 mmol) was added to a solution of C24 (1.47 g, 3.63 mmol) in methanol (30 mL) and ethyl acetate (10 mL), and the mixture was hydrogenated (50 psi) on a Parr shaker for 18 hours at room temperature. The reaction mixture was filtered through diatomaceous earth, and the filter pad was rinsed with ethyl acetate; the combined filtrates were concentrated in vacuo and triturated with heptane, affording the product as a white solid, judged to be a mixture of diastereomeric atropisomers from its 1H NMR spectrum. Yield: 1.01 g, 3.21 mmol, 88%. 1 H NMR (400 MHz, CDCl 3 ), characteristic peaks: δ 6.74-6.85 (m, 3H), 6.12-6.17 (m, 1H), 4.15-4.23 (m, 1H), 3.76-3.84 (m, 1H), 2.28-2.41 (m, 1H), 1.99 and 2.01 (2 s, total 3H), 1.97 and 1.98 (2 s, total 3H), 1.89 and 1.89 (2 s, total 3H). Step 9. Synthesis of 5-(4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl)-4,6-dimethyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C26) To a resealable pressure tube were added C3 (38.9 mg, 0.25 mmol), C25 (66 mg, 0.21 mmol), cesium carbonate (205 mg, 0.63 mmol) and dimethyl sulfoxide (15 mL). The reaction mixture was heated to 120° C. for 6 hours, then cooled to room temperature and diluted with ethyl acetate. The mixture was washed sequentially with water and with saturated aqueous sodium chloride solution, then dried over magnesium sulfate. The solvent was removed in vacuo and the residue was used in the next step without further purification. LCMS m/z 433.1 [M+H] + . Step 10. Synthesis of 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (6) To a solution of C26 (from the previous step, <0.21 mmol) in dichloromethane was added a solution of hydrogen chloride in 1,4-dioxane (4 M, 1.61 mL, 6.45 mmol). The reaction mixture was stirred at room temperature overnight, whereupon it was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were dried over sodium sulfate. The solvent was removed in vacuo and the resulting solid was triturated with diethyl ether to afford the product as a tan solid. Yield: 56.5 mg, 0.16 mmol, 76% over two steps. LCMS m/z 349.2 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.56 (s, 1H), 7.68 (d, J=2.5 Hz, 1H), 7.26-7.28 (m, 1H, assumed; partially obscured by solvent peak), 7.23 (br dd, J=8, 2 Hz, 1H), 7.08 (d, J=8 Hz, 1H), 6.83 (d, J=2.5 Hz, 1H), 2.11 (s, 3H), 2.03 (s, 3H), 1.97 (s, 3H). Step 11. Isolation of (+)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (7) and (−)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]-4,6-dimethylpyridazin-3(2H)-one (8) Compound 6 was separated into its atropenantiomers using supercritical fluid chromatography (Column: Chiral Tech OJ-H, 5 μm; Eluent: 4:1 carbon dioxide/methanol). Example 7 (designated the (+)-atropenantiomer according to its observed rotation data) was the first-eluting isomer, followed by Example 8. Example 8 was designated the (−)-atropenantiomer according to its observed rotation data. 7: 1 H NMR (400 MHz, CDCl 3 ) δ 8.58 (s, 1H), 7.70 (d, J=2.4 Hz, 1H), 7.21-7.27 (m, 2H), 7.10 (d, J=8.2 Hz, 1H), 6.84 (d, J=2.4 Hz, 1H), 2.13 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H). 8: 1 H NMR (400 MHz, CDCl 3 ) δ 10.83 (brs, 1H), 8.58 (s, 1H), 7.70 (d, J=2.4 Hz, 1H), 7.21-7.26 (m, 2H), 7.10 (d, J=8.2 Hz, 1H), 6.84 (d, J=2.4 Hz, 1H), 2.13 (s, 3H), 2.02 (s, 3H), 1.98 (s, 3H). Example 9 6-[4-(Furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1,5-dimethylpyrimidine-2,4(1H, 3H)-dione (9) Step 1. Synthesis of 6-amino-1,5-dimethylpyrimidine-2,4(1H,3H)-dione, hydrochloride salt (C27) A solution of sodium methoxide in methanol (4.4 M, 27 mL, 119 mmol) was added to a solution of ethyl 2-cyanopropanoate (95%, 13.2 mL, 99.6 mmol) and 1-methylurea (98%, 8.26 g, 109 mmol) in methanol (75 mL), and the reaction mixture was heated at reflux for 18 hours, then cooled to room temperature. After removal of solvent in vacuo, the residue was repeatedly evaporated under reduced pressure with acetonitrile (3×50 mL), then partitioned between acetonitrile (100 mL) and water (100 mL). Aqueous 6 M hydrochloric acid was slowly added until the pH had reached approximately 2; the resulting mixture was stirred for 1 hour. The precipitate was collected via filtration and washed with tert-butyl methyl ether, affording the product as a white solid. Yield: 15.2 g, 79.3 mmol, 80%. LCMS m/z 156.1 [M+H] + . 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.38 (br s, 1H), 6.39 (s, 2H), 3.22 (s, 3H), 1.67 (s, 3H). Step 2. Synthesis of 6-bromo-1,5-dimethylpyrimidine-2,4(1H,3H)-dione (C28) A 1:1 mixture of acetonitrile and water (120 mL) was added to a mixture of C27 (9.50 g, 49.6 mmol), sodium nitrite (5.24 g, 76 mmol), and copper(II) bromide (22.4 g, 100 mmol) {Caution: bubbling and slight exotherm!}, and the reaction mixture was allowed to stir at room temperature for 66 hours. Addition of aqueous sulfuric acid (1 N, 200 mL) and ethyl acetate (100 mL) provided a precipitate, which was collected via filtration and washed with water and ethyl acetate to afford the product as a light yellow solid (7.70 g). The organic layer of the filtrate was concentrated to a smaller volume, during which additional precipitate formed; this was isolated via filtration and washed with 1:1 ethyl acetate/heptane to provide additional product (0.4 g). Total yield: 8.1 g, 37 mmol, 75%. GCMS m/z 218, 220 [M + ]. 1 H NMR (400 MHz, DMSO-d 6 ) δ 11.58 (br s, 1H), 3.45 (s, 3H), 1.93 (s, 3H). Step 3. Synthesis of 6-bromo-3-(3,4-dimethoxybenzyl)-1,5-dimethylpyrimidine-2,4(1H,3H)-dione (C29) 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU, 98%, 5.57 mL, 36.5 mmol) was added to a suspension of C28 (4.00 g, 18.3 mmol) and 4-(chloromethyl)-1,2-dimethoxybenzene (5.16 g, 27.6 mmol) in acetonitrile (80 mL), and the reaction mixture was heated at 60° C. for 18 hours. After removal of solvent in vacuo, the residue was purified via silica gel chromatography (Gradient: 25% to 50% ethyl acetate in heptane) to afford the product as a white solid. Yield: 5.70 g, 15.4 mmol, 84%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.08-7.12 (m, 2H), 6.80 (d, J=8.0 Hz, 1H), 5.07 (s, 2H), 3.88 (s, 3H), 3.85 (s, 3H), 3.65 (s, 3H), 2.14 (s, 3H). Step 4. Synthesis of 3-(3, 4-dimethoxybenzyl)-6-(4-hydroxyphenyl)-1,5-dimethylpyrimidine-2,4(1H, 3H)-dione (C30) To a solution of C29 (3.5 g, 9.5 mmol) in 1,4-dioxane (100 mL) were added 4-hydroxyphenyl boronic acid (2.7 g, 19 mmol), 1,1′-bis(diphenylphosphino)ferrocene palladium(II) chloride, dichloromethane complex (592 mg, 0.711 mmol), and aqueous potassium carbonate solution (3 M, 9 mL, 27 mmol). The reaction mixture was heated at 100° C. overnight, then cooled to room temperature, diluted with ethyl acetate and water, and filtered through diatomaceous earth to remove solids. The organic layer was washed sequentially with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, then dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel chromatography (Gradient: 25% to 50% ethyl acetate in heptane) to afford the product as a white solid. Yield: 3.4 g, 8.9 mmol, 94%. LCMS m/z 383.2 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 7.20 (m, 2H), 7.05 (m, 2H), 6.96 (m, 2H), 6.82 (d, J=8.0 Hz, 1H), 5.15 (s, 2H), 3.89 (s, 3H), 3.86 (s, 3H), 3.06 (s, 3H), 1.70 (s, 3H). Step 5. Synthesis of 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1,5-dimethylpyrimidine-2,4(1H,3H)-dione (9) The title compound was generated as part of a library using the following protocol: to a 2-dram vial were added C3 (0.13 mmol), C30 (38.2 mg, 0.1 mmol), cesium carbonate (98 mg, 0.3 mmol), di-tert-butyl[3,4,5,6-tetramethyl-2′,4′,6′-tri(propan-2-yl)biphenyl-2-yl]phosphane (10 mg, 20 μmol) and degassed 1,4-dioxane (1 mL). The reaction was degassed with nitrogen and shaken and heated at 110° C. for 20 hours. The reaction mixture was then partitioned between water (1.5 mL) and ethyl acetate (2.5 mL) and filtered through diatomaceous earth; the organic layer was eluted through a solid-phase extraction cartridge charged with sodium sulfate, and the filtrate was concentrated in vacuo. The residue was treated with methoxybenzene (0.1 mL) and trifluoroacetic acid (1.25 mL), and this reaction mixture was shaken and heated at 90° C. for 48 hours, whereupon it was concentrated. The residue (35 mg) was purified via reversed phase HPLC (Column: Waters XBridge C18, 5 μm; Mobile phase A: 0.03% ammonium hydroxide in water (v/v); Mobile phase B: 0.03% ammonium hydroxide in acetonitrile (v/v); Gradient: 5% to 100% B). Yield: 2.6 mg, 7.4 μmol, 7%. LCMS m/z 351.2 [M+H] + . 1 H NMR (600 MHz, DMSO-d 6 ) δ 8.58 (s, 1H), 8.18 (d, J=2.4 Hz, 1H), 7.51 (br AB quartet, J AB =8.7 Hz, Δν AB =11.1 Hz, 4H), 7.07 (d, J=2.4 Hz, 1H), 2.94 (s, 3H), 1.56 (s, 3H). Example 10 4,6-Dimethyl-5-[2-methyl-4-([1,2]thiazolo[4,5-c]pyridin-4-yloxy)phenyl]pyridazin-3(2H)-one (10) Step 1. Synthesis of 4-(tert-butylsulfanyl)-2-chloropyridine-3-carbaldehyde (C31) A mixture of 2,4-dichloropyridine-3-carbaldehyde (838 mg, 4.76 mmol), 2-methylpropane-2-thiol (429 mg, 4.76 mmol), and potassium carbonate (987 mg, 4.76 mmol) in N,N-dimethylformamide (10 mL) was heated at 50° C. for 3 hours. After the reaction mixture had been cooled to room temperature, it was diluted with water and extracted with dichloromethane (3×30 mL). The combined organic layers were washed with water (3×15 mL) and dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel chromatography (Gradient: 0% to 20% ethyl acetate in heptane) to afford the product as a yellow oil. Yield: 840 mg, 3.66 mmol, 77%. LCMS m/z 230.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 10.56 (s, 1H), 8.30 (d, J=5.5 Hz, 1H), 7.52 (d, J=5.5 Hz, 1H), 1.55 (s, 9H). Step 2. Synthesis of (E)-1-[4-(tert-butylsulfanyl)-2-chloropyridin-3-yl]-N-hydroxymethanimine (C32) To a stirred solution of C31 (840 mg, 3.66 mmol) in N,N-dimethylformamide (10 mL) at room temperature were added hydroxylamine hydrochloride (145 mg, 4.39 mmol) and sodium bicarbonate (1.84 g, 21.9 mmol). The reaction mixture was stirred at room temperature overnight, and then heated to 50° C. for 2 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate, washed with water and with saturated aqueous sodium chloride solution, and dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel chromatography (Gradient: 0% to 20% ethyl acetate in heptane) to afford the product as a white solid. Yield: 482 mg, 1.97 mmol, 54%. LCMS m/z 245.1 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.48 (s, 1H), 8.28 (d, J=5.5 Hz, 1H), 7.68 (d, J=5.5 Hz, 1H), 1.50 (s, 9H). Step 3. Synthesis of 1-[({(E)-[4-(tert-butylsulfanyl)-2-chloropyridin-3-yl]methylidene}amino)oxy]ethanone (C33) A mixture of C32 (250 mg, 1.02 mmol) and acetic anhydride (225 mg, 2.05 mmol) in pyridine (10 mL) was heated at reflux for 1 hour. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed with saturated aqueous potassium carbonate solution. The organic layer was dried over magnesium sulfate, filtered, and concentrated in vacuo; the residue was purified via chromatography on silica gel (Gradient: 0% to 20% ethyl acetate in heptane) to afford the product as a white solid. Yield: 199 mg, 0.69 mmol, 68%. LCMS m/z 284.9 [M−H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 8.70 (s, 1H), 8.27 (d, J=5.5 Hz, 1H), 7.48 (d, J=5.5 Hz, 1H), 2.30 (s, 3H), 1.49 (s, 3H). Step 4. Synthesis of 4-chloro[1,2]thiazolo[4,5-c]pyridine (C34) A solution of C33 (170 mg, 0.59 mmol) in dimethyl sulfoxide (5 mL) was heated at 100° C. for 5 hours, whereupon it was cooled to room temperature and diluted with dichloromethane. The mixture was washed sequentially with water and with saturated aqueous sodium chloride solution, then dried over magnesium sulfate. The solvent was removed in vacuo and the residue was purified by silica gel chromatography (Gradient: 0% to 20% ethyl acetate in heptane) to afford the product as a white solid. Yield: 55 mg, 0.32 mmol, 54%. LCMS m/z 171.0 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 9.11 (s, 1H), 8.36 (d, J=5.7 Hz, 1H), 7.83 (dd, J=5.7, 1 Hz, 1H). Step 5. Synthesis of 4,6-dimethyl-5-[2-methyl-4-([1,2]thiazolo[4,5-c]pyridin-4-yloxy)phenyl]-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C35) To a solution of C25 (122 mg, 0.39 mmol) in 1,4-dioxane (5 mL) were added C34 (55 mg, 0.32 mmol), cesium carbonate (316 mg, 0.97 mmol), palladium(II) acetate (7.4 mg, 33 μmol) and di-tert-butyl[3,4,5,6-tetramethyl-2′,4′,6′-tri(propan-2-yl)biphenyl-2-yl]phosphane (31 mg, 62 μmol). The reaction mixture was heated to 80° C. overnight, then cooled to room temperature and filtered through diatomaceous earth. The filter pad was rinsed with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was purified first by chromatography on silica gel (Gradient: 0% to 100% ethyl acetate in heptane, followed by elution with 20% methanol in dichloromethane) and then via reversed phase HPLC (Column: Phenomenex Gemini NX-C18, 5 μm; Mobile phase A: 0.1% ammonium hydroxide in water; Mobile phase B: 0.1% ammonium hydroxide in methanol; Gradient: 50% to 100% B) to afford the product as a white solid. Yield: 16 mg, 36 μmol, 11%. LCMS m/z 447.2 [M−H + ]. 1 H NMR (400 MHz, CDCl 3 ) δ 8.24 (d, J=5.5 Hz, 1H), 8.03 (d, J=5.5 Hz, 1H), 7.33 (d, J=5.5 Hz, 1H), 7.12 (m, 1H), 7.00 (m, 2H), 6.13 (m, 1H), 4.19 (m, 2H), 3.79 (m, 1H), 2.32 (m, 1H), 2.05 (s, 3H), 1.99 (s, 3H), 1.91 (s, 3H), 1.74 (m, 2H), 1.54 (m, 2H). Step 6. Synthesis of 4,6-dimethyl-5-[2-methyl-4-([1,2]thiazolo[4,5-c]pyridin-4-yloxy)phenyl]pyridazin-3(2H)-one (10) To a stirred solution of C35 (41 mg, 91 μmol) in dichloromethane (5 mL) was added a solution of hydrogen chloride in 1,4-dioxane (4 M, 0.68 mL, 2.7 mmol). The reaction mixture was stirred at room temperature for 3 hours, whereupon it was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were dried over sodium sulfate. The solvent was removed in vacuo and the residue was triturated with diethyl ether to afford the product as a white solid. Yield: 29 mg, 79 μmol, 87%. LCMS m/z 365.2 [M+H] + . 1 H NMR (400 MHz, CDCl 3 ) δ 9.19 (s, 1H), 8.10 (d, J=5.7 Hz, 1H), 7.60 (dd, J=5.8, 0.9 Hz, 1H), 7.26 (m, 2H), 7.24 (m, 1H), 7.09 (d, J=8.2 Hz, 1H), 2.12 (s, 3H), 2.02 (s, 3H), 1.98 (s, 3H). PREPARATIONS Preparations below describe preparation of P1 that can be used as starting materials for preparation of certain examples of compounds of the invention. Preparation P1 5-(4-Hydroxy-2-methylphenyl)-4-methyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (P1) Step 1. Synthesis of 4, 5-dichloro-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C36) A mixture of 4,5-dichloropyridazin-3-ol (42 g, 250 mmol), 3,4-dihydro-2H-pyran (168 g, 2.00 mol) and p-toluenesulfonic acid (8.8 g, 51 mmol) in tetrahydrofuran (2 L) was heated at reflux for 2 days. After cooling to room temperature, the reaction mixture was concentrated in vacuo and purified by silica gel chromatography (Gradient: 3% to 5% ethyl acetate in petroleum ether). The product was obtained as a white solid. Yield: 42 g, 170 mmol, 68%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (s, 1H), 6.01 (br d, J=11 Hz, 1H), 4.10-4.16 (m, 1H), 3.70-3.79 (m, 1H), 1.99-2.19 (m, 2H), 1.50-1.80 (m, 4H). Step 2. Synthesis of 4-chloro-5-methyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C37) and 5-chloro-4-methyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C38) To a mixture of C36 (40 g, 0.16 mol), methylboronic acid (9.6 g, 0.16 mol) and cesium carbonate (156 g, 479 mmol) in 1,4-dioxane (500 mL) and water (50 mL) was added [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (5 g, 7 mmol). The reaction mixture was stirred at 110° C. for 2 hours, whereupon it was cooled to room temperature and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 3% to 6% ethyl acetate in petroleum ether) afforded compound C37 as a pale yellow solid. Yield: 9.0 g, 39 mmol, 24%. LCMS m/z 250.8 [M+Na + ]. 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (s, 1H), 6.07 (dd, J=10.7, 2.1 Hz, 1H), 4.10-4.18 (m, 1H), 3.71-3.81 (m, 1H), 2.30 (s, 3H), 1.98-2.19 (m, 2H), 1.53-1.81 (m, 4H). Also obtained was C38, as a pale yellow solid. Yield: 9.3 g, 41 mmol, 26%. LCMS m/z 250.7 [M+Na + ]. 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (s, 1H), 6.02 (dd, J=10.7, 2.1 Hz, 1H), 4.10-4.17 (m, 1H), 3.71-3.79 (m, 1H), 2.27 (s, 3H), 1.99-2.22 (m, 2H), 1.51-1.79 (m, 4H). Step 3. Synthesis of 5-[4-(benzyloxy)-2-methylphenyl]-4-methyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (C39) A solution of C20 (7.30 g, 22.5 mmol), C38 (2.7 g, 12 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.3 g, 1.8 mmol) and cesium carbonate (7.7 g, 24 mmol) in 1,4-dioxane (100 mL) was heated at reflux for 7 hours. The reaction mixture was then filtered through a pad of diatomaceous earth, and the filtrate was concentrated in vacuo. Silica gel chromatography (Gradient: 10% to 50% ethyl acetate in petroleum ether) afforded the product as a brown gel, presumed to be a mixture of diastereomeric atropisomers from its 1 H NMR spectrum. Yield: 2.5 g, 6.4 mmol, 53%. 1 H NMR (400 MHz, CDCl 3 ), characteristic peaks: δ 7.66 (s, 1H), 7.35-7.49 (m, 5H), 6.96-7.03 (m, 1H), 6.94 (br d, J=2 Hz, 1H), 6.89 (dd, J=8.3, 2 Hz, 1H), 6.14-6.20 (m, 1H), 5.10 (s, 2H), 4.15-4.24 (m, 1H), 3.76-3.86 (m, 1H), 2.18-2.32 (m, 1H), 2.12 and 2.14 (2 s, total 3H), 2.00 (s, 3H), 1.71-1.86 (m, 3H). Step 4. Synthesis of 5-(4-hydroxy-2-methylphenyl)-4-methyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one (P1) A mixture of C39 (2.5 g, 6.4 mmol) and wet palladium on carbon (0.8 g) in methanol (80 mL) was stirred under 50 psi of hydrogen for 3 days, whereupon the reaction mixture was filtered through diatomaceous earth. The filtrate was concentrated in vacuo, and the residue was purified via silica gel chromatography (Gradient: 10% to 60% ethyl acetate in petroleum ether) to provide the product as a white solid, judged to be a mixture of diastereomeric atropisomers from its 1 H NMR spectrum. Yield: 1.6 g, 5.3 mmol, 83%. LCMS m/z 301 [M+H]+. 1 H NMR (400 MHz, CDCl 3 ), characteristic peaks: δ 7.64-7.68 (s, 1H), 6.90-6.97 (m, 1H), 6.73-6.82 (m, 2H), 6.14-6.19 (m, 1H), 4.14-4.23 (m, 1H), 3.76-3.85 (m, 1H), 2.17-2.31 (m, 1H), 2.09 and 2.11 (2 s, total 3H), 2.00 (s, 3H), 1.72-1.85 (m, 3H). Table 1 below lists some additional examples of compounds of invention (Examples 11-23) that were made using methods, starting materials or intermediates, and preparations described herein. TABLE 1 Examples 11-23 (including Method of Preparation, Non-Commercial starting materials, Structures and Physicochemical Data). Method of Preparation; 1 H NMR (600 MHz, DMSO-d 6 ) δ (ppm); Non- Mass spectrum, observed ion m/z commercial [M + H] + or HPLC retention time; Mass Example starting spectrum m/z [M + H] + (unless number materials Structure otherwise indicated) 11 Example 2; C5 1 H NMR (400 MHz, CD 3 OD) δ 8.90 (s, 1H), 8.36 (s, 1H), 7.89 (d, J = 5.8 Hz, 1H), 7.42 (d, J = 5.6 Hz, 1H), 7.27 (s, 1H), 7.19 (s, 2H), 2.71 (s, 6H), 2.05 (s, 3H); 332.1 12 Example 2 1 1 H NMR (400 MHz, CD 3 OD) δ 9.21 (s, 1H), 8.38 (s, 1H), 7.94 (d, J = 5.8 Hz, 1H), 7.45 (d, J = 4.0 Hz, 1H), 7.33 (m, 2H), 7.25 (d, J = 9.8 Hz, 1H), 2.47 (s, 3H), 2.15 (s, 3H); 343.0 13 Example 6 2 1 H NMR (400 MHz, CD 3 OD) δ 8.40 (s, 1H), 7.85 (d, J = 2.7 Hz, 1H), 7.36 (m, 2H), 7.26 (m, 2H), 7.33 (m, 2H), 6.86 (d, J = 2.5 Hz, 1H), 1.99 (s, 3H), 1.88 (s, 3H); 335.2 14 Example 6 3 ; P1 Retention time, 2.44 minutes; 335.0 15 Example 9 4 ; C30 8.19 (d, J = 6.1 Hz, 1H), 7.53 (d, J = 6.1 Hz, 1H), 7.49 (d, J = 8.6, 2H), 7.47 (d, J = 8.6 Hz, 1H), 2.94 (s, 3H), 2.71 (s, 3H), 1.58 (s, 3H); 365.0 16 Example 6; C25 8.19 (d, J = 6.1 Hz, 1H), 7.51 (d, J = 6.1 Hz, 1H), 7.32 (s, 1H), 7.26 (dd, J = 8.6, 2.2 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 2.69 (s, 3H), 2.49 (s, 3H), 2.04 (s, 3H), 1.88 (s, 3H); 363.1 17 Example 3; C17 8.20 (d, J = 6.1 Hz, 1H), 8.03 (s, 1H), 7.52 (d, J = 6.1 Hz, 1H), 7.39 (dd, J = 8.3, 2.1 Hz, 1H), 7.33 (d, J = 8.1 Hz, 1H), 3.08 (s, 3H), 2.69 (s, 3H), 2.10 (s, 3H), 1.93 (s, 3H); 363.1 18 Example 9 5 8.59 (s, 1H), 8.18 (d, J = 2.2 Hz, 1H), 7.52 (s, br, 4H), 7.05 (d, J = 2.2 Hz, 1H), 2.92 (s, 3H), 1.97 (q, J = 7.3 Hz, 2H), 0.86 (t, J = 7.3 Hz, 3H); 365.2 19 Example 9 6 8.57 (s, 1H), 8.17 (d, J = 2.6 Hz, 1H), 7.49 (m, br, 4H), 7.03 (d, J = 2.6 Hz, 1H), 3.61 (t, J = 6.1 Hz, 2H), 3.34 (t, J = 6.1 Hz, 2H) 3.09 (s, 3H), 1.51 (s, 3H); 395.2 20 Example 9 7 8.59 (s, 1H), 8.19 (d, J = 2.2 Hz, 1H), 7.53 (s, br, 4H), 7.05 (d, J = 2.2 Hz, 1H), 3.49 (q, J = 7.0 Hz, 2H), 1.52 (s, 3H), 0.98 (t, J = 7.0 Hz, 3H); 365.2 21 Example 9 8 8.57 (s, 1H), 8.17 (d, J = 2.6 Hz, 1H), 7.54 (dt, J = 9.6, 0.7 Hz, 2H), 7.45 (dt, J = 9.6, 0.7 Hz, 2H), 7.03 (d, J = 2.6 Hz, 1H), 2.6 (m, 1H), 1.60 (s, 3H), 0.57 (m, 2H), 0.51 (m, 2H); 377.2 22 Example 9 9 8.58 (s, 1H), 8.18 (d, J = 2.2 Hz, 1H), 7.57 (d, J = 8.8 Hz, 2H), 7.46 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 2.2 Hz, 1H), 2.54 (q, J = 7.3 Hz, 2H), 2.03 (t, J = 7.3 Hz, 3H); 391.2 23 Example 9 10 8.60 (s, 1H), 8.19 (d, J = 2.2 Hz, 1H), 7.55 (d, J = 8.8 Hz, 2H), 7.53 (d, J = 8.8 Hz, 2H), 7.02 (d, J = 2.2 Hz, 1H), 3.45 (q, J = 7.0 Hz, 2H), 1.93 (q, J = 7.5 Hz, 2H), 0.99 (t, J = 7.0 Hz, 3H), 0.85 (t, J = 7.5 Hz, 3H); 379.2 1. The requisite intermediate 5-(4-hydroxy-2-methylphenyl)-6-methylpyrimidine-4-carbonitrile was prepared following a procedure similar to that described for the preparation of C5 from 5-bromo-6-methylpyrimidine-4-carbonitrile. The final product was obtained following the coupling and deprotection conditions described in the preparation of Example 2. 2. The requisite 5-(4-hydroxyphenyl)-4,6-dimethyl-2-(tetrahydro-2H-pyran-2-yl)pyridazin-3(2H)-one was prepared from 1-(benzyloxy)-4-bromobenzene following the procedure described for preparation of C25. 3. Analytical HPLC conditions. Column: Waters Atlantis dC18, 4.6 x 50 mm, 5 μm; Mobile phase A: 0.05% trifluoroacetic acid in water (v/v); Mobile phase B: 0.05% trifluoroacetic acid in acetonitrile (v/v); Gradient: 5.0% to 95.0% B, linear, over 4.0 minutes; Flow rate: 2 mL/minute. 4. The final coupling step was carried out using cesium carbonate in dimethyl sulfoxide at 80° C. 5. The requisite 3-(3,4-dimethoxybenzyl)-5-ethyl-6-(4-hydroxyphenyl)-1-methylpyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanobutanoate and 1-methylurea. 6. The requisite 3-(3,4-dimethoxybenzyl)-6-(4-hydroxyphenyl)-1-(2-methoxyethyl)-5-methylpyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanopropanoate and 1-(2-methoxyethyl)urea. 7. The requisite 3-(3,4-dimethoxybenzyl)-1-ethyl-6-(4-hydroxyphenyl)-5-methylpyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanopropanoate and 1-ethylurea. 8. The requisite 1-cyclopropyl-3-(3,4-dimethoxybenzyl)-6-(4-hydroxyphenyl)-5-methylpyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanopropanoate and 1-cyclopropylurea. 9. The requisite 1-cyclopropyl-3-(3,4-dimethoxybenzyl)-5-ethyl-6-(4-hydroxyphenyl)pyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanobutanoate and 1-cyclopropylurea. 10. The requisite 3-(3,4-dimethoxybenzyl)-1,5-diethyl-6-(4-hydroxyphenyl)pyrimidine-2,4(1H,3H)-dione was prepared following a procedure similar to that described for the preparation of C30, starting from ethyl 2-cyanobutanoate and 1-ethylurea. Example AA Human D1 Receptor Binding Assay and Data The affinity of the compounds described herein was determined by competition binding assays similar to those described in Ryman-Rasmussen et al., “Differential activation of adenylate cyclase and receptor internalization by novel dopamine D1 receptor agonists”, Molecular Pharmacology 68(4):1039-1048 (2005). This radioligand binding assay used [ 3 H]-SCH23390, a radiolabeled D1 ligand, to evaluate the ability of a test compound to compete with the radioligand when binding to a D1 receptor. D1 binding assays were performed using over-expressing LTK human cell lines. To determine basic assay parameters, ligand concentrations were determined from saturation binding studies where the K d for [ 3 H]-SCH23390 was found to be 1.3 nM. From tissue concentration curve studies, the optimal amount of tissue was determined to be 1.75 mg/mL per 96 well plate using 0.5 nM of [ 3 H]-SCH23390. These ligand and tissue concentrations were used in time course studies to determine linearity and equilibrium conditions for binding. Binding was at equilibrium with the specified amount of tissue in 30 minutes at 37° C. From these parameters, K i values were determined by homogenizing the specified amount of tissue for each species in 50 mM Tris (pH 7.4 at 4° C.) containing 2.0 mM MgCl 2 using a Polytron and spun in a centrifuge at 40,000×g for 10 minutes. The pellet was resuspended in assay buffer [50 mM Tris (pH 7.4@ RT) containing 4 mM MgSO 4 and 0.5 mM EDTA]. Incubations were initiated by the addition of 200 μL of tissue to 96-well plates containing test drugs (2.5 μL) and 0.5 nM [ 3 H]-SCH23390 (50 μL) in a final volume of 250 μL. Non-specific binding was determined by radioligand binding in the presence of a saturating concentration of (+)-Butaclamol (10 μM), a D1 antagonist. After a 30 minute incubation period at 37° C., assay samples were rapidly filtered through Unifilter-96 GF/B PEI-coated filter plates and rinsed with 50 mM Tris buffer (pH 7.4 at 4° C.). Membrane bound [ 3 H]-SCH23390 levels were determined by liquid scintillation counting of the filterplates in Ecolume. The IC 50 value (concentration at which 50% inhibition of specific binding occurs) was calculated by linear regression of the concentration-response data in Microsoft Excel. K i values were calculated according to the Cheng-Prusoff equation: K i = IC 50 1 + ( [ L ] / K d ) where [L]=concentration of free radioligand and K d =dissociation constant of radioligand for D1 receptor (1.3 nM for [ 3 H]-SCH23390). Example BB D1 cAMP HTRF Assay and Data The D1 cAMP (Cyclic Adenosine Monophosphate) HTRF (Homogeneous Time-Resolved Fluorescence) Assay used and described herein is a competitive immunoassay between native cAMP produced by cells and cAMP labeled with XL-665. This assay was used to determine the ability of a test compound to agonize (including partially agonize) D1. A Mab anti-cAMP labeled Cryptate visualizes the tracer. The maximum signal is achieved if the samples do not contain free cAMP due to the proximity of donor (Eu-cryptate) and acceptor (XL665) entities. The signal, therefore, is inversely proportional to the concentration of cAMP in the sample. A time-resolved and ratiometric measurement (em 665 nm/em 620 nm) minimizes the interference with medium. cAMP HTRF assays are commercially available, for example, from Cisbio Bioassays, IBA group. Materials and Methods Materials: The cAMP Dynamic kit was obtained from Cisbio International (Cisbio 62AM4PEJ). Multidrop Combi (Thermo Scientific) was used for assay additions. An EnVision (PerkinElmer) reader was used to read HTRF. Cell Cuture: A HEK293T/hD1#1 stable cell line was constructed internally (Pfizer Ann Arbor). The cells were grown as adherent cells in NuncT 500 flasks in high glucose DMEM (Invitrogen 11995-065), 10% fetal bovine serum dialyzed (Invitrogen 26400-044), 1×MEM NEAA (Invitrogen 1140, 25 mM HEPES (Invitrogen 15630), 1×Pen/Strep (Invitrogen 15070-063) and 500 μg/mL Genenticin (Invitrogen 10131-035) at 37° C. and 5% CO 2 . At 72 or 96 hours post-growth, cells were rinsed with DPBS, and 0.25% Trypsin-EDTA was added to dislodge the cells. Media was then added and cells were centrifuged and media removed. The cell pellets were re-suspended in Cell Culture Freezing Medium (Invitrogen 12648-056) at a density of 4e7 cells/mL. One mL aliquots of the cells were made in Cryo-vials and frozen at −80° C. for future use in the D1 HTRF assay. D1 cAMP HTRF Assay Procedure: Frozen cells were quickly thawed, re-suspended in 50 mL warm media and allowed to sit for 5 min prior to centrifugation (1000 rpm) at room temperature. Media was removed and cell pellet was re-suspended in PBS/0.5 μM IBMX generating 2e5 cells/mL. Using a Multidrop Combi, 5 μL cells/well was added to the assay plate (Greiner 784085), which already contained 5 μL of a test compound. Compound controls [5 μM dopamine (final) and 0.5% DMSO (final)] were also included on every plate for data analysis. Cells and compounds were incubated at room temperature for 30 min. Working solutions of cAMP-D2 and anti-cAMP-cryptate were prepared according to Cisbio instructions. Using Multidrop, 5 μL cAMP-D2 working solution was added to the assay plate containing the test compound and cells. Using Multidrop, 5 μL anti-cAMP-cryptate working solutions was added to assay plate containing test compound, cells and cAMP-D2. The assay plate was incubated for 1 hour at room temperature. The assay plate was read on an EnVision plate reader using Cisbio recommended settings. A cAMP standard curve was generated using cAMP stock solution provided in the Cisbio kit. Data Analysis: Data analysis was done using computer software. Percent effects were calculated from the compound controls. Ratio EC 50 was determined using the raw ratio data from the EnVision reader. The cAMP standard curve was used in an analysis program to determine cAMP concentrations from raw ratio data. cAMP EC 50 was determined using the calculated cAMP data. TABLE 2 Biological Data and Compound Name for Examples 1-23. Human D1 Receptor Binding, K i (nM); Geometric mean Example of 2-4 determinations number (unless otherwise indicated) IUPAC Name 1 166 a 4-[4-(4,6-dimethylpyrimidin-5-yl)-3- methylphenoxy]furo[2,3-d]pyrimidine 2 374 a 4-[3-methyl-4-(6-methylimidazo[1,2-a]pyrazin-5- yl)phenoxy]-1H-imidazo[4,5-c]pyridine 3 196 a 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]- 1,5-dimethylpyrazin-2(1H)-one 4 127   (−)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2- methylphenyl]-1,5-dimethylpyrazin-2(1H)-one 5 400 a (+)-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2- methylphenyl]-1,5-dimethylpyrazin-2(1H)-one 6   44.7 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]- 4,6-dimethylpyridazin-3(2H)-one 7   30.7 (+)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2- methylphenyl]-4,6-dimethylpyridazin-3(2H)-one 8   40.2 (−)-5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2- methylphenyl]-4,6-dimethylpyridazin-3(2H)-one 9 142 a 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1,5- dimethylpyrimidine-2,4(1H,3H)-dione 10   32.7 4,6-dimethyl-5-[2-methyl-4-([1,2]thiazolo[4,5- c]pyridin-4-yloxy)phenyl]pyridazin-3(2H)-one 11 912 a 4-[4-(4,6-dimethylpyrimidin-5-yl)-3-methylphenoxy]- 1H-imidazo[4,5-c]pyridine 12 367   5-[4-(1H-imidazo[4,5-c]pyridin-4-yloxy)-2- methylphenyl]-6-methylpyrimidine-4-carbonitrile 13   70.3 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-4,6- dimethylpyridazin-3(2H)-one 14 372 a 5-[4-(furo[2,3-d]pyrimidin-4-yloxy)-2-methylphenyl]- 4-methylpyridazin-3(2H)-one 15 280 a 1,5-dimethyl-6-{4-[(3-methyl[1,2]oxazolo[4,5- c]pyridin-4-yl)oxy]phenyl}pyrimidine-2,4(1H,3H)- dione 16 326 a 4,6-dimethyl-5-{2-methyl-4-[(3- methyl[1,2]oxazolo[4,5-c]pyridin-4- yl)oxy]phenyl}pyridazin-3(2H)-one, trifluoroacetic acid salt 17 1730 a   1,5-dimethyl-6-{2-methyl-4-[(3- methyl[1,2]oxazolo[4,5-c]pyridin-4- yl)oxy]phenyl}pyrazin-2(1H)-one, trifluoroacetic acid salt 18 274 a 5-ethyl-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1- methylpyrimidine-2,4(1H,3H)-dione 19 900 a 6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-1-(2- methoxyethyl)-5-methylpyrimidine-2,4(1H,3H)-dione 20 179 a 1-ethyl-6-[4-(furo[2,3-d]pyrimidin-4-yloxy)phenyl]-5- methylpyrimidine-2,4(1H,3H)-dione 21 122 a 1-cyclopropyl-6-[4-(furo[2,3-d]pyrimidin-4- yloxy)phenyl]-5-methylpyrimidine-2,4(1H,3H)-dione 22 142 a 1-cyclopropyl-5-ethyl-6-[4-(furo[2,3-d]pyrimidin-4- yloxy)phenyl]pyrimidine-2,4(1H,3H)-dione 23 309 a 1,5-diethyl-6-[4-(furo[2,3-d]pyrimidin-4- yloxy)phenyl]pyrimidine-2,4(1H,3H)-dione a K i value is from a single determination Various modifications of the invention, in addition to those described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appendant claims. Each reference (including all patents, patent applications, journal articles, books, and any other publications) cited in the present application is hereby incorporated by reference in its entirety.
The present invention provides, in part, compounds of Formula (I) and pharmaceutically acceptable salts thereof; processes for the preparation of; intermediates used in the preparation of; and compositions containing such compounds or salts, and their uses for treating D1-mediated (or D1-associated) disorders including, e.g., schizophrenia (e.g., its cognitive and negative symptoms), schizotypal personality disorder, cognitive impairment (e.g., cognitive impairment associated with schizophrenia, AD, PD, or pharmacotherapy therapy), ADHD, Parkinson's disease, anxiety, and depression.
2
FIELD OF THE INVENTION [0001] The present invention relates to a device for providing instant cooling, particularly for treating parts of the human body or items in general. More particularly, the invention relates to a device which is adapted to generate cold or heat instantly, so as to reduce or increase the temperature of parts of the human body for therapeutic purposes or to reduce or increase the temperature of items, such as helmets or bottle-carrying baskets. BACKGROUND OF THE INVENTION [0002] As is known, for example after a specific surgical procedure, it is necessary to keep the affected part for a period of time at a temperature which is lower than the rest of the body in order to avoid the onset of acute inflammatory conditions. For this purpose, special plastic containers are normally used which contain chemical components which, when mixed together at the time of use, react and cause a drop in temperature. Such containers, placed in contact with the affected part, cool it. [0003] Although these containers are widely used, their drawback is the fact that they have a preset duration, and once the chemical reaction has ended they remain inert, no longer generating cold, and in any case they do not offer temperature control. Substantially, this means that the containers go from being extremely cold when the chemical reaction is triggered, with discomfort for the person who uses them, and then gradually decrease their efficiency and become substantially useless. [0004] Moreover, the entire surface of the containers reaches a low temperature, and this causes the moisture that is present in the environment to tend to condense on the containers, generating a copious production of water which is an additional discomfort for the person who uses such containers. SUMMARY OF THE INVENTION [0005] The aim of the present invention is to provide a device for providing instant cooling, particularly for application to body parts or items, which allows to lower the temperature of the body part or item when it is placed in contact with such part or item. [0006] Within this aim, an object of the present invention is to provide a device for providing instant cooling which can be used at any time and whose duration is not limited by the duration of a chemical reaction which triggers cooling. [0007] Another object of the present invention is to provide a device for providing instant cooling which can be carried conveniently in one of the user's pockets and can be applied in each instance to the body part to be treated. [0008] Still another object of the present invention is to provide a device for providing instant cooling which is capable of maintaining a temperature which is always constant over time. [0009] This aim and these and other objects, which will become better apparent hereinafter, are achieved by a device for providing instant cooling, particularly for treating parts of the human body or items in general, characterized in that it comprises diffuser means which are adapted to be charged with a gas, the diffuser means being provided with a plurality of holes for releasing the gas, the diffuser means being accommodated in a container which contains a thermally insulating material which is adapted to absorb the low temperature generated by the gas, the container being sealed around the diffuser means. BRIEF DESCRIPTION OF THE DRAWINGS [0010] Further characteristics and advantages of the invention will become better apparent from the description of a preferred but not exclusive embodiment of the device according to the invention, illustrated by way of non-limiting example in the accompanying drawings, wherein: [0011] FIG. 1 is an exploded perspective view of the device according to the present invention; [0012] FIG. 2 is a perspective view of the propellant bottle to be used in combination with the device according to the present invention; [0013] FIG. 3 is a schematic view of the device according to the invention when used as a bottle-carrying basket. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0014] With reference to the figures, the device according to the invention, generally designated by the reference numeral 1 , comprises means for distributing a gas, which are constituted conveniently by a diffuser 2 , which is made for example of sheet metal and is adapted to contain a gas which allows cooling. [0015] Conveniently, the diffuser 2 has, at its face designed to be gripped by the user's hand, a layer 3 of thermally insulating material so as to eliminate the discomfort that the user may experience when holding an extremely cold body. [0016] The diffuser 2 has, at the surface that lies opposite the one on which the layer 3 of material is provided, a plurality is of holes 4 which are adapted to allow the escape of the gas introduced in the diffuser 2 . [0017] Conveniently, the diffuser 2 is provided with means adapted to allow the introduction of the gas in the diffuser, provided for example by a nozzle 5 which allows to connect the diffuser 2 to a bottle 6 of gas, which when needed is connected to the nozzle 5 in order to inject gas into the diffuser 2 , and therefore allows the escape of the gas through the holes 4 . [0018] Conveniently, the diffuser 2 is accommodated within a containment pouch or container 8 , which contains a thermally insulating material, designated by the reference numeral 9 , which is constituted for example by soapstone powder with a suitable particle size, which has the task of absorbing the low temperature generated by the expanding gas and of retaining it as long as possible as a function of the amount of soapstone powder and of the amount of gas. [0019] The pouch 8 is sealed around the diffuser 2 , with only the nozzle 5 protruding from the pouch 8 , in order to allow the connection of the bottle 6 of propellant. [0020] Operation of the device according to the present invention is as follows: [0021] If it is necessary to have instant cold, the user connects the bottle 6 of propellant to the nozzle 5 of the diffuser 2 , which is accommodated within the pouch 8 , and the gas immediately begins to expand from the diffuser 2 through the holes 4 into the pouch 8 , and the soapstone powder absorbs the low temperature that is thus generated. [0022] The soapstone powder is designed to maintain as long as possible the selected low temperature, which can also be a function of the amount of gas injected into the diffuser 2 . Therefore, depending on the application, it is possible to give the user an indication as to how much gas he will have to introduce in the diffuser 2 in order to obtain a given temperature. [0023] The device according to the invention is perfectly reusable, since it is only necessary optionally to replace the bottle 6 of propellant in order to have a fresh fill of gas. [0024] The device according to the invention is particularly compact in its dimensions, can be carried easily and can be applied at any time to any part of the body, or to any item, without the generated cold temperature undergoing rapid decay over time and most of all without the device, once in contact with the environment, forming condensation and generating a copious production of water, as occurs with known types of devices. [0025] Conveniently, the diffuser 2 is made of very thin sheet metal, so as to allow it to be highly flexible, indeed to allow the user to adapt the diffuser 2 , accommodated in the pouch 8 , in the best possible manner to the affected body part. [0026] The device according to the invention, with the same structure described above, can also be used for applications which are different from the one proposed above. [0027] In particular, the device can be provided with an outer container or pouch 8 shaped like a basket and therefore can act as a bottle-carrying basket, so as to allow to preserve the bottles at a given temperature. [0028] In this case, the container can be made of plexiglass or other material, with the layer 3 of thermally insulating material arranged internally to the container. The diffuser means 2 are then arranged, with the thermally insulating means 9 inside the container 8 , leaving a free space at the center for accommodating a bottle-container 10 . [0029] Another possible application of the device according to the invention provides for its integration within a protective helmet, such as a motorcyclist's helmet and the like. In this case, the purpose would be to keep at a controlled temperature the head of the person who wears the helmet, preventing, especially in the summer months, the heat within the helmet from becoming excessive. [0030] Further applications can provide for use for example in rucksacks, picnic bags and the like. [0031] The device thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the appended claims; all the details may further be replaced with other technically equivalent elements. [0032] In practice, the materials used, as well as the contingent shapes and dimensions, may be any according to requirements and to the state of the art. [0033] The disclosures in Italian Patent Application no. MI2006A002278, from which this application claims priority, are incorporated herein by reference.
A device for providing instant cooling, particularly for treating parts of the human body or items in general, comprising a diffuser which is adapted to be charged with a gas, the diffuser being provided with a plurality of holes for releasing the gas, the diffuser being accommodated in a container which contains a thermally insulating material which is adapted to absorb the low temperature generated by the gas, the container being sealed around the diffuser.
5
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 12/271,293 filed Nov. 14, 2008, now U.S. Pat. No. 7,608,588, which is a continuation of U.S. patent application Ser. No. 11/549,391 filed Oct. 13, 2006, now U.S. Pat. No. 7,495,076, and claims the benefit of U.S. provisional Patent Application Ser. No. 60/596,695 filed Oct. 13, 2005, the entireties of which are incorporated herein by reference. FIELD OF THE INVENTION The present invention relates generally to dietary supplements, in particular to mineral collagen chelate compounds, compositions containing such compounds, methods for making such compounds and methods of administering same. BACKGROUND OF THE INVENTION Collagen has been available in the United States since about 1986 as a food supplement. Collagen I/III can be extracted from calf skin and hydrolyzed for use in nutritional products. U.S. Pat. No. 4,804,745 (Koepff et al.) discloses agents containing collagen peptides produced by enzymatic hydrolysis for the treatment of degenerative joint diseases. These peptides can be obtained from animal skin, animal bones and other connective tissue with average molecular weights of 30-45 kilo-Daltons. U.S. Pat. No. 6,025,327 (Alkayali) and U.S. Pat. No. 6,838,440 (Stiles) disclose therapeutic compositions and method for the protection, treatment and repair of joint cartilage in mammals, comprising hydrolyzed collagen type II between 15 KD to 50 KD average molecular weight obtained from chicken sternal cartilage. In addition, collagen preparations from other animals, such as from donkey skin as in the Chinese traditional Medicine “e-jiao”, has also been used for hundreds of years as a skin health/beauty product. Minerals perform many different functions in the body such as the formation of bone and cartilage, maintenance of fluid and acid/base balance, transportation of oxygen in the blood, normal functioning of muscles and nerves, and production of hormones. Minerals work with vitamins, enzymes, and other minerals in the body to produce their effects. Minerals can be grouped into macro and micro categories. Macro-minerals are needed in greater amounts in the diet, and are found in larger amounts in the body than micro-minerals. Macro-minerals include Calcium (Ca), Phosphorus (P), Magnesium (Mg), Potassium (K), Sodium (Na) and Chloride (Cl), while micro-minerals include Copper (Cu), Iodine (I), Iron (Fe), Manganese (Mn), Selenium (Se), Silicon, and Zinc (Zn). Minerals such as calcium and magnesium are essential for bone and joint health. Minerals such as zinc are necessary for skin health. Iron and copper are important elements for the function of hemoglobin. The proper balance of minerals in the mammalian body is extremely important and related to the amount of each mineral in the diet, the ability of the animal to absorb the minerals from the intestine, and any disease conditions which could cause excess loss or retaining of various minerals. A high quality mineral supplement which contains the proper balance of minerals can be highly beneficial. However, if supplementation is attempted with minerals of unknown or unreliable bioavailability, it can create imbalances and possibly disrupt nutritional health. Too much or too little of one mineral can affect the action of others. Therefore, it is vital that if supplementation is being practiced that it be carried out using supplements the bioavailability of which are highly predictable and consistent. It has been shown that minerals can interact with food to form precipitates, thus preventing the mineral from being absorbed properly in the small intestine. Soy protein mineral chelate and rice protein mineral chelate products have been available as more bioavailable organic mineral supplements. Mineral proteinate protects the mineral from unwanted chemical reactions in the gastrointestinal tract, delivering more mineral for optimum absorption in small intestine. Wedekind et al., J. Anim. Sci. 70:178 (1992). According to the Association of American Feed Control Officials (AAFCO) definition, mineral proteinate is the product resulting from the chelation of a soluble salt with amino acids and/or partially hydrolyzed protein. However, some scientific reports that addressed the bioavailability of mineral proteinate supported that mineral proteinate products were superior to mineral supplementation alone, while some indicated that no advantage was provided. Brown T. F. and Zeringue L. K. 1994 J Dairy Sci. 77:181-189. SUMMARY OF THE INVENTION A need exists for collagen mineral chelates which have maximum and consistent bioavailability. While not being bound to any single theory, the inventors believe at least one reason for the disparity in the tested bioavailability of mineral proteinate is the fact that the tested products, which have similar names (e.g. “metal proteinate”) are actually produced by different processes that can result in variable concentrations of minerals and variable sizes of peptides between products. The present inventors have found that surprisingly, collagen fragments can be sized to provide optimum bioavailability of minerals in collagen mineral chelate compositions. In at least one aspect, the present invention relates to preparation of collagen fragments of optimum size for binding minerals in mineral collagen peptide chelated products that can be delivered into organisms for different nutritional and medical purposes. More specifically, this invention relates to compositions including selected mineral cations bound with optimally-sized collagen or hydrolyzed collagen ligands. Depending on the minerals incorporated, these products support bone/joint health, skin/beauty health in animals and humans. Mineral collagen peptide chelate compounds in accordance with the present invention are useful in producing dietary supplements for supporting joint and bone health. Compositions containing the compounds increase bioavailability of the minerals and stimulate cartilage cell secretion to support healthy bone and joint, and also support skin health/beauty. Mineral collagen peptide chelate compounds in accordance with the present invention can be included in foods and beverages, food additives, animal feeds and feed additives as well as compositions including pharmaceutically acceptable carriers. It is therefore an object of the present invention to prepare the mineral proteinates by ensuring that the peptide ligands that bind to the mineral have the optimum size for binding the mineral in addition to maximizing its bioavailability. Collagen from any source can be used as starting material to produce collagen peptides of optimum size with different minerals for joint/bone health (such as Ca++, Mg++, Cu++, etc) and skin health/beauty (such as Iron, Cu++, Zn++, Mg++, etc). BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graphical representation of Protease K-digested collagen peptides according to the present invention. DETAILED DESCRIPTION OF THE INVENTION In the following description, for purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one having ordinary skill in the art that the invention may be practiced without these specific details. In some instances, well-known features may be omitted or simplified so as not to obscure the present invention. Furthermore, reference in the specification to phrases such as “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of phrases such as “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment. Collagen fragments of optimum size are provided for binding minerals in mineral collagen chelates that can be delivered into organisms for different nutritional and medical purposes. As used herein “mineral collagen chelate” describes an association of a metal ion having a valence of two or more to form a structure wherein the positive electrical charges of the metal ion are neutralized by the electrons available through collagen/hydrolyzed collagen. The binding represents physical associations including ionic, covalent, coordinate covalent bonding, or a combination thereof. These compositions are absorbed as a complex or digested into small collagen peptides and minerals released at the site of absorption into biological tissues and, because of either the specific collagen selected or the specific bound metals, migrate to specific tissue target sites where the complex is utilized as is or is dissociated into mineral cations and digested collagens or peptides. Collagen fragments in accordance with the present invention may be prepared by hydrolyzation. Hydrolyzation of protein is the process of breaking down the ester bond (—O—C═O) or amine (—N—C═O) bond by reaction with H2O. Hydrolyzation can be used to break down protein to smaller peptides through acid (such as HCl), alkaline (such as NaOH) and enzymatic hydrolysis. Enzymes useful in embodiments employing enzyme hydrolyzation preferably include but are not limited to single enzymes or mixture of enzymes that can digest collagens and other components in tissue, such as, but not limited to collagenase, papain, pepsin, Bromelain, trypsin, bacterial protease, fungal protease, pancreatin and the like. Any available collagen can be used in the present invention. Animal sources of tissue include but are not limited to chicken, porcine, bovine, fish and the like. Minerals include one or more members selected from the group including, but not limited to calcium, magnesium, boron, zinc, copper, manganese, iron, silica, and sulfur. Collagen fragments in accordance with the present invention surprisingly exhibit enhanced mineral binding which increases bioavailability of the minerals. Collagen fragments prepared in accordance with the present invention are employed to form chelates with any mineral to produce mineral collagen chelate compounds with enhanced bioavailability. When administered, the compounds stimulate cartilage cell secretion to support bone, joint and skin health, depending on the mineral incorporated in the compound. In one embodiment compositions including mineral collagen chelate compounds are provided in the form of dietary supplements for supporting joint and bone health as well as skin health. Mineral collagen chelate compounds in accordance with the present invention can be included in foods and beverages, food additives, animal feeds and feed additives as well as compositions including pharmaceutically acceptable carriers. In one embodiment methods for preparing mineral collagen chelate compounds are provided in which collagen fragments of a selected size are combined with a selected mineral to form a mineral collagen chelate. In one embodiment collagen is hydrolyzed, such as by digestion with a selected enzyme for a selected time period, to generate collagen fragments of a desired size and combined with a mineral. In one embodiment collagen source materials such as skin, cartilage from animals and the like are digested using enzymes to collagen peptides with average molecular weight ranging from 0.2 KD to 50 KD, preferably 0.5 KD-2 KD, most preferably about 1-2 KD. To the digested mixture, soluble mineral sources are added and the pH adjusted to form a precipitate. In another embodiment a method is disclosed of determining the optimum collagen fragment length for binding to a particular mineral. The optimum length is determined by the amount or percentage of mineral that can be bound to the collagen fragment. EXPERIMENTS Experiment 1 Bovine hydrolyzed Collagen I/III powder with an average molecular weight of about 4 KD (obtained from AIDP, Inc. of City of Industry, Calif.), was made into a 500 mg/l solution in water and subjected to enzymatic treatment with Collagenase (catalogue # c5138 from Sigma, St. Louis, USA) at 1 mg/ml final concentration at 25° C. water bath with occasional mixing for various amounts of time to render different sized fragments as follows: Sample 1: Collagen I/III untreated Sample 2: Collagen I/III Collagenase digestion for 15 minutes Sample 3: Collagen I/III Collagenase digestion for 30 minutes Sample 4: Collagen I/III Collagenase digestion for 60 minutes Sample 5: Collagen I/III Collagenase digestion for 2 hours Sample 6: Collagen I/III Collagenase digestion for 24 hours At the end of the treatment, samples were boiled for 5 minutes to stop the enzyme action and cooled to 22° C. in water bath. 100 ml of the digested samples were added to a beaker, mixed constantly with 5 mM CaCl 2 (final concentration) for 5 minutes, to which was then added 20 mM (final concentration) sodium phosphate buffer (ph 7.8) and stirred at room temperature for 30 minutes. pH was maintained at 7.8 by adjusting with NaOH as well as HCl, using a pH meter during the stirring process. At the end of 30 minutes, insoluble calcium phosphate precipitates were removed by filtering through a 0.45 uM membrane and the calcium content in the soluble mineral collagen chelate were analyzed using ICP method. Results were as follows: Soluble Ca (Calcium bound to collagen) Sample # (mg/l) Sample 1 1.74 Sample 2: 29.87 Sample 3: 72.56 Sample 4: 3.54 Sample 5: 5.26 Sample 6: 4.51 It is clear that binding of calcium to collagen depends on the size of collagen fragment, and the maximum amount of binding achieved at 30 minutes of digestion time with Collagenase, which is about 42 times better than the commercially available collagen I/III untreated. Since hydrolyzed collagen concentration was at 500 mg/l and maximum binding was achieved at 72.56 mg/l, the maximum calcium binding by digested collagen was 72.56 mg/500 mg=14.5% in this experiment. Experiment 2 The same procedures as experiment 1 were followed except that the enzyme Collagenase was replaced with Protease K from Sigma (Catalogue # p2308) at 100 ug/ml final concentration. Samples were treated at 25° C. as follows: Sample 1: Collagen I/III untreated Sample 2: Collagen I/III protease K digestion for 15 minutes Sample 3: Collagen I/III protease K digestion for 30 minutes Sample 4: Collagen I/III protease K digestion for 60 minutes Sample 5: Collagen I/III protease K digestion for 2 hours Sample 6: Collagen I/III protease K digestion for 6 hours Sample 7: Collagen I/III protease K digestion for 24 hours Calcium binding assay were carried out as in experiment 1. Results were as follows: Soluble Ca (Calcium bound to peptides) Sample # (mg/l) Sample 1 1.74 Sample 2. 5.045 Sample 3. 11.19 Sample 4: 50.96 Sample 5: 89.07 Sample 6: 34.94 Sample 7: 6.284 Based on the results and as further shown in FIG. 1 , maximum binding of calcium occurred at about 2 hours of Protease K digestion, which resulted in calcium binding of 89.07 mg/l. Since the collagen concentration was 500 mg/l, the maximum calcium binding to collagen was 89.07 mg/500 mg=17.8% calcium binding in this experiment. To examine the size of the peptide digested with the optimum condition, a MS-HPLC assay for Sample 5 was performed, showing an estimated average molecular weight of 1.629 KD. Collagen that is prepared in accordance with the present invention releases more epitopes for further mineral binding, and is clearly vastly superior to commercially available collagen in binding minerals. In the case of Experiment 1, about 42 fold more calcium is bound with optimum-size collagen fragments than untreated collagen. In the case of Experiment 2, 51 fold more calcium is bound with optimum-size collagen fragments. As will be apparent to one having ordinary skill in the art, these experimental conditions can be modified to produce mineral collagen chelate compounds in accordance with the present invention in commercial production quantities, by working out the optimum digestion condition for generating collagen fragments with size ranges preferentially 0.5 KD-2 KD, more specifically about 1-2 KD. EXAMPLES Prophetic Example 1 Commercially available collagen I/III from bovine skin is placed in a large tank with water and protease enzymes including, but not limited to Pancreatin, Bromelain, papain, or a mixture of these enzymes under stirring conditions. The digestion conditions are monitored to produce the collagen hydrolysate to average molecular weight between 1-2 KD with MS-HPLC and/or appropriately-sized filters selected to separate collagen fragments of a desired size. The enzymes are inactivated and the solution is filtered. To the filtered solution, a soluble mineral source such as calcium carbonate is added, the mixture is stirred for several hours, and pH is adjusted to 8.5 with NaOH to form a precipitate. The mixture, sprayed dry in a powdered form, contains about 15% of Calcium with average molecular weight 1-2 KD. Prophetic Example 2 The procedure of example 1 is followed except that fresh skin from bovine, pig or other animals is used instead of the commercially available collagen I/III. The skin is defatted, cut into small pieces and washed prior to addition to the mixing tank. Prophetic Example 3 The procedure of example 1 is followed except that gelatin, which consists primarily of collagen I/III, is used instead of collagen I/III. Prophetic Example 4 The procedure of example 1 is followed except that cartilage from bovine, chicken, shark or other animals is used after defatting, cutting into small pieces and washing. These tissues contain mainly collagen II. Prophetic Example 5 The procedure of example 1 is followed except that more than one soluble mineral source is used. In this Example calcium chloride/magnesium chloride in a 2:1 ratio mixture is employed. Prophetic Example 6 The procedure of example 1 is followed except that soluble mineral source is ferrous sulfate. Prophetic Example 7 The procedure of example 1 is followed except that soluble mineral source is zinc chloride. Prophetic Example 8 The procedure of example 1 is followed except that soluble mineral source is cupric chloride. Prophetic Example 9 The procedure of example 1 is followed except that soluble mineral source is manganese chloride. Examples of Supplements In addition, compounds made in accordance with any of examples 1-9 hereinabove can be formulated with one or more of an amino sugar or a salt thereof, a glycosaminoglycan or a salt thereof, an anti-inflammatory agent such as nonsteroidal anti-inflammatory drugs (NSAIDs) and herb extracts including but not limited to Boswellia, Ashwagandha, Ginger, and Turmeric, and anti-oxidants such as but not limited to Vitamin C and Vitamin E. These formulations can be used in producing dietary supplements, foods and drinks, food additives, animal feeds and feed additives, and drugs which are be administered to individuals/animals to reduce/prevent joint pain or joint deterioration from osteoarthritis, degenerative joint disease, joint defect, and rheumatoid arthritis. Compounds made in accordance with any of examples 1-9 hereinabove can be formulated with one or more of vitamin D, vitamin C, vitamin K1, and vitamin K2. These formulations can be used in producing dietary supplements, foods and drinks, food additives, animal feeds and feed additives, and drugs which are be administered to individuals/animals to support bone health and reduce or prevent osteoporosis. A preferred composition in accordance with this embodiment includes calcium/magnesium collagen chelate. Compounds made in accordance with any of examples 1-9 hereinabove can be formulated with one or more of a long chain polysaccharide, such as HA; an anti-oxidant such as Vitamin C, Vitamin E, OPC/grape seed, mangosteen extract, and green tea extract; and nutrients from the following niacin, thiamin, folic acid, iodine, vitamin A, vitamin B 6 , vitamin B 12 , vitamin D, aloe and mixtures thereof. These formulations can be used in producing dietary supplements, foods and drinks, food additives, animal feeds and feed additives, and drugs which are be administered to individuals/animals to support skin health. A preferred composition in accordance with this embodiment includes ferrous/Zinc collagen chelate. General Administration and Nutritional/Pharmaceutical Compositions When used as nutraceutical/pharmaceuticals, the compounds of the invention are typically administered in the form of a nutraceutical/pharmaceutical composition. Such compositions can be prepared using procedures well known in the nutraceutical/pharmaceutical art and comprise at least one compound of the invention. The compounds of the invention may also be administered alone or in combination with adjuvants that enhance stability of the compounds of the invention, facilitate administration of nutraceutical/pharmaceutical compositions containing them in certain embodiments, provide increased dissolution or dispersion, increased inhibitory activity, provide adjunct therapy, and the like. The compounds according to the invention may be used on their own or in conjunction with other active substances according to the invention, optionally also in conjunction with other nutraceutically/pharmacologically active substances. In general, the compounds of this invention are administered in a therapeutically or nutraceutically/pharmaceutically effective amount, but may be administered in lower amounts for diagnostic or other purposes. Administration of the compounds of the invention, in pure form or in an appropriate nutraceutical/pharmaceutical composition, can be carried out using any of the accepted modes of administration of nutraceutical/pharmaceutical compositions. Thus, administration can be, for example, orally, in the form of solid, semi-solid, lyophilized powder, or liquid dosage forms, such as, for example, tablets, pills, soft elastic and hard gelatin capsules, powders, solutions, suspensions, or the like, preferably in unit dosage forms suitable for simple administration of precise dosages. The nutraceutical/pharmaceutical compositions will generally include a conventional nutraceutical/pharmaceutical carrier or excipient and a compound of the invention as the/an active agent, and, in addition, may include other nutraceutical agents, medicinal agents, pharmaceutical agents, carriers, adjuvants, diluents, vehicles, or combinations thereof. Such nutraceutically/pharmaceutically acceptable excipients, carriers, or additives as well as methods of making nutraceutical/pharmaceutical compositions for various modes or administration are well-known to those of skill in the art. The state of the art is evidenced, e.g., by Remington: The Science and Practice of Pharmacy, 20th Edition, A. Gennaro (ed.), Lippincott Williams & Wilkins, 2000 ; Handbook of Pharmaceutical Additives , Michael & Irene Ash (eds.), Gower, 1995 ; Handbook of Pharmaceutical Excipients , A. H. Kibbe (ed.), American Pharmaceutical Ass'n, 2000; and H. C. Ansel and N. G. Popovish, Pharmaceutical Dosage Forms and Drug Delivery Systems, 5th ed., Lea and Febiger, 1990; each of which is incorporated herein by reference in their entireties to better describe the state of the art. As one of skill in the art would expect, the forms of the compounds of the invention utilized in a particular nutraceutical/pharmaceutical formulation will be selected that possess suitable physical characteristics (e.g., water solubility) that is required for the formulation to be efficacious. Solid dosage forms for oral administration of the compounds include capsules, tablets, pills, powders, and granules. For such oral administration, a nutraceutically/pharmaceutically acceptable composition containing a compound(s) of the invention is formed by the incorporation of any of the normally employed excipients, such as, for example, nutraceutical/pharmaceutical grades of mannitol, lactose, starch, pregelatinized starch, magnesium stearate, sodium saccharine, talcum, cellulose ether derivatives, glucose, gelatin, sucrose, citrate, propyl gallate, and the like. Such solid nutraceutical/pharmaceutical formulations may include formulations, as are well-known in the art, to provide prolonged or sustained delivery of the drug to the gastrointestinal tract by any number of mechanisms, which include, but are not limited to, pH sensitive release from the dosage form based on the changing pH of the small intestine, slow erosion of a tablet or capsule, retention in the stomach based on the physical properties of the formulation, bioadhesion of the dosage form to the mucosal lining of the intestinal tract, or enzymatic release of the active drug from the dosage form. Liquid dosage forms for oral administration of the compounds include emulsions, microemulsions, solutions, suspensions, syrups, and elixirs, optionally containing nutraceutical/pharmaceutical adjuvants in a carrier, such as, for example, water, saline, aqueous dextrose, glycerol, ethanol and the like. These compositions can also contain additional adjuvants such as wetting, emulsifying, suspending, sweetening, flavoring, and perfuming agents. Topical dosage forms of the compounds include ointments, pastes, creams, lotions, gels, powders, solutions, sprays, inhalants, eye ointments, eye or ear drops, impregnated dressings and aerosols, and may contain appropriate conventional additives such as preservatives, solvents to assist drug penetration and emollients in ointments and creams. Topical application may be once or more than once per day depending upon the usual medical considerations. The formulations may also contain compatible conventional carriers, such as cream or ointment bases and ethanol or oleyl alcohol for lotions. Such carriers may be present as from about 1% up to about 98% of the formulation, more usually they will form up to about 80% of the formulation. In all of the above nutraceutical/pharmaceutical compositions, the compounds of the invention are formulated with an acceptable carrier or excipient. The carriers or excipients used must, of course, be acceptable in the sense of being compatible with the other ingredients of the composition and must not be deleterious to the recipient. The carrier or excipient can be a solid or a liquid, or both, and is preferably formulated with the compound of the invention as a unit-dose composition, for example, a tablet, which can contain from 0.05% to 95% by weight of the active compound. Such carriers or excipients include inert fillers or diluents, binders, lubricants, disintegrating agents, solution retardants, resorption accelerators, absorption agents, and coloring agents. Suitable binders include starch, gelatin, natural sugars such as glucose or β-lactose, corn sweeteners, natural and synthetic gums such as acacia, tragacanth or sodium alginate, carboxymethylcellulose, polyethylene glycol, waxes, and the like. Lubricants include sodium oleate, sodium stearate, magnesium stearate, sodium benzoate, sodium acetate, sodium chloride, and the like. Disintegrators include starch, methyl cellulose, agar, bentonite, xanthan gum, and the like. Nutraceutical/Pharmaceutically acceptable carriers and excipients encompass all the foregoing additives and the like. Examples of Nutraceutical Formulations JOINT HEALTH SUPPORT FORMULA Dosage Recommended: 2 capsules 3 times daily Serving Size: 1 capsule, 600 mg Amount Per Serving: % DV Calcium Collagen Chelate 300 mg Glucosamine HCL 200 mg Turmeric extract 30 mg Boswellia Serrata Extract (gum) 25 mg Ester C comparable formula 20 mg Vitamin E 5 iu Zinc (picolinate) 5 mg Magnesium (carbonate) 10 mg Manganese (sulfate) 1 mg L-Cystine 5 mg L-Lysine 5 mg BONE HEALTH SUPPORT FORMULA Dosage Recommended: 2 capsules 3 times daily Serving Size: 1 capsule Amount Per Serving: % DV Calcium Collagen Chelate 300 mg Vitamin D 120 IU Vitamin K1 25 ug Vitamin K2 25 ug Ester C comparable formula 20 mg Zinc (picolinate) 5 mg Magnesium (carbonate) 10 mg Manganese (sulfate) 1 mg Examples of Formulations A. TABLETS Component Amount per tablet (mg) active substance 400 lactose 40 corn starch 40 polyvinylpyrrolidone 15 magnesium stearate 5 TOTAL 500 The finely ground active substance, lactose, and some of the corn starch are mixed together. The mixture is screened, then moistened with a solution of polyvinylpyrrolidone in water, kneaded, wet-granulated and dried. The granules, the remaining corn starch and the magnesium stearate are screened and mixed together. The mixture is compressed to produce tablets of suitable shape and size. B. TABLETS Component Amount per tablet (mg) active substance 300 lactose 20 corn starch 20 polyvinylpyrrolidone 15 magnesium stearate 2 microcrystalline cellulose 23 sodium-carboxymethyl starch 20 TOTAL 400 The finely ground active substance, some of the corn starch, lactose, microcrystalline cellulose, and polyvinylpyrrolidone are mixed together, the mixture is screened and worked with the remaining corn starch and water to form a granulate which is dried and screened. The sodium-carboxymethyl starch and the magnesium stearate are added and mixed in and the mixture is compressed to form tablets of a suitable size. C. COATED TABLETS Component Amount per tablet (mg) active substance 65 Lactose 10 corn starch 11.5 polyvinylpyrrolidone 3 magnesium stearate 0.5 TOTAL 90 The active substance, corn starch, lactose, and polyvinylpyrrolidone are thoroughly mixed and moistened with water. The moist mass is pushed through a screen with a 1 mm mesh size, dried at about 45° C. and the granules are then passed through the same screen. After the magnesium stearate has been mixed in, convex tablet cores with a diameter of 6 mm are compressed in a tablet-making machine. The tablet cores thus produced are coated in known manner with a covering consisting essentially of sugar and talc. The finished coated tablets are polished with wax. D. CAPSULES Component Amount per capsule (mg) active substance 460 corn starch 38.5 magnesium stearate 1.5 TOTAL 500 The substance and corn starch are mixed and moistened with water. The moist mass is screened and dried. The dry granules are screened and mixed with magnesium stearate. The finished mixture is packed into size 1 hard gelatin capsules. While the preferred embodiments have been described and illustrated it will be understood that changes in details and obvious undisclosed variations might be made without departing from the spirit and principle of the invention and therefore the scope of the invention is not to be construed as limited to the preferred embodiment.
Collagen peptide chelated mineral products, pharmaceutical formulations thereof and methods for preparing same are provided. Also provided is a method for generating the optimal size of collagen peptide for optimum mineral chelation as well as optimum biological function for supporting bone health and joint health. Also disclosed are methods of increasing bone density/preventing osteoporosis, of reducing joint pain and/or joint deterioration from osteoarthritis, degenerative joint disease, joint defect, and rheumatoid arthritis.
2
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 60/557,950, filed on Mar. 31, 2004, which is expressly incorporated herein in its entirety by reference thereto. FIELD OF THE INVENTION [0002] The present invention relates to a communication system or information system for a motor vehicle, the communication system or information system, e.g., having an interface for the exchange of data between the communication system and a mobile telephone, or for the exchange of data between the information system and a mobile data memory or a mobile computer. BACKGROUND INFORMATION [0003] German Published Patent Application No. 203 10 288 describes a hands-free conversing device for mobile telephones in a motor vehicle, which includes a holding receptacle to be permanently placed in the motor vehicle. On one side, this holding receptacle is to be electrically connected to an electronics unit installed in the vehicle and connected to a corresponding vehicle interface, and on the other side, it has a plug connector for the electrical and mechanical connection to telephone holders adapted to different mobile telephones, a Bluetooth adapter with an integrated plug connector being provided for the electrical and mechanical coupling to the plug connector of the holding device. [0004] German Published Patent Application No. 198 35 433 describes a communication terminal or telephone, in particular for Internet telephony, which has a touch-sensitive display as input/output interface and means for displaying an HTML-like page on the display via which the functions of the terminal are able to be operated. The telephone includes a freely configurable operating surface. To this end, the telephone has a touch-sensitive display and an Internet browser to process so-called HTML pages. The display is used as input and output interface for a user. The Internet browser or www-browser may be called a conversion device or an interpreter of HTML pages. In addition to text, control characters that may lead to other pages or trigger functions are also representable on the HTML page. The browser function may run in the telephone on an already available processor or on an additional processor. In an analogous manner, the HTML page is able to be stored in the telephone. Via the HTML page, the operating surface of the telephone may be freely configured by any provider of telecommunication services. The browser represents this specific operating surface on the telephone. The HTML page may be supplemented by Java applets or corresponding technologies. The provider loads the HTML pages into the telephone or terminal via the Internet protocol, for instance. The terminal is usable, for example, only after the user surface has been imported by the operator of the provider. [0005] U.S. Pat. No. 5,619,684 describes the display of numerical keys and function keys for a telephone on a display disposed below a touch screen is known. SUMMARY [0006] Example embodiments of the present invention may improve the operability of a communication system or information system for a vehicle, the system including an interface for the exchange of data between the communication system and a mobile telephone, or for the exchange of data between the information system and a mobile data memory or a mobile computer. [0007] An example embodiment of the present invention may provide a communication system for a motor vehicle, the communication system including an interface for the exchange of data between the communication system and a mobile telephone; a display having an associated control device to display an image of the mobile telephone, the image including at least one operating element, or a portion of an image of the mobile telephone, the image including at least one operating element; and a touch screen disposed above the display, to operate the mobile telephone by touching the touch screen in the region of the displayed operating element or by pressing on the touch screen in the region of the displayed operating element. In this manner, an operator who is familiar with operating the mobile telephone is able to operate it with the aid of the touch screen in the same manner as when using the operating elements of the mobile telephone. There is no need for the operator to adjust to a new man-machine interface. Instead, he may operate the mobile telephone also via the operating elements operable with the aid of the touch screen, in a manner with which the user is familiar. [0008] An upper portion of the mobile telephone may be able to be displayed on the display next to a lower portion of the mobile telephone. [0009] Information about the image of the mobile telephone or the portion of the image of the mobile telephone in XML format may be able to be used (by the control device) for display on the display. Details regarding the display of images stored in XML format may be gathered from U.S. Pat. No. 6,640,169 (incorporated by reference), U.S. Patent Application Publication No. 2003/0120397 (incorporated by reference), U.S. Patent Application Publication No. 2002/0138178 (incorporated by reference) and European Published Patent Application No. 1 245 430. [0010] Information about the image of the mobile telephone or the portion of the image of the mobile telephone may be able to be transmitted from the mobile telephone to the communication system, it being possible to read the information about the image of the mobile telephone or the portion of the image of the mobile telephone in to the communication system, e.g., via the interface. [0011] The communication system may also include an information memory to store information about the image of the mobile telephone or the portion of the image of the mobile telephone. The communication system may also include an identification module to identify the type of the mobile telephone and, e.g., a selection module to select information about the image of the mobile telephone or the portion of the image of the mobile telephone as a function of the identified type of the mobile telephone. [0012] The interface may be an interface for wireless communication, e.g., a Bluetooth interface. [0013] In a method for operating a communication system for a motor vehicle, a data link between the communication system and a mobile telephone is established via a previously mentioned interface, e.g., and an image, including at least one operating element, of the mobile telephone or a portion of an image, including at least one operating element, of the mobile telephone is displayed on a display. For example, the mobile telephone may be operated by touching a touch screen, disposed above the display, in the region of the displayed operating element, or by pressing on the touch screen in the region of the displayed operating element. [0014] Information about the image of the mobile telephone or the portion of the image of the mobile telephone may be transmitted from the mobile telephone to the communication system, e.g., prior to display of the image, including at least one operating element, of the mobile telephone, or the portion of the image, including at least one operating element, of the mobile telephone on the display. This transmission is implemented in a wireless manner, for example. [0015] The type of the mobile telephone may be identified, and information about the image of the mobile telephone or the portion of the image of the mobile telephone may be selected from an information memory as a function of the identified type of the mobile telephone. Information about at least one image of at least two mobile telephones in each case, or at least one portion of at least one image of at least two mobile telephones in each case may be able to be stored, or may be stored, in the information memory. [0016] In an information system for a motor vehicle, the information system includes an interface for the exchange of data between the information system and a mobile data memory, e.g., a PDA, and/or a mobile computer; a display having an assigned control system to display an image of the mobile data memory and/or the mobile computer, the image including at least one operating element, or a portion of the image of the mobile data memory and/or the mobile computer, the image including at least one operating element; and a touch screen disposed above the display to operate the mobile data memory and/or the mobile computer by touching the touch screen in the region of the displayed operating element or by pressing on the touch screen in the region of the displayed operating element. In this manner, an operator who is familiar with operating the mobile data memory and/or the mobile computer is able to operate it via the touch screen in the same manner as when using the operating elements of the mobile data memory and/or the mobile computer. There is no need for the operator to adjust to a new man-machine interface. Instead, he may operate the mobile data memory and/or the mobile computer in the familiar manner also via the operating elements operable with the aid of the touch screen. [0017] An upper portion of the mobile data memory and/or the mobile computer may be displayable on the display next to a lower portion of the mobile data memory and/or the mobile computer. [0018] The control system may be able to use information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer in XML format for display on the display. Details regarding the display of images stored in XML format may be gathered from U.S. Pat. No. 6,640,169 (incorporated by reference), U.S. Patent Application Publication No. 2003/0120397 (incorporated by reference), U.S. Patent Application Publication No. 2002/0138178 (incorporated by reference) and European Published Patent Application No. 1 245 430. [0019] Information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer may be able to be transmitted from the mobile data memory and/or the mobile computer to the information system, it being possible to read the information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer, in to the information system via the interface, for example. [0020] The information system may also include an information memory to store information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer. The information system may also include an identification module to identify the type of the mobile data memory and/or the mobile computer, and, for example, a selection module to select information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer as a function of the identified type of the mobile data memory and/or the mobile computer. [0021] The interface may be an interface for wireless communication, e.g., a Bluetooth interface. [0022] In a method for operating an information system for a motor vehicle, a data link is established between the information system and a mobile data memory and/or a mobile computer, e.g., via a previously mentioned interface; and an image, including at least one operating element, of the mobile data memory and/or the mobile computer, or a portion of an image, including at least one operating element, of the mobile data memory and/or the mobile computer is displayed on a display. For example, the mobile data memory and/or the mobile computer may be operated by touching a touch screen, disposed above the display, in the region of the displayed operating element, or by pressing on the touch screen in the region of the displayed operating element. [0023] Information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer may be transmitted from the mobile data memory and/or the mobile computer to the information system, e.g., prior to the display of the image, including at least one operating element, of the mobile data memory and/or the mobile computer, or the portion of the image, including at least one operating element, of the mobile data memory and/or the mobile computer on the display. This transmission is implemented in a wireless manner, for example. [0024] The type of the mobile data memory and/or the mobile computer may be identified; and information about the image of the mobile data memory and/or the mobile computer, or the portion of the image of the mobile data memory and/or the mobile computer may be selected from an information memory as a function of the identified type of the mobile data memory and/or the mobile computer; it being possible to store information about at least one image of at least two mobile telephones, mobile data memories and/or mobile computers in each case, or at least one portion of at least one image of at least two mobile telephones, mobile data memories and/or mobile computers in each case in the information memory. [0025] A motor vehicle includes an interface for the exchange of data between the information system and a mobile telephone, a mobile data memory, e.g., a PDA, and/or a mobile computer; a display having an assigned control system to display an image, including at least one operating element, of the mobile telephone, the mobile data memory and/or the mobile computer, or a portion of an image, including at least one operating element, of the mobile telephone, the mobile data memory and/or the mobile computer; and a touch screen, disposed above the display, to operate the mobile telephone, the mobile data memory and/or the mobile computer by touching the touch screen in the region of the displayed operating element, or by pressing on the touch screen in the region of the displayed operating element. [0026] A motor vehicle may include a land vehicle that may be used individually in road traffic. Motor vehicles are not restricted to land vehicles having an internal combustion engine. [0027] Further aspects and details of exemplary embodiments of the present invention are described below with reference to the appended Figures. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a view of the interior of a motor vehicle; [0029] FIG. 2 illustrates an exemplary embodiment of a communication system; [0030] FIG. 3 illustrates a method sequence implemented in a communication system; [0031] FIG. 4 illustrates an exemplary embodiment of a mobile telephone; [0032] FIG. 5 illustrates an exemplary embodiment of a display of an image of the mobile telephone illustrated in FIG. 4 ; [0033] FIG. 6 illustrates an exemplary embodiment of a mobile telephone; [0034] FIG. 7 illustrates an exemplary embodiment of a display of an image of the mobile telephone illustrated in FIG. 6 ; [0035] FIG. 8 illustrates an exemplary embodiment of a communication system; [0036] FIG. 9 illustrates a method sequence implemented in a communication system; [0037] FIG. 10 illustrates an exemplary embodiment of a mobile data memory and computer; [0038] FIG. 11 illustrates an exemplary embodiment of a display of an image of the data memory and computer illustrated in FIG. 10 ; and [0039] FIG. 12 illustrates an exemplary embodiment of a display of an image of the mobile telephone illustrated in FIG. 4 , and an image of the data memory and computer illustrated in FIG. 10 . DETAILED DESCRIPTION [0040] FIG. 1 is a view of the interior of a motor vehicle 1 . Motor vehicle 1 has a steering wheel 2 into which a display device 3 is integrated. However, as an alternative, display device 3 may also be arranged in an instrument panel 4 , or be arranged in an instrument panel 4 as additional display device. [0041] Furthermore, motor vehicle 1 includes a communication system 10 , illustrated in FIG. 2 , which has a control system 13 that includes a Bluetooth interface 12 for the exchange of data CTRL, AUDIO_IO, HMI between communication system 10 and a mobile telephone 11 . In addition, communication system 10 includes a microphone 14 , which generates a signal MIC, and a loudspeaker 15 to output a loudspeaker signal SPEAK. Control system 13 together with microphone 14 and loudspeaker 15 forms a hands-free telephone device for mobile telephone 11 . Signal MIC and loudspeaker signal SPEAK are transmitted as audio input and audio output signal AUDIO_IO between control system 13 and mobile telephone 11 via Bluetooth interface 12 . This data exchange is controlled by a control signal CTRL. Microphone 14 and loudspeaker 15 may also be part of another system such as a music system. [0042] Furthermore, communication system 10 has display device 3 , which is able to be utilized by other components as well, for instance, a climate-control device, an infotainment system or a navigation system. Such a display device is described in PCT International Published Patent Application No. WO 00/21795, for example. Display device 3 includes a display 16 to display an image, including at least one operating element, of mobile telephone 11 , or a portion of an image, including at least one operating element, of mobile telephone 11 ; as well as a touch screen 17 , disposed above display 16 , to operate mobile telephone 11 by touching touch screen 17 in the region of the displayed operating element and/or by pressing on touch screen 17 in the region of the displayed operating element. To this end, an information item HMI about the image of mobile telephone 11 or the portion of the image of mobile telephone 11 is transmitted from mobile telephone 11 to communication system 10 and/or control system 13 in XML format via Bluetooth interface 12 . Table 1 shows an exemplary embodiment for such information HMI in XML format. Details regarding the display of images in XML format may be gathered from U.S. Pat. No. 6,640,169 (incorporated by reference), U.S. Patent Application Publication No. 2003/0120397 (incorporated by reference), U.S. Patent Application Publication No. 2002/0138178 (incorporated by reference) and European Published Patent Application No. 1 245 430. [0000] TABLE 1 <device name=“Motorola 280i”> <panel name=“defaultScreen”> <label name=“batteryLevel”/> <button name=“phoneBook”/> <button name=“message”/> </panel> <panel name=“phoneBook”> ... </device> [0043] FIG. 3 illustrates a method sequence, implemented in control system 13 and thus in communication system 10 , for displaying the image of mobile telephone 11 or a portion of the image of mobile telephone 11 . To this end, it is first queried via a query 20 whether a data link is to be established between a mobile telephone and control system 13 . If a data link is to be established between a mobile telephone, such as mobile telephone 11 and control device 13 , query 20 is followed by a step 21 in which an information item HMI with regard to the image of this mobile telephone 11 , or the portion of the image of this mobile telephone 11 , is transmitted from this mobile telephone 11 to communication system 10 or control system 13 in XML format via Bluetooth interface 12 . Otherwise, query 20 is followed by another query 20 . [0044] If display device 3 is utilized by other functions as well, such as an air-conditioning system, an infotainment system or a navigation system, step 21 is followed by a query 22 as to whether mobile telephone 11 is to be operated with the aid of display device 3 or with the aid of touch screen 17 . Otherwise, step 21 is followed by a step 23 in which an image of mobile telephone 11 , or the portion of the image of mobile telephone 11 , is displayed on display 16 . If mobile telephone 11 is to be operated with the aid of display device 3 or with the aid of touch screen 17 , query 22 is followed by step 23 . Otherwise, query 22 is followed by another query 22 . [0045] If display device 3 is utilized by other functions as well, such as an air-conditioning system, an infotainment system or a navigation system, step 23 is followed by a query 24 as to whether the operation of mobile telephone 11 with the aid of display device 3 or with the aid of touch screen 17 is to be ended. Otherwise, step 23 is followed by query 22 . If the operation of mobile telephone 11 with the aid of display device 3 or with the aid of touch screen 17 is to be ended, query 24 is followed by query 22 . Otherwise, query 24 is followed by another query 24 . [0046] FIG. 4 and FIG. 6 each illustrate an exemplary embodiment of a mobile telephone, and FIG. 5 and FIG. 7 illustrate an exemplary embodiment of a display of an image of these mobile telephones illustrated in FIG. 4 and FIG. 6 . FIG. 4 illustrates a Motorola 280i, and FIG. 5 illustrates an image of a Motorola 280i displayed with the aid of display device 3 . An upper portion 30 of the Motorola 280i is illustrated next to a lower portion 31 of the Motorola 280i. By touching display device 3 or touch screen 17 in the region of displayed operating elements 32 , or by pressing on display device 3 or touch screen 17 in the region of displayed operating elements 32 , an operator who is familiar with operating the Motorola 280i is able to operate it via display device 3 or touch screen 17 in the same manner as the Motorola 280i illustrated in FIG. 4 . It may be provided that a telephone display 33 is able to be displayed via display device 3 as well. In this context, it may be provided that information represented on telephone display 33 , displayed with the aid of display device 3 , is displayed in the same manner as when using the same operation on actual telephone display 33 of the Motorola 280i. [0047] If the Motorola 280i in motor vehicle 1 is exchanged for an Ericsson T39m, illustrated in FIG. 6 , display device 3 displays an image of the Ericsson T39m instead of the Motorola 280i, as illustrated in FIG. 7 . An upper portion 40 of the Ericsson T39m is displayed next to a lower portion 41 of the Ericsson T39m lying underneath a cover 44 . [0048] By touching display device 3 or touch screen 17 in the region of displayed operating elements 42 , which are arranged underneath the cover in the Ericsson T39m, or by pressing on display device 3 or touch screen 17 in the region of displayed operating elements 42 situated arranged underneath cover 44 in the Ericsson T39m, an operator who is familiar with operating the Ericsson T39m is able to operate it via display device 3 or touch screen 17 in the same manner as the actual Ericsson T39m illustrated in FIG. 6 . It may be provided that a telephone display 43 is also able to be imaged with the aid of display device 3 . In this context, it may be provided that information is displayed on telephone display 43 , displayed with the aid of display device 3 , in the same manner as when using the same operation on actual telephone display 43 of the Ericsson T39m. [0049] FIG. 8 illustrates a communication system 50 as an alternative to communication system 10 illustrated in FIG. 2 , identical reference numerals denoting identical or similar subject matters as those illustrated in FIG. 2 . Like communication system 10 illustrated in FIG. 2 , communication system 50 illustrated in FIG. 8 has a Bluetooth interface 12 for the exchange of data CTRL, AUDIO_IO between a communication system 50 having a control system 53 , and a mobile telephone 51 . Furthermore, communication system 50 includes a microphone 14 , which generates a signal MIC, and a loudspeaker 15 to output a loudspeaker signal SPEAK. Control system 53 together with microphone 14 and loudspeaker 15 forms a hands-free telephone device for mobile telephone 51 . Signal MIC and loudspeaker signal SPEAK are transmitted as audio input and audio output signal AUDIO_IO between control system 53 and mobile telephone 51 via Bluetooth interface 12 . This data exchange is controlled by a control signal CTRL. Microphone 14 and loudspeaker 15 may also be part of another system such as a music system. [0050] Furthermore, communication system 50 has display device 3 , which is able to be utilized by other components as well, for instance, a climate-control device, an infotainment system or a navigation system. Display device 3 includes a display 16 to display, as shown in FIG. 4 and FIG. 6 , for example, an image, including at least one operating element 58 , of mobile telephone 51 , or a portion of an image, including at least one operating element 58 , of mobile telephone 51 ; as well as a touch screen 17 , disposed above display 16 , to operate mobile telephone 51 by touching touch screen 17 in the region of displayed operating element 58 , and/or by pressing on touch screen 17 in the region of displayed operating element 58 . Furthermore, communication system 50 includes an information memory 57 to store an information item HMI about the image of mobile telephone 51 or the portion of the image of mobile telephone 51 . [0051] To display an image, including at least one operating element 58 , of mobile telephone 51 , or a portion of an image, including at least one operating element 58 , of mobile telephone 51 , a method sequence as illustrated in FIG. 9 is implemented in control system 53 . To this end, it is first queried via a query 60 whether a data link is to be established between a mobile telephone and control system 53 . [0052] If a data link is to be established between a mobile telephone such as mobile telephone 51 , and control system 53 , query 60 is followed by a step 61 to identify the type of mobile telephone 51 , for instance, Motorola 280i or Ericsson T39m, with the aid of an identification module 55 illustrated in FIG. 8 , and to select an information item HMI in XML format about the image of mobile telephone 51 , or the portion of the image of mobile telephone 51 , from information memory 57 as a function of the identified type of mobile telephone 51 , with the aid of a selection module 56 illustrated in FIG. 8 . Otherwise, query 60 will be implemented again. [0053] If display device 3 is utilized by other functions as well, such as an air-conditioning system, an infotainment system or a navigation system, step 61 is followed by a query 62 as to whether mobile telephone 51 is to be operated with the aid of display device 3 or with the aid of touch screen 17 . Otherwise, step 61 is followed by a step 63 in which an image of mobile telephone 5 , or the portion of the image of mobile telephone 51 is displayed on display 16 . If mobile telephone 51 is to be operated with the aid of display device 3 or with the aid of touch screen 17 , query 62 is followed by step 63 . Otherwise, query 62 is followed by another query 62 . [0054] If display device 3 is utilized by other functions as well, such as an air-conditioning system, an infotainment system or a navigation system, step 63 is followed by a query 64 as to whether the operation of mobile telephone 51 with the aid of display device 3 or with the aid of touch screen 17 is to be ended. Otherwise, step 63 is followed by query 62 . If the operation of mobile telephone 51 with the aid of display device 3 or with the aid of touch screen 17 is to be ended, query 64 is followed by query 62 . Otherwise, query 64 is followed by another query 64 . [0055] It may be provided that communication system 10 illustrated in FIG. 2 , and communication system 50 illustrated in FIG. 8 , are also usable or alternatively usable together with a mobile data memory, e.g., a PDA and/or a mobile computer. In this instance, reference numerals 10 and 50 denote an information system. Such an information system 10 or 50 , provided it is not also able to be used in connection with a mobile telephone, generally has neither microphone 14 nor loudspeaker 15 . [0056] FIG. 10 illustrates a PALM Tungsten E, denoted by reference numeral 70 , as an exemplary embodiment of a mobile data memory and computer. As illustrated in FIG. 11 , its image 71 is displayable in a similar manner as described with reference to mobile telephones Motorola 280i or Ericsson T39m in order to operate the PALM Tungsten E with the aid of display device 3 . In an alternative arrangement, an upper portion of the PALM Tungsten E is displayable on the display next to a lower portion of the PALM Tungsten E. [0057] It may be provided that communication system 10 illustrated in FIG. 2 , and communication system 50 illustrated in FIG. 8 are also able to be used together with a mobile data memory, e.g., a PDA and/or a mobile computer. In this instance, it may be provided that a mobile telephone and the mobile data memory or mobile computer as illustrated in FIG. 12 are able to be displayed and operated simultaneously with the aid of display device 3 . For instance, FIG. 12 illustrates the simultaneous display of an image 72 of a Motorola 280i and an image 71 of a PALM Tungsten E. [0058] Control systems 13 and 53 may be implemented on a MGT5100 hardware platform, for example. LIST OF REFERENCE CHARACTERS [0000] 1 motor vehicle 2 steering wheel 3 display device 4 instrument panel 10 , 50 communication system 11 , 51 mobile telephone 12 interface 13 , 53 control system 14 microphone 15 loudspeaker 16 display 17 touch screen 18 , 32 , 42 , 58 operating element 20 , 22 , 24 , 60 , 62 , 64 query 21 , 23 , 61 , 63 step 30 , 40 upper portion 31 , 41 lower portion 33 , 43 telephone display 44 cover 55 identification module 56 selection module 57 information memory 70 PALM Tungsten E 71 , 72 image AUDIO_IO audio input and audio output signal CTRL control signal HMI information MIC signal SPEAK loudspeaker signal
In a communications system for a motor vehicle, the communications system includes: an interface for exchanging data between the communications system and a mobile telephone; a display with an assigned controller for displaying an image of the mobile telephone, the image including at least one control element, or for displaying a portion of an image of the mobile telephone, the portion of the image also having at least one control element; and a touch screen, which is located above the display and serves to operate the mobile telephone by touching the touch screen in the area of the displayed control element or by pressing upon the touch screen in the area of the displayed control element.
7
BACKGROUND OF THE INVENTION Pulse power requirements, for driving electrical apparatus used in magnetic fusion, laser fusion and similar processes, have grown substantially over the past ten years, with the result that pulse power availability is now a major limitation on technological progress in such applications. FIELD OF THE INVENTION The invention relates to broadband pulsed power apparatus for providing multi-megawatt power of time intervals of the order of a few nanoseconds. One apparatus for switching a high voltage power supply, disclosed in U.S. Pat. No. 4,158,803 issued to Berger, uses two high voltage and frequency planar triodes as source and sink, respectively, for the current to a highly capacitive load. The source tube conducts only when the sink tube is non-conducting. With an input pulse applied to the source tube through a source error amplifier and shunt comparator that is also connected to the sink tube, the sink tube is caused by the comparator to conduct, thus switching the source tube to a non-conducting state, whenever the pulse amplitude exceeds a pre-determined dc reference carried by the comparator. The source and sink tube rapidly charge and discharge, respectively, the output capacitance. The overall circuit appears to be tuned, and the source and sink tubes appear to be operated in the conventional regime, with voltage risetimes of the order of microseconds; but no circuit parameters of tube characteristics are specified in the patent disclosure or claim. SUMMARY OF THE INVENTION One object of the invention is to provide apparatus for generating pulse power of ≈2 megawatts over time intervals of the order of 2 nanoseconds, with associated risetimes of the order of 200 picoseconds or less. Another object is to provide broadband pulse power apparatus with a dynamic frequency range of the order of 1000:1. A third object is to provide apparatus to obtain peak pulse power of the order of ≳170 kilowatts from a conventional triode with nominal cathode area (≈2 cm 2 ). A fourth object is to provide a means of concatenating additional stages of the tubes and associated circuitry, without additional engineering being required, to provide even higher power output over substantially the same time intervals. Other objects of the invention, the advantages thereof, will become clear by reference to the detailed description and the accompanying drawings. To achieve the foregoing objects, the invention in one embodiment may comprise a high voltage avalanche source to provide up to 2 kilowatts power; a first biased, grid-grounded triode amplifier tube circuit with cathode coupled across a first capacitor to the output of the high voltage avalanche; a first voltage step-down transformer that is coupled across a second capacitor to the anode of the first triode tube circuit; a second biased, grid-grounded triode amplifier tube circuit with cathode coupled to the output of the first voltage step-down transformer; with the anode of the second triode tube being coupled across a third capacitor to three, substantially identical circuits in parallel, each circuit comprising a voltage step-down transformer that is coupled to the cathode of a biased, grid-grounded triode amplifier tube; with these latter three circuits being coupled across a common capacitor to the output point. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A and 1B are a schematic view of a preferred embodiment of the invention. FIG. 2 is a functional representation of the embodiment of FIG. 1. FIGS. 3A, 3B and 3C exhibit three components of an alternative embodiment of the high voltage avalanche source of FIG. 2, with a trigger circuit replacing the transistor transformer front end combination shown in FIG. 1. DETAILED DESCRIPTION The subject invention is a planar triode amplifier that operates in three (or more) stages, in one embodiment, to provide 500 kilowatts (KW) power over ≲1 nanosecond (nsec.) or 2 megawatts (MW) power over ≲2 nsec. The adjacent stages are coupled through broadband transmission line transformers that permit multiple stage operation with a tube (or tubes) that is (are) part of a single stage. Microwave planar triodes (in three or more stages) are part of broadband circuits, each including several 50 ohm transmission lines in parallel, connected to the cathode of each tube in the corresponding stage; the tube anode(s) is (are) connected to a 150 ohm load formed by the primary of a transmission line transformer. One feature of the invention is that the input and the output elements (coupling to adjacent stages) are sufficiently broadband that dynamic frequency ranges of 1000:1 or greater are available. No tuned circuit elements are used in the signal path(s) throughout the network. The microwave triode grids are all grounded, which elminates the deleterious Miller effect (frequency-dependent grid-cathode capacitance multiplication) and enhances gain linearity across a broad frequency range, a second feature of the invention. This configuration (grid-grounded, cathode-driven) is possible because of the low impedance transformer characteristics achieved with the inter-stage transmission lines used. A third feature, present because of the incorporation of the first two features, is that one can obtain peak pulse power greater than 170 KW (as compared to 10 KW by conventional operation) from a single 2 cm 2 cathode area at 12 KV anode voltage; and the pulse risetime to full power is less than one nanosecond. Using the techniques incorporated above, risetimes of 200 picoseconds or less are possible, although the present amplifier output risetime is limited by the input risetime available. Operation in this mode (Δt risetime ≲1 nsec.) requires the triode(s) to operate in a wholly different regime than the conventional regime (Δt risetime ≈1 μsec.) where the tube is operated in a resonant cavity. As a result, the tube amplification factor is reduced from 200:1 (conventional) to ≈5:1 here. The preferred embodiment uses three stages to achieve, say, 0.5 MW power by use of 5 KV through 50 ohms. As a fourth feature of the invention higher power levels are achievable by simply adding additional stages incorporating the first two features described above. Grounding of the tube grids requires that all current for the cathode drive at any stage, plus the associated grid losses (≈20-25%) at that stage, be supplied by the prior stage. At the last stage (third stage here) approximately 120 amps are available with the subject invention. A fifth feature of the subject invention allows impedance matching of the anode of stage n (≧1) with the cathode impedance of the stage n+1 so that stages can be concatenated without further engineering or scaleup difficulties. The embodiment shown and described here has three stages, producing up to 120 amps; but additional (or fewer) stages may be added without changing the design philosophy. A sixth feature is that the low impedance (Z) into the cathode allows a low associated time constant τ for cathode charge-up for repeat pulses for a given grid cathode capacitance C; alternatively, this allows operation with higher C for a given τ. A seventh feature is that the use of an n:1 voltage step-down transformer as input to any stage allows an n:1 power increase to that stage. With reference to FIG. 1, the "input" to the apparatus is through two transformers T1 and T2 and corresponding resistors R1 and R2 (≈50 ohms each) and base inputs to two npn transistors Q1 and Q2. The emitter of Q2 is grounded, and its collector is coupled to the base of a third npn transistor Q3 to form an avalanche stack. The collector of Q3 is resistively coupled (through R4≈20 ohms) through two 50 ohm parallel transmission lines TL1 and TL2; and the emitter of Q1 is coupled through two more 50 ohm transmission lines TL3 and TL4, all through a common input feed point IP1 to the cathode of a triode tube V1, preferably the Varian Eimac 8940/Y-690 tube. All lines TL1-4 are broadband; and the voltage at IP1 is arranged to be substantially 300 volts (input on) and -80 volts (input off). With input power at 1.8 KW inputs at IP1 are directly connected to the cathode of the triode V1 and produce ≈7.5 KW output power at anode output point OP1. A high voltage source (≈400 volts) HV1 is coupled across a resistor R7 (≈10 5 ohms), which is in turn grounded through a 10 nanofarad capacitor C1, to the collector of transistor Q1 with a corresponding drain time Δt≈0.1 msec. The grid of the triode V1 has a -80 V bias applied from source HV2, and the grid is in turn grounded through a capacitor C2 (≈2 nf). Because of the high capacitance chosen for C2, the tube V1 is effectively grid-grounded in the rf regime. At the anode output point OP1 of tube V1, an 8 KV bias is applied from a source HV3 across a resistor R6 (≈10 3 ohms). The signal at OP1 is capacitively coupled across C3 (≈11 nf) to three parallel 50 ohm transmission lines TL5, TL6 and TL7 that together produce 16.67 ohms impedance to match the input (cathode) impedance of another grid-grounded triode V2 (preferably, also 8940/Y-690) terminated by a resistor R8 (≈50 ohms). Little or no power is lost in transmission of the signal from output point OP1 to the input point IP2 to the cathode of triode V2 so that the power input at IP2 is substantially 7.5 KW. The output power at the anode output point OP2 of V2 is increased to about 70 KW; and the output signal is capacitively coupled through C10 (≈11 nf) to three 50 ohm transmission lines TL8, TL9 and TL10 in parallel. Again, a voltage bias source HV4 (≈-80 V) is coupled to the grid of V2. The grid of V2 is grounded through a capacitor C4 (≈2 nf) so that this tube is also effectively grid-grounded in the rf regime. At the anode output point OP2 of tube V1, an 8 KV bias is applied from a source HV5 across a resistor R9 (≈10 3 ohms). Each of the transmission lines TL8, TL9 and TL10 is in turn coupled to four 50 ohm transmission lines TL11, TL12, TL13 . . . , TL22 in parallel as shown. The separate combinations of four transmission lines (e.g. TL11, TL12, TL13 and TL14) produce an input impedance of 12.5 ohms at the input point IP3 terminated by R10 (≈50 ohms) of a triode tube V3 with, for example, the signal that passes through transmission line TL8 and TL11 then passing directly to the cathode input point IP3 of another grid-grounded triode V3 (preferably 8940/Y-690) with a grid that is grounded through a capacitor C5 (≈2 nf). Similarly, the transmission lines TL9, TL15, TL16, TL17, TL18 (TL10, TL19, TL20, TL21, TL22) communicate directly with the cathode input point IP4 (IP5) terminated by R11 (R12) of the grid-grounded triode V4 (V5). Finally, the anodes of the three triodes V3, V4 and V5 communicate with a common output point OP3 that couples to the output of the amplifier through a capacitor C8 (≈50 nf). The grids of the tubes V3, V4 and V5 are coupled directly to voltage bias source HV6, HV7 and HV8, respectively, (each -80 V); and the common anode point OP3 of the three tubes is coupled to a voltage bias source HV9 (≈8 KV) across a resistor R28 (≈1 K). The shields of all transmission lines TL1, TL2, . . . , TL22 are grounded. The embodiment of FIG. 1 can be represented generically as in FIG. 2. One begins with a high voltage avalanche source 11 that is coupled to a biased, grid-grounded triode amplifier tube and circuit 17. The output of this last circuit is capacitively coupled across C3 to a voltage step-down transformer 21 and is then fed to a second biased, grid-grounded triode amplifier tube and circuit 23. The output of the circuit 23 is capacitively coupled across C10 to three substantially identical, parallel voltage step-down transformers 27, 29 and 31 that each coupled directly and independently, to a separate biased, grid-grounded triode amplifier tube and circuit 33, 35 and 37, with these three tubes and circuits being substantially identical and with the anodes of these tubes being connected across a common capacitor C8 to the output point of the apparatus. As an alternative to the high voltage avalanche source 11 (FIG. 2) shown in FIG. 1, at the front end, one may use a trigger circuit as shown in FIG. 3A (pulse input), FIG. 3B (turn-on circuit) and 3C (turn-off circuit). This embodiment allows the user to input an arbitrary trigger signal, for example, 5 volts into 50 ohms; and the embodiment of FIGS. 3 will produce the appropriate inputs to drive the cathode of the first tube V1. The user enters an arbitrary trigger signal (within prescribed limits) through a 3:1 transformer TR101 (FIG. 3A) and across a resistance R101 (≈50 ohms) to the base of npn transistor T101 whose collector is connected to the emitter of a second npn transistor T103. The collector of the second transistor is coupled to ground across a capacitor C101, which may have a value substantially 200 picofarads, and the base and emitter of this transistor are tied together. The emitter of the transistor T101 is coupled to ground across a resistor R103 and is further coupled to a first transmission line TL31 across a resistor R105 and to a second transmission line TL32 across another resistor R107, with both resistors having substantially equal resistance values ≈47 ohms. The other end of transmission line TL31 (FIGS. 3A and 3B) is coupled across a second 3:1 transformer TR103 and across a resistor R116 (≈50 ohms) to a first feed point FP1 that is in turn connected to the bases of three npn transistors T105, T107 and T109 whose emitters are all grounded (FIG. 3B). The collectors of the respective transistors T105, T107 and T109 are electrically connected to the base and emitter of three more npn transistors T111, T113 and T115, respectively. The collector and emitter of each of transistors T105, T107, T109, T111, T113 and T115 are connected, respectively, across resistors R115, R121, R127, R113, R123 and R129, each having a resistance of ≈10 ohms. The base and emitter of each of transistors T111, T113 and T115 are tied together. The collecter of transistor T111 is coupled to a second feed point FP2 across a resistor R111 (≈75 ohms) and a capacitor C103 (≈100 picofarads) in parallel. Similarly, the collector of transistor T113 (respectively, T115) is coupled to feed point FP2 across a resistor R125 (respectively, R131) (≈75 ohms) and a capacitor C105 (respectively, C107) (≈100 picofarads) in parallel. Feed point FP2 is coupled across a resistor R133 (≈50 kilohms) to an 800 volt source S1, is coupled to ground across a capacitor C108 (≈60 picofarads), and is coupled across a capacitor C109 (≈15 nanofarads) to a third feed point FP3 that feeds two shield-grounded, 50 ohm transmission lines TL33 and TL34 that serve the same purposes as the transmission lines TL1 and TL2 of FIG. 1. The third feed point is coupled to ground across a resistor R110 (≈1 kilohm). The turn-on circuit and high voltage source of FIG. 3B is arranged to provide a leakage current to ground of ≈300 μamps to provide faster pulse response. The second feedpoint FP2 is also resistively connected across R109 (≈10 5 ohms) to the collector of transistor T103. The other end of transmission line TL32 (FIGS. 3A and 3C) is coupled across a third 3:1 transformer TR105 and across a resistor R131 (≈50 ohms) to a fourth feed point FP4 that is in turn connected to the bases of three npn transistors T117, T119 and T121 whose emitters are electrically connected to both the base and collector of three more npn transistors R123, T125 and T127, respectively (FIG. 3C). The emitter of transistor T123 is coupled to fifth feed point FP5 across a resistor R135 (≈75 ohms) and a capacitor C111 (≈100 picofarads) in parallel. Similarly, the collector of transistor T125 (respectively, T127) is coupled to feed point FP5 across a resistor R137 (respectively, R139) (≈75 ohms) and a capacitor C113 (respectively, C115) (≈100 picofarads) in parallel. The feed point FP5 is coupled to ground across a capacitor C117 (≈15 picofarads) and is coupled to an 800 volt source S2 across a resistor R141 (≈50 kilohms). The emitters of transistors T117, T119 and T121 are coupled across resistors R143, R145 and R147 (each ≈10 ohms), respectively, to the collectors of these respective transistors. Finally, the collectors of transistors T117, T119 and T121 are connected to a sixth feed point FP6, which is connected to ground across a capacitor C119 (≈60 picofarads) and is connected across a capacitor C121 (≈15 nf) to a seventh feed point FR7 that feeds two transmission lines TL35 and TL36 that serve the same purposes as the transmission lines TL3 and TL4 in FIG. 1. Feed point FP7 is coupled to ground across a resistor R155 (≈1 kilohm). The turn-off circuit and high voltage source of FIG. 3C is arranged to provide a leakage current to ground of ≈300 μamps to provide faster pulse response. Each of the "vertical" circuits T105/T111, T107/T113, T109/T115, T123/T117, T125/T119, T127/T121 provides a boost in power for the corresponding turn-on or turn-off circuit; and the use of three such "vertical" circuits in parallel in each of the turn-on and turn-off circuits provides the required current. Although the preferred embodiments of the invention have been shown and described herein, variation and modification may be made without departing from what is regarded as the scope of the invention.
A high voltage pulse generator for generating at least 500 kilowatts power over a time interval of substantially two nanoseconds with short risetime, using a high voltage avalanche source, a plurality of biased triode amplifier tubes and circuits and a voltage step-down transformer between any two consecutive tube stages.
7
BACKGROUND OF THE INVENTION 1. Technical Field The subject invention relates to a motion transmitting remote control assembly of the type for transmitting forces along a curved path by flexible motion transmitting core element movably supported by a flexible conduit, and more particularly to an improved assembly for adjusting the relative lengths between the core element and the conduit. 2. Background Art Motion transmitting remote control assemblies for transmitting motion in a curved path are used in aircraft, automotive, and marine environments. Typical of the use of such remote control assemblies is the positioning of throttle control members in automobiles. In such applications, it is frequently desirable to adjust the length or position of the of the core element once the assembly has been installed. Such assemblies normally include one or more fittings secured to the conduit for attaching the conduit to a support structure of the automobile, and the core element is adapted at one end to be attached to a member to be controlled whereas the other end is attached to a manually graspable knob for longitudinally moving the core element. After the assembly has been installed, the position of the knob must be adjusted to correspond with the position of the member to be controlled so that both the knob and member to be controlled reach their terminal end stroke positions at exactly the same time. This is accomplished by either adjusting the length of the core element or the length of the conduit, as is well known in the art. An example of the prior art adjustment arrangement is shown in U.S. Pat. No. 3,662,617 to Bennett issued May 16, 1972, assigned to the assignee of the subject invention. This reference discloses an adjustment means attached to the conduit for adjusting the effective length of the conduit. A further example of the prior art adjustment arrangement is shown in U.S. Pat. No. 3,665,784 to Bennett issued May 30, 1972, assigned to the assignee of the subject invention. This reference discloses an adjustment means attached to the core element for adjusting the effective length of the core element. These arrangements, however, do not allow the adjustment means to be manually looked into positions after adjusting the overall length of one of the conduit and the core element to a desired length and then unlocked to readjust the length of the conduit or core element. U.S. Pat. No. 4,765,199 to Andersen, et al, issued Aug. 23, 1988 and assigned to the assignee of the subject invention discloses a motion transmitting remote control assembly including a coupling for nonadjustably connecting a conduit to a support housing. The coupling includes a female member having a plurality of resilient fingers for engaging a male member. A locking ring is manually moved to a locked position about the female member to prevent uncoupling between the male and female members. This arrangement does not permit adjustment of the relative length of the core element or conduit. SUMMARY OF THE INVENTION AND ADVANTAGES According to the present invention, there is provided a motion transmitting remote control assembly of the type for transmitting forces along a curved path by a motion transmitting core element. The assembly comprises a conduit and a motion transmitting core element moveably supported by the conduit. An adjustment means adjusts the relative length of one of the conduit and the core element. The adjustment means includes a female member matingly receiving a male member in one of various positions. The female member includes a radially flexible pawl which engages the external surface of the male member to allow axial positioning of the male member relative to the female member. The invention is characterized by a collar means slidably disposed over the female member for preventing relative movement between the male and female members. Accordingly, the collar means of the present invention in combination with the adjustment means permits the relative length of one of the conduit and the core element to be adjusted as required by the particular application and then locked in the adjusted position The adjustment means and collar means of the present invention is durable, simply designed, easy to manufacture, and easily unlocked to allow readjustment. BRIEF DESCRIPTION OF THE DRAWINGS Other advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein: FIG. 1 is a cross-sectional view of the preferred embodiment of the assembly showing the conduit adjusted to a maximum length and the collar means disposed in the locked position; FIG. 2 is a cross-sectional view as in FIG. 1 but showing the conduit adjusted to a minimum length; FIG. 3 is a side view of the assembly showing the male and female members of the adjustment means in an unengaged position and the collar means in an unlocked position; FIG. 4 is an enlarged, fragmentary cross-sectional view of the annular ridge and annular groove; FIG. 5 is an enlarged, fragmentary cross-sectional view of the external and internal teeth of the male and female members in a no-load condition; FIG. 6 is an enlarged, fragmentary cross-sectional view as in FIG. 5 showing the external and internal teeth loaded in compression; FIG. 7 is an enlarged, fragmentary cross-sectional view as in FIG. 5 showing the external and internal teeth loaded in tension; FIG. 8 is a cross-sectional view of an alternate embodiment of the assembly showing the male and female members of the adjustment means in an unengaged position and, the collar means in an unlocked position; FIG. 9 is a cross-sectional view of an alternate embodiment of the assembly as in FIG. 8 showing the male and female members of the adjustment means and the collar means in an engaged position; FIG. 10 is a cross-sectional view of a second alternate embodiment of the assembly in an engaged position; FIG. 11 is a cross-sectional view of an alternate embodiment of the collar means; FIG. 12 is a cross-sectional view of the collar means taken along lines 12--12 of FIG. 11; and FIG. 13 is a cross-sectional view of a second alternate embodiment of the collar means showing the expansion slot hyperextended for clarity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIGS. 1-7, wherein like numerals indicate like or corresponding parts throughout the several views, the preferred embodiment of a manually operated terminal adjust assembly constructed in accordance with the instant invention is generally shown at 20. The assembly 20 includes a conduit 22 and a motion transmitting core element 24 which is movably supported by the conduit 22. The conduit 22 is preferably of the type including an inner tubular member made of an organic polymeric material and surrounded by a plurality of long lay wires disposed helically thereabout with a casing of organic polymeric material disposed about the long lay wires and the inner tubular member. The organic polymeric materials may be of the various well know plastics such as polyethylene, etc. The assembly 20 includes an adjustment means, generally indicated at 26 in FIGS. 1-2, for adjusting the length of the conduit 22. In other words, the adjustment means 26 is attached to the conduit 22 for telescopic relative movement to adjust the length of the conduit 22 relative to the core element 24. The adjustment means 26 comprises a male member, generally indicated at 28, a female member, generally indicated at 30, and a collar means, generally indicated at 32. The male member 28 is matingly received by the female member 30 at any one of various positions for length adjustment axially along the male member 28 with the collar 32 slideably disposed surrounding the female member 30 and moveable to a locked position on the female member 30 to restrain axial movement between the male member 28 and the female member 30. The male member 28, the female member 30 and the collar means 32 are preferably of organic polymeric material and may be formed using injection molding techniques. The male member 28 includes an external surface 34 on which is disposed a plurality of endlessly annular external teeth 36 and a seal, preferably an O-ring 38 as shown in FIG. 3. The female member 30 includes a plurality of radially flexible pawls 40 defined by a plurality of axially extending slots 42 as best shown in FIG. 3. The slot 42 configuration can be varied depending on the number and length of slots 42 used. For example, the slot 42 configuration shown in FIG. 3 includes two diametrically opposed slots 42 forming two pawls 40, with the slots 42 each including an enlarged rounded end 44 to reduce the stress concentrations during flexure of the pawls 40. Alternatively, an oval end (not shown) can be formed at the end of each of three or more slots to form three or more pawls 40. The female member 30 includes an internal surface 46 and an external surface 48. A plurality of arcuate internal teeth 50 are disposed on the internal surface 46 of the flexible pawls 40. An annular ridge 52 is encirclingly disposed on the external surface 48 of the female member 30. Referring now to FIGS. 5-7 the internal teeth 50 are defined by a rearward facing inclined surface 54 and a forward facing inclined surface 56 which project from the internal surface 46 and converge at alternating crests and roots. Similarly, the external teeth 36 are defined by a rearward facing inclined surface 58 and a forward facing inclined surface 60 which extend from the external surface 34 and intersect. The collar means 32 has a tubular configuration which is defined by a back end 62, a front end 64, and an interior surface 66 as best shown in FIG. 3. A retaining means 67, as best shown in FIG. 4, between the female member 30 and the collar means 32 retains the collar means 32 in the locked position. The retaining means 67 includes an annular groove 68 disposed in the interior surface 66 of the collar means 32 to receive the annular ridge 52 disposed on the external surface 48 of the female member 30. The front end 64 of the collar means 32 is rounded to define a cam shoulder 70 for enabling the collar means 32 to slide over the annular ridge 52 as the collar means 32 is being moved into locking position. A stop means, generally indicated at 72 in FIGS. 1 and 2, limits the axial movement of the collar means 32 in at least one direction relative to the female member 30, which is to the right in FIGS. 1 and 2. The stop means 72 includes an annular shoulder 73 disposed at the back end 62 of the collar means 32. The annular shoulder 73 extends inwardly toward the female member 30 forming a channel 74 through which the conduit 22 passes. When the collar means 32 is surrounding disposed on the female member 30, the annular shoulder 73 abuts against the internal teeth 50 and is prevented from continued forward movement. An O-ring 38 is disposed between the external surface 34 of the male member 28 and the interior surface 46 of the female member 30 so as to prevent fluids from entering the adjustment means 26 and the conduit 22. The O-ring 38 is disposed in a second annular groove 76 on the external surface 34 of the male member 28. In operation the internal teeth 50 coact with the external teeth 36 to allow axial adjustment between the female member 30 and the male member 28 in the unlocked position. The radial pawls 40 deflect outwardly during adjustment to allow the external teeth 36 to move relative to the internal teeth 50. In other words, the internal teeth 50 ratchet with the external teeth 36 to affect an adjustment of the length of the conduit 22. When the length of the conduit 22 is adjusted relative to the length of the core element 24, as for example either maximally extended as shown in FIG. 1 or maximally contracted as shown in FIG. 2, the collar means 32 is manually slid over the female member 30 to prevent further axial movement of the male member 28 relative to the female member 30 by preventing radial deflection of the pawls 40. Thus the internal teeth 50 remain engaged with the external teeth 36 thereby preventing axial movement. The constricting force exerted by the collar means 32 on the flexible pawls 40 is such that the flexible pawls 40, and therefore the internal teeth 50, are not in direct contact with the external teeth 36 of the male member 28 and a tolerance space 78 is defined between the interacting internal 50 and external 36 teeth, as shown in FIG. 5. In a no-load condition, that is, no force being exerted on the male member 28 in either a forward or a rearward direction, the tolerance space 78 is evenly distributed between the external 36 and internal 50 teeth. In the no-load condition the male member 28 therefore rotates freely axially within the female member 30 thereby allowing the male member 28 to be self-aligning as is described in more detail below. When a force is applied to the male member 28 in a forward direction the forward inclined surface 60 of the external teeth 36 bear on the rearward inclined surface 54 of the internal teeth 50 and displacing the tolerance space 78 thereby inhibiting rotation of the male member 28 as shown in FIG. 6. In other words the external teeth 36 and internal teeth 50 are loaded in tension. When a force is applied to the male member 28 in a rearward direction the rearward inclined surface 58 of the external teeth 36 bear on the forward inclined surface 56 of the internal teeth 50 displacing the tolerance space 78 thereby inhibiting rotation of the male member 28 as shown in FIG. 7. In other words the external teeth 36 and internal teeth 50 are loaded in compression. A snap-in fitting is generally indicated at 82 and is secured to the female member 30 as shown in FIG. 2. The snap-in fitting 82 is provided to support the assembly 10 in an aperture 84 in a wall 86 or the like with a spaced bracket 88 with an opening 90. The snap-in fitting 8 includes a forward end 92, a plurality of orientation ribs 94, and a pair of support ribs 96. The forward end 92 includes an O-ring 98 and a pair of flexible legs 100. The forward end 92 is passed through the opening 90 in the spaced bracket 88 and the O-ring 98 is engaged in a receiving groove 102 in the aperture 84 to seal. The flexible legs 100 are urged inward to pass through the opening 90 in the spaced bracket 88 and then extend outwardly after passing through the bracket 88 to retain the fitting 82 in the aperture 89. Access to the flexible legs 100 is thus maintained to allow for removal. The orientation ribs 94 are spaced so as to have a configuration specific to the assembly 10. The opening 90 is configured to receive only the specific orientation ribs 94 for the assembly 10 thus conferring on the snap-in fitting 82 a distinct orientation. An opposite end (not shown) of the assembly 10 from the snap-in fitting 82, includes an end fitting (not shown) secured to a support (not shown). The end fitting is configured to have a specific orientation to be received in the support. The orientation of the snap-in fitting 82 and the end fitting are random with respect to each other. In other word, the snap-in fitting 82 and therefore the attached female member 30 are not aligned with the end fitting and, when not aligned, the conduit 22 is biased. The male member 28 is directly attached to the conduit 22. The male member 28 rotating freely axially within the female member 30 thereby allows the decrease of bias of the conduit 22. In other words the male member 28 is self-aligning. DESCRIPTION OF ALTERNATE EMBODIMENTS FIGS. 8-9 illustrate a first alternative of the subject assembly 20', with the prime designations being used to identify like or corresponding parts with the preferred embodiment of FIGS. 1-7. The assembly 20' differs from the preferred embodiment assembly 20 in that the external surface 34' of the male member 28' does not include external teeth. The male member 28' is matingly received by the female member 30' at any one of infinite positions for length adjustment axially along the male member 28'. In operation the internal teeth 46' are urged into biting contact with the smooth, untoothed external surface 34' and maintained in this position by the collar means 32'. In this embodiment the male member 28' is not free to rotate within the female member 30'. FIG. 10 illustrates another alternative embodiment of the subject assembly 20", with the double prime designation being used to identify like or corresponding parts with the preferred embodiments of FIGS. 1-7. The assembly 20" illustrated in FIG. 6 differs from the preferred embodiment assembly 20 in that the adjustment means 26" is fixedly secured to and extends from the core element 24" for adjusting the length of the core element 24" relative to the conduit 22". The O-ring 38 is not required in the assembly 20". A support fitting 104" is disposed about the conduit 22" and is adapted for attachment to a support structure (not shown). In all other respects, the embodiment of assembly 20" shown in FIG. 6 is structurally similar and functions the same as the embodiment of assembly 20 shown in FIGS. 1-3. FIGS. 11-12 illustrate a first alternative of the collar means 32a, with the letter designation "a" being used to identify like or corresponding parts with the preferred embodiment of FIGS. 1-7. In order to vary the constricting force on the flexible pawls, the collar means 32a may be polymeric material with imbedded glass fibers or the like. At least one expansion slot 80a is required for the collar means 32a to allow radial flexibility as best shown in FIGS. 11-12. Expansion slot 80a is disposed adjacent to and spaced from the front end 64a of the collar means 32a. FIG. 13 illustrates another alternative embodiment of the collar means 32b, with the letter designation "b" being used to identify like or corresponding parts with the preferred embodiments of FIGS. 1-7. In order to vary the constricting force on the flexible pawls, the collar means 32b may be metal. At least one expansion slot 80b is required for the collar means 32b to allow radial flexibility as shown in FIG. 13. The expansion slot 80b extends through the front end 64b of the collar means 32b. The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims wherein reference numerals are merely for convenience and are not to be in any way limiting, the invention may be practiced otherwise than as specifically described.
A motion transmitting remote control assembly including a conduit and a motion transmitting core element moveably supported by the conduit. A female member matingly receives a male member in one of various positions for adjustment of the relative length of one of the conduit and the core element. The female member includes a radially flexible pawl which engages the external surface of the male member to allow axial positioning of the male member relative to the female member. A collar surrounds and is slidably disposed over the female member for preventing relative movement between the male and female members.
5
BACKGROUND OF THE INVENTION [0001] Switch and receptacle plates are mandated by building code law in every nation on the globe where electricity is available. [0002] The average home now being built in America has over 150 wall plates, primarily mandated, with some extra wall plates installed for owner convenience. [0003] Globally, hundreds of millions of wall plates are sold annually, with an increasing number of them wrapped in wallpaper, or, as with recent wall plate design, having a transparent-plastic-shielded insert that is commonly a patterned wallpaper to match the pattern of the wallpaper around the wall plate. [0004] Whether the patterned wallpaper is cut to wrap around the wall plate or cut to insert into a decor-shielded wall plate, matching the pattern of the wallpaper cut for the wall plate with the pattern of the wallpaper surrounding the wall plate is commonly a trial-and-error, time consuming task for even professional wallcovering applicators. Pattern-matching for the non-professional applicator is commonly accomplished only after cutting-and-trying several times to gain an imperfect but acceptable match. [0005] This invention organizes the steps to a flawless, first time, every time matching of remotely-cut patterned wallcovering that is to be applied on wall plates surrounded by the same patterned wallcovering on a finished wall. SPECIFICATION [0006] A template of transparent plastic with, [0007] 1. (a) various holes die cut therein, said holes configured to match various electrical switch and/or receptacle configurations including attachment screw and other holes, [0008] (b) with various printing thereon to guide the user to the impermanent attachment of the template to the desired installed switches, receptacles or combinations thereof on a wall on which wallcovering has been applied, [0009] (c) said transparent template surface-textured to allow the user, when template is secured over the desired combination of switches and/or receptacles, to pencil-mark certain chosen pattern-keys on the template over the wallcovering thereunder at points near the periphery of the template. [0010] 2. Detached from chosen switch and/or receptacle combinations, said template is, [0011] (a) taken to the identical wallcovering and pattern unrolled flat on a table-like surface, [0012] (b) momentarily attached with drafting tape over the same pattern keys on the identical wallcovering, [0013] (c) the template openings for switches and/or receptacles, and the perimeter of the wallcovering to be cut for said wall plates are pencil-marked on said wallcovering, [0014] (d) the attachment tape and template are removed from the wallcovering, pencil markings erased for the template's reuse, [0015] (e) and the matching pattern wallcovering insert or cover is cut for use in or on the wall plate, depending on the wall plate assembly design configuration. BRIEF DESCRIPTION OF THE DRAWINGS [0016] A more complete understanding of this invention and its advantages will be apparent from the detailed description when related to the following drawings in which: [0017] [0017]FIG. 1 Is a front elevation of this invention. [0018] [0018]FIG. 2 Is a front elevational view of this invention temporarily attached on a double switch combination and over an applied patterned wallcovering with the pattern keys pencil-drawn on the template. [0019] [0019]FIG. 3 Is a down-looking view of this invention positioned and temporarily corner-taped over the same pattern on an identical wallcovering material on a table-like surface remote from the double switches and applied wallcovering, having the four corner cut-keys penciled in on the rolled-out wallcovering. [0020] [0020]FIG. 4 Is another down-looking view of that same corner-marked wallcovering with the wall plate assembly decor backer-plate temporarily drafting-tape-secured within the four corner cut-keys preparatory to using the decor backer-plate as a template for using a razor-pointed knife to cut the matched pattern insert for the double switch plate. [0021] [0021]FIG. 5. Is a front elevational view of the cut pattern-matched wallcovering that is the insert now enclosed and shielded in the wall plate assembly mounted on the two switches. The screws attaching this assembly to the switches are concealed. [0022] [0022]FIG. 6 is a cross sectional view of this invention attached to a switch by means of a temporary attachment fastener. DETAILED DESCRIPTION [0023] [0023]FIG. 1 referring in detail to the drawings, this invention includes the transparent template 1 on which are the switch openings 2 , receptacle openings 3 , attachment openings 4 , cut-guideline openings 5 for conventional wall plate cover-wrapping, cut guideline curved slot openings 6 for custom wall plate inserts, and graphic outline guides 7 delineating the several switch and/or receptacle combinations included in this one template tool. [0024] [0024]FIG. 2 is an elevational view of this invention showing the template 1 mounted over a double switch 8 around which wallcovering 12 is applied to the wall, the template 1 attached to the switch 8 mechanism by means of temporary attachment fasteners 9 . [0025] Three pattern-key elements 11 of the surrounding wallcovering 12 are shown pencil-drawn in outline on the template 1 over the outline of the pattern-key figures on the wallcovering 12 thereunder.. [0026] [0026]FIG. 3 illustrates the template 1 with the pattern-key elements 11 of wallcovering identical to but remote from the wallcovering in FIG. 2 pencil-drawn on the template 1 , said template 1 temporarily taped over the pattern of the remote wallcovering 12 exactly matching that immediately surrounding the double switch openings 2 in the template, said openings shown astride the double switches illustrated in FIG. 2. [0027] Wallcovering cut-key guideline openings 5 marking the four corners of the matching wallcovering to be cut to wrap a conventional wall plate are shown. [0028] For cutting a match-pattern insert for wall plates designed to enclose and shield that wallcovering insert, only the pencil-marking of the four curved cut-key corners 6 on the underlaying wallcovering 12 is necessary to accurately cut said match-patterned insert. [0029] [0029]FIG. 4 illustrates a double switch decor backer-plate 20 centered within the four curved cut-key corners 6 penciled on the patterned wallcovering 12 that the template which is the centerpiece of this invention has located on the remote rolled-out same-pattern wallcovering 12 . [0030] The pattern-matched insert thereunder 13 can now be cut in a variety of ways. A recommended method is scissor-cutting a two-inch-oversized piece of the wallcovering 12 in which the decor backer-plate 20 , taped to and centered in the four cut-key corners which exactly outline the corners of the desired pattern-matched insert 13 , is cut out of the rolled-out wallcovering 12 . Using a razor-point blade, with the decor backer-plate 20 as a template taped 14 over the pattern-matched insert 13 , and with an out-dated magazine as a cutting board, first cutting the two switch holes 2 . [0031] Finally, cutting the perimeter of the insert 13 , using the edge of the periphery of the decor backer-plate 20 as a guide, but cutting the wallcovering under the four strips of tape 14 one at a time, replacing each strip of tape 14 after the wallcovering under its position is cut when the remainder of the insert's 13 perimeter is cut. [0032] [0032]FIG. 5 illustrates the matched-pattern wallcovering insert 13 shielded in a wall plate assembly 22 , the pattern match of the insert 13 and the adjacent wallcovering 12 now being clear. [0033] [0033]FIG. 6 is a cross sectional view of one quick-attachment type of fastener 9 temporarily securing the template 1 to a switch 8 and over the wallcovering 12 . [0034] The template 1 may also be temporarily attached to switches 8 and/or receptacles by means of the flathead screws that are included with the wall plate assembly 22 . [0035] Many modifications can be made in the exemplary structure described above without exceeding the scope of the present invention. The invention is applicable also to switches and receptacles of any configuration and the cover plates therefor by simply producing the tool of a different size and holes configuration. [0036] While a certain embodiment of the present invention has been described in detail herein and shown in the accompanying drawings, it is obvious that minor changes may be made in the form and construction of the invention without departing from the material spirit thereof.
A template to guide wallcovering applicators, be they professional or amateur, in the matching and cutting of any patterned wallcovering used to cover electrical switch and/or receptacle plates with the same patterned wallcovering applied to the wall contiguous to said wall plates.
4
TECHNICAL FIELD [0001] The invention relates to a valve control device, more particularly to a pressurized fluid control device, yet more particularly a pressurized fluid control device comprising a demultiplication of the control force and/or of the mechanical locking means. STATE OF THE ART [0002] Various devices for pneumatic valve control are known to the state of the art. [0003] Document U.S. Pat. No. 4,763,690 discloses such a device coupled with a valve for a pressurized gas bottle. This control device comprises a body adapted to be affixed to the body of a valve. The body of the device comprises a control rod at its center and movable along its longitudinal axis. The lower portion of the rod is adapted to be mechanically connected by being coupled to a movable portion of the valve itself. The upper portion of the rod is mechanically connected to a piston, movable in translation along the longitudinal axis. The upper portion of the body comprises an attached part forming the cavity in which the piston is housed. This cavity and the upper surface of the piston form a control chamber of the device. A connection port for pressurized fluid is provided at the center of the attached upper portion of the body. A spring is provided between the lower surface of the piston and the body of the device in order to maintain the control rod in the upper position in the absence of pressure in the control chamber. This position corresponds to a closed position of the valve. When the control chamber is supplied with pressurized fluid, the piston exerts a force opposing that of the spring, causing the rod to move down and open the valve. A mechanical locking device is provided. It consists in blocking the rod in the upper position by means of a control thumbwheel acting on a conical-ended rod sliding along a direction, perpendicular to the longitudinal axis. A groove corresponding to the conical end is housed in the rod. [0004] The device is advantageously simply designed, yet has a slew of drawbacks. Indeed, the locking means are outside of the device and not integrated. Moreover, the means require a manual control of the tightening, which can cause the locking means to deteriorate and/or possibly, an unsatisfactory locking. The locking of this device, because of its mechanical design, has limited power and cannot be applied to an actuator with a demultiplication of the force. Indeed, having a larger piston surface might cause, if the pressurized control fluid is present in the chamber, the blocker of the seat to be blocked and thus to slightly open the valve in spite of the locking means. [0005] Document EP 1 426 626 A1 discloses a valve for a gas bottle comprising a closing valve and a control device of the valve. The valve per se is of the conventional type, that is, comprising a movable blocker along the longitudinal axis and cooperating in a sealed manner with a machined seat in the body of the valve. The control device is of the pneumatic type, that is, activated by intake of pressurized air. It comprises a piston, movable along the longitudinal axis of the valve and connected to the blocker via demultiplication means. These means comprise four rollers housed in a chamber, symmetrically with respect to a plane comprising the longitudinal axis. A needle is rigidly connected to the piston and has the ability to come in contact via its inclined surfaces with two of the four rollers. The penetration of the needle in the rollers causes the two upper rollers to move apart which, because of their lateral displacement, push the two lower rollers downward. These two lower rollers are connected to a common movable bearing which is supported on the control rod of the actuator. The pressure of the needle thus causes the valve to close. The piston is subjected to the closing forces of the valve generated by two concentric springs. A chamber is formed by the inner surface of the piston and the cavity of the body. This chamber can be supplied with pressurized air in order to move the piston upward so as to open the valve. The device comprises locking means at the top of the body of the device. These means comprise a threaded ring with a lower surface having an inclined wall, two diametrically opposed pushers in contact with the inclined wall of the ring and in contact with a top tapered portion of the piston. Making the ring move down by a tightening movement displaces, via its tapered lower surface, the two pushers toward the center of the device. These two pushers come into pressure against the tapered surface of the top portion of the piston and thus prevent the latter from returning upward at all. [0006] Although this device has an interesting functionality, it also has several drawbacks. Indeed, manufacturing this device is rather complicated because of the large number of pieces, some of which require a complex and costly machining such as, for example, the rollers, the bearing of the rollers, and the pushers. Assembling such a device is also rather complex because of the number of pieces which need to be precisely adjusted. Additionally, activating the locking means requires a tightening operation which, with the teaching of the previous document, can cause the locking means to deteriorate and/or possibly to have unsatisfactory locking. DESCRIPTION OF THE INVENTION [0007] The object of the invention is to overcome at least one of the above-mentioned drawbacks. The invention consists of a device for controlling a valve, comprising: a body of the device with a longitudinal axis; a control member of the valve, housed at least partially in the body at a bottom portion along the longitudinal axis; a piston, movable along the longitudinal axis, the piston being housed in a portion of the body forming, with the piston, the control chamber of the piston; this chamber being adapted to be connected to a pressurized fluid intake; the device being built so that the piston is adapted to transmit its movement to the control member in view of controlling the valve; the device further comprising an element, movable in rotation with respect to the longitudinal axis on an upper portion of the body; the movable element comprising a connection port of the pressurized fluid off-centered with respect to the longitudinal axis; the control chamber comprising, opposite the movable element, a passage, also off-centered to the connection port; sealing means between the movable element and the control chamber in the area of the connection port and/or of the passage, so as to provide sealing of the feedstream when the connection port and the passage are aligned by adequately manipulating the movable element. [0008] This device has a simple security measure consisting in acting directly on the pressurized fluid intake. This security is particularly interesting in that it acts directly on the source of the force and can be activated by simple rotation of a movable element of the device. This makes it possible to combine it with other locking means which can thus be activated or deactivated by a simple single manipulation. [0009] Advantageously, the movable element comprises a disc-shaped portion, perpendicular to the longitudinal axis and comprising the connection port, the control chamber comprises an outer planar surface vis-à-vis which the disc-shaped portion of the movable element moves in rotation. [0010] Advantageously, the movable element comprises a generally cylindrical portion. The control chamber is formed by an open cavity of the body on which a lid-shaped element is fixed, preferably by being screwed, said lid-shaped element comprising the outer planar surface of the control chamber. [0011] Advantageously, the sealing means are placed in the area of the movable element. [0012] Advantageously, the sealing means comprise a joint housed in a groove outlining the orifice of the connection port and formed in the inner surface of the disc-shaped portion of the movable element. [0013] Advantageously, the outer planar surface of the control chamber comprises a track for the sealing means placed in the area of the movable element. [0014] Advantageously, the track cooperates in a sealed manner with the sealing means of the movable element so as to form the connection port when it is spaced from the passage of the control chamber. [0015] Advantageously, the sealing means are placed in the area of the control chamber, preferably the sealing means comprise a joint placed in a groove outlining the passage and formed in the outer planar surface of the control chamber. [0016] Advantageously, the disc-shaped portion of the movable element comprises a track moving by gliding on the sealing means during the rotation of the movable element. [0017] Advantageously, the device comprises mechanical blocking means of the control member of the valve with respect to the body of the device, the mechanical blocking means being preferably activated by the rotation of the movable element. [0018] Advantageously, the mechanical blocking means comprise a ring for activating said means, the ring being mounted around the body of the device via a threading, the ring comprising a mechanical connection in rotation with the movable element. [0019] Advantageously, the body comprises a push-button adapted to cooperate with the activation ring in view of indexing its position. [0020] Advantageously, the movable element is located opposite the ring and comprises a series of cylindrical elements mounted in bores parallel to the corresponding longitudinal axis and cooperating with corresponding notches housed in the ring along the longitudinal axis. [0021] Advantageously, the mechanical blocking means comprise radial compression elements cooperating with a surface, inclined with respect to the longitudinal axis of the ring and a surface, inclined with respect to the longitudinal axis of the control member. [0022] Advantageously, the radial compression elements comprise steel beads. [0023] Advantageously, means for visualizing the opening or closing state of the valve connected to the device are provided in the area of the central and upper portions of the device. [0024] These means can consist in an element attached to the piston and adapted to slide in a sealed manner with the upper wall of the control chamber. [0025] Other particularities of the invention will become apparent from the description of the example of embodiment shown in the drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0026] FIG. 1 is a planar view of the valve control device according to the invention; [0027] FIG. 2 is a cross-sectional view along the axis C-C of the device of FIG. 1 ; [0028] FIG. 3 is a cross-sectional view along the axis D-D of the device of FIG. 2 . BEST EMBODIMENT OF THE INVENTION [0029] The following description makes reference to geographical terms such as “upper”, “top”, “lower”, and “bottom”. These terms are used by way of example only in relation to the orientation of the device in the drawings, and for clarification purposes. These terms must not be interpreted as absolute and limiting, but rather only in relation to the orientation and application of the device according to the drawings. [0030] A valve control device according to the invention is shown in FIGS. 1 , 2 , and 3 . FIG. 2 shows best the details of construction of the device, FIGS. 1 and 3 showing best certain particular technical aspects. The description of the construction of the device shall therefore be based, first on FIG. 2 , and then on FIGS. 1 and 3 for the corresponding technical aspects. [0031] The valve control device 1 shown in FIG. 2 comprises a body constituted essentially of two elements, a main element 2 and an element 3 threadably attached. A control member 6 is housed slidably along the longitudinal axis of the device. This control member 6 comprises, at its lower end, means for attachment to a valve blocker (not shown). These attachment means are made, in the case of this embodiment, by a threaded bore 7 . The control member 6 is part of a mechanism for stepping down the control force which is described hereinafter. [0032] A piston 4 is housed in the upper element 3 of the body of the device. This element 3 comprises a lower cylindrical portion in which the piston 4 is housed so as to slide along the longitudinal axis of the device. The main element 2 of the body further comprises a through-hole for guiding the lower end of the control member 6 , a cavity essentially symmetrical in revolution adapted to receive the control member. The latter comprises a larger cylindrical portion adapted to slide in the body 2 . The inner surface of this cylindrical portion defines, with the sealing means present between the cylindrical portion and the cavity of the body 2 and between the lower end and the through-hole of the body 2 , a high-pressure chamber 11 filled with oil. The control member further comprises a narrower upper portion shaped as a chimney. A stack of springs 9 of the Belleville type is pulled on around this top portion of the control member. These springs are supported on an abutment 8 housed and fixed in the body 2 by threading. These elastic means thus exert a permanent force on the control member 6 directed downwardly in the closing direction of the valve. [0033] The top portion of the control member comprises a cylindrical bore opening out onto its upper end. A hydraulic piston 5 is housed slidably and sealedly in this bore. The hydraulic piston 5 is rigidly connected to the pneumatic piston 4 . The sealing means (here conventionally an O-ring type joint) between the hydraulic piston and the bore of the control member form the hydraulic chamber 11 . The hydraulic piston 5 comprises means for filling with control and closing oil. [0034] The upper surface of the pneumatic piston 4 and the upper element 3 of the body of the device form a control chamber of the piston. In FIG. 3 , the chamber is reduced to an almost null volume since the piston is in contact with the inner surface of the disc-shaped portion of the upper element 3 . Once this chamber has been supplied with compressed air, the upper surface of the piston 4 is subjected to a force resulting from the air pressure present in the chamber and from the effective surface of the piston. This force makes the pneumatic piston 4 and the hydraulic piston 5 move down. The latter, by moving downwardly, increases the oil pressure in the chamber 11 , which makes the control member 6 move back up against the force of the springs 9 and causes the valve to open. This demultiplication mechanism allows for reversing the control force of the pneumatic piston and also for amplifying the control force. Indeed, the force to which the control member 6 is subjected by the hydraulic fluid in the chamber 11 corresponds to the control force of the pistons 4 and 5 multiplied by the ratio of surfaces between the effective surface of the control member (the ring on its lower surface) and the effective surface of the hydraulic piston 5 (neglecting friction losses). [0035] Mechanical locking means are provided in the area of the control member 6 . They comprise three pairs of beads arranged in through-holes perpendicular to the longitudinal axis. Each pair of beads is housed in a respective through-hole; these through-holes are uniformly distributed along axes at 120° from one another. Each through-hole opens out onto the outside and the inside of the main element 2 of the body. The control member comprises a section whose lateral surface is inclined. The most central bead of each pair is in contact with this surface section. These pairs of beads are movable along the through-hole axis so as to serve as a mechanical abutment for the surface section of the control member. A ring 12 for activating locking means is provided around the main element 2 of the body of the device. This ring 12 has a generally cylindrical shape with an outer surface that is knurled to facilitate manipulation. The ring 12 is mounted on the body by means of a threading in order to be able to displace it along the longitudinal axis by a manipulation in rotation. It comprises opposite the through-holes in which the beads are housed a continuous symmetrical surface in revolution which is inclined. The effect of the progressive downward movement of the ring 12 by manipulation in rotation is to displace the pairs of beads slightly toward the longitudinal axis of the device and to put them in pressure against the section of inclined surface of the control member, thus ensuring a mechanical locking. The surface section is inclined so that the pressure of the beads on it generates a force directed downwardly, which is the closing direction of the valve. [0036] The air or fluid intake under pressure in the control chamber is controlled by the position of the movable element 13 . The latter has the shape of a bell or that of a cylinder closed at the top by a disc-shaped surface. It is movably mounted in rotation on the body of the device supported on the outer surface of the main element 2 and the upper element 3 of the body of the device. It is kept in place by a series of screws arranged radially in the thickness of the skirt so as to cooperate with a groove (no reference number) provided in the top portion of the main element 2 of the body. The location of these screws can be visualized by the two small circles in the area of the skirt of the movable element 13 of FIG. 1 . The movable element 13 comprises a port 19 for connecting to a source of pressurized fluid. This port is in fact a threaded orifice in which a connection coupling 15 is screwed. This connection port 19 is off-centered with respect to the longitudinal axis. The orifice of the port 19 opens out onto the inner surface of the disc-shaped portion of the movable element 13 . The outer upper surface of the upper element 3 of the body of the device is located opposite the inner surface of the disc-shaped portion of the movable element 13 . It comprises a through orifice 17 similarly off-centered with respect to the connection port 19 . This through orifice is directly connected to the control chamber of the pneumatic piston 4 and constitutes the only connection for supplying this chamber with compressed fluid. Sealing means are provided in the area of the connection port 19 . They consist of a joint 16 , typically of the O-ring type, arranged in a groove formed in the inner surface of the movable element 13 and surrounding the orifice of the connection port 19 . This joint 16 is adapted to ensure the sealing of the feedstream supplying the control chamber when the connection port 19 and the through orifice 17 are aligned. [0037] Housing the joint into a groove ensures a better hold than a simple spot facing. In addition, the inner diameter of the joint is greater by a ratio of at least 2 to 1, preferably 3 to 1, with respect to the inner diameter of the through orifice. This measurement allows for the joint to pass above the through orifice without getting hooked. The outer upper surface of the upper element 3 of the body of the device constitutes a track along which the joint 16 slides when the movable element 13 is manipulated in rotation. When the movable element 13 is in an angular position such that the joint 16 is completely spaced from the through orifice 17 , the pressurized fluid intake is closed and, in addition, the control chamber of the pneumatic piston 4 is open out to the air by the intrinsic leaks between the outer and the inner surfaces of the upper element 3 of the body and the movable element 13 , respectively. The manipulation in rotation of the movable element plays the role of a valve for pressurizing or placing in the air the control chamber and also the role of closing the pressurized fluid intake. This constitutes an additional security which can become necessary due to the large demultiplication ratio of the device. Indeed, although the mechanical locking means act directly on the control member 6 of the valve, they can become insufficient to prevent the closing, even partial, of the valve when the control chamber of the pneumatic piston is supplied with air. Cutting the air supply of the chamber provides additional security. [0038] Connecting means in rotation are provided between the movable element 13 and the locking ring 12 . They consist of small cylinders or pins 14 housed in parallel to the longitudinal axis in through holes in the section of the lower portion of the movable element 13 . These through holes are uniformly distributed on the periphery of the movable element 13 . These pins 14 project slightly over the section of the lower portion of the movable element 13 . The outer surface of the ring 12 is provided, at its upper edge, with a series of recesses 20 , partially cylindrical and parallel to the longitudinal axis of the device and uniformly distributed on the periphery so as to correspond with the pins 14 . Thus, the ends of the projecting pins of the movable element 13 cooperate with the recesses or notches 20 so as to provide a rotational connection between the movable element and the activation ring of the mechanical locking means while allowing for a relative displacement between these two along the longitudinal axis. The rotational manipulation of the ring 12 thus drives the movable element 13 . [0039] A push-button 18 is provided at the bottom of the main element of the body of the device, arranged along a radial direction, perpendicular to the longitudinal axis. The push-button thus cooperates with a corresponding orifice provided in the lower portion or skirt of the ring 12 . During the rotational manipulation of the ring, the push-button, once aligned, penetrates in the orifice of the skirt of the ring 12 . This corresponds to the operational position of the device whereby the mechanical locking means are deactivated and the connection port 19 and the through-orifice 17 of the control chamber are aligned. [0040] Means for visualizing the closed and/or open state of the valve connected to the device can be provided at the top of the device (not shown in the drawings). These means can comprise an element attached to the piston 4 and capable of moving along the longitudinal direction in a sealed manner with the upper element 3 of the body forming the upper wall of the control chamber. Indeed, this upper element can have a central extension in the shape of a chimney or cylinder with sealing means cooperating with a visualization cylindrical element (not shown) moving along the longitudinal axis along with the piston 4 . The movable element can comprise a central opening at its upper portion which cooperates with the cylindrical extension at the top of the upper element of the body of the device. This cylindrical portion can have the shape of a chimney or boss depending on the application. A transparent lid could be fixed at the top of the device to protect this visualization element and the sealing means while allowing for visualizing the position of the element. Various alternatives or improvements of the visualization means known to one having ordinary skill in the art are naturally applicable to this device, knowing that it is the fact of off-centering the port of connection to the pressurized fluid that frees, in an inventive manner, the central portion of the top of the device. [0041] Although the invention is fully realized in combination with a mechanism for amplifying the force resulting from the pneumatic portion and with mechanical locking means, nevertheless, the very essence of the invention is applicable to other configurations, in particular to a control device comprising a pneumatic portion and without amplification and/or without locking means. The principle of controlling the supply of pressurized fluid remains applicable and presents the same advantages of security. [0042] Various alternatives to the exemplary embodiment described above can be envisioned. Indeed, the amplification device with the oil chamber can be replaced with other amplification devices. The movement inversion provided by the device of amplification with oil is not compulsory. Indeed, it could be envisioned for the chamber in question to be on the other surface of the piston portion of the control member so as to displace it downwardly in case of pneumatic piston control. In this case, the springs or other elastic means would be arranged on the other side, that is, on the side of the chamber according to FIGS. 1-3 and the device would be applicable to a valve whose closing would be carried out by an upward movement of the blocker. The mechanical blocking means do not necessarily have to comprise beads. Various equivalent alternatives can be envisioned, such as, for example, cylindrical pushers. Only one or three beads per through hole is also possible as a function of the thickness of the wall of the body of the device. The number of through holes depends on the overall size of the device. Only two diametrically opposed through holes or four or even more, distributed uniformly, or not, could also be provided. [0043] The sealing means between the connection port 19 and the through orifice 17 of the control chamber can be arranged on the outer surface of the upper element 3 of the body, similarly to the arrangement of FIGS. 1-3 . In this case, the connection port would be opened out to the air as soon as it would be spaced from the sealing means. In such position, the control chamber would be closed insofar as the sealing means would be in sealed contact with the inner surface of the movable element. The portion of this surface serving as a track for the sealing means could also be made to prevent leaks and place the chamber in ambiance. [0044] Other rotational connection means between the movable element and the activation ring of the mechanical locking means can be envisioned.
The invention relates to a valve control device, the device including a hydropneumatic mechanism for amplifying the force resulting from the presence of a pressurised fluid in a control chamber consisting of a piston ( 4 ) housed in the body ( 2, 3 ) of the device. The piston ( 4 ) is rigidly connected to a piston ( 5 ) with a smaller cross-section and tightly engaging with a control member ( 6 ). The downward movement of the piston with the smaller cross-section ( 5 ) engages with a hydraulic chamber so as to increase the pressure inside said chamber and to move the control member ( 6 ) in the opposite direction. A connection port ( 19 ) for supplying the pressurised fluid is provided on a rotatably mobile element ( 13 ) on top of the device. Said port ( 19 ) is off-centre relative to the longitudinal axis, so as to be aligned with an opening ( 17 ) for supplying the control chamber. A seal is provided between the two surfaces comprising the port ( 19 ) and the opening ( 17 ) so as to seal the fluid stream when both elements are aligned. The mobile element ( 13 ) is rotatably attached to the ring ( 12 ) for activating the mechanical locking means ( 10 ) of the control member ( 6 ). In this way, a single operation of the ring ( 12 ) makes it possible to deactivate the mechanical locking means and to supply the control chamber with pressurised fluid.
5
FIELD OF THE INVENTION [0001] The present invention relates to the field of pneumatic drilling machines, more specifically, pneumatic drilling machines which automatically terminate the supply of compressed air to the machine after a drilling cycle is complete. BACKGROUND OF THE INVENTION [0002] Positive feed pneumatic power drilling machines are widely used in many industries. Such drilling machines normally have a single motor for turning a spindle through a drive gear train. The spindle is threaded into a feed gear that turns at a predetermined rate faster than the turning rate of the spindle for advancing the spindle as the drill progresses through a work piece. The feed gear is driven by a gear train from the same motor as the drive gear train. The gear ratio of the drive gear train is selected to be slightly less than the gear ratio of the feed gear train so the feed gear will turn slightly faster than the drive gear. In that way, the spindle is advanced a predetermined amount for each turn. Once the spindle has been advanced sufficiently, a mechanism is actuated to disengage the spindle feed gear train from the motor and lock it in place. As the motor continues to drive the spindle in the same direction, the spindle threads turn inside the locked feed gear to rapidly retract the spindle. [0003] Prior art mechanisms for disengaging the gear trains from the motor have included mechanical switches for interrupting the supply of compressed air to the motor. The inclusion of mechanical switches in a pneumatic drilling machine have certain disadvantages. First, they are difficult to assemble, requiring delicate placement of the moving parts within the switch. Further, the delicate parts of the switch are prone to wear and tear, and detract from the longevity of the drilling machine as a whole, which otherwise benefits from a reduction in the number of moving parts that pneumatic tools generally provide. [0004] Another aspect of prior art drilling machines is that they include pneumatic counting devices, for counting the number of drive cycles carried out by the machine. This allows the owner to carry out the required maintenance on the machine at a proper interval. However, a feature of the prior art counters is that they typically have been configured to add one cycle to the total count each time the motor is switched on. This is disadvantageous because a drill user will often turn the drill off, and then on again, a number of times in the middle of the feed mode. Thus, a single feed cycle may be counted as a number of cycles. This has the undesirable effect of indicating that the drill has been used more often than it really has been, and leads to uneconomical servicing of the machine. [0005] Thus, a need exists in the art for a pneumatic drill with a pneumatically operated switch for turning off the motor. A need also exists for a counting system that counts feed cycles of the drill only at the completion of a feed cycle. It is believed that the present invention addresses these and other needs. SUMMARY OF THE INVENTION [0006] According to a preferred embodiment of the invention a pneumatic drilling machine with an automatic control system is described. [0007] In a preferred embodiment, the drilling machine comprises a pneumatic motor, a tool holder spindle, and a drive mechanism connecting the motor to the spindle. The drive mechanism is configured to drive the spindle through a driving cycle, the driving cycle commencing and ending with the spindle being stationary. The driving cycle also includes a feed mode and a retraction mode. [0008] In a preferred embodiment, the drive mechanism will include a pneumatic circuit and a control valve positioned in the circuit. The control valve is movable between a first position to select the feed mode, and a second position to select the retraction mode. [0009] A supply valve is provided, positioned in the pneumatic circuit for supplying compressed air to the motor. The supply valve is movable between a closed position in which compressed air to the motor is interrupted and an open position in which air to the motor is supplied. A coupling shaft is also provided for changing the driving mode of the driving mechanism. The coupling shaft is axially biased by a coupling spring into a coupling chamber positioned in the pneumatic circuit. [0010] The drive mechanism is configured to send, at the end of the driving cycle, a pneumatic signal to the supply valve via the pneumatic circuit, and the supply valve is configured to close upon receiving the pneumatic signal. In a preferred embodiment, the pneumatic signal is a bolus of air expelled from the coupling chamber by the bias of the coupling spring. [0011] Another aspect of the invention is that the pneumatic circuit includes a connector for receiving compressed air, and the control valve is configured in relation to the pneumatic circuit so that, when the control valve is in the first position the coupling chamber is not open to the connector via the pneumatic circuit, but is open to the shut-off chamber. Yet another aspect of the invention is that the control valve is configured in relation to the pneumatic circuit so that, when the control valve is in the second position the coupling chamber is open to the connector via the pneumatic circuit, but is not open to the shut-off chamber. [0012] A still further aspect of the invention is that the supply valve includes a shut-off piston positioned within a shut-off chamber and the coupling shaft includes a coupling piston positioned within the coupling chamber. In a preferred embodiment, the diameter of the shut-off piston is at least twice as large as the diameter of the coupling piston. In this embodiment, the bolus of air expelled from the coupling chamber is directed by the pneumatic circuit to the shut-off chamber of the supply valve. The bolus of air raises the pressure in the shut-off chamber to close the supply valve, and hence interrupt the supply of air to the motor. [0013] A further feature of the invention is that the drive mechanism further includes a cycle counter configured to add one count only at the commencement of a retraction mode of driving the spindle. [0014] These and other advantages of the invention will become more apparent from the following detailed description thereof and the accompanying exemplary drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0015] FIG. 1 represents a perspective view of a portable pneumatic drilling machine showing features of the invention. [0016] FIG. 2 is a schematic view showing aspects of a driving mechanism which controls the power supply and automatic shutoff of compressed air supply to the drilling machine of FIG. 1 , schematically showing aspects of the drive mechanism in standby mode. [0017] FIG. 3 is the schematic view of the preceding Figure, schematically showing aspects of the drive mechanism in idle mode. [0018] FIG. 4 is the schematic view of the preceding Figures, schematically showing aspects of the drive mechanism in feed mode. [0019] FIG. 5 is the schematic view of the preceding Figures, schematically showing aspects of the drive mechanism in retraction mode. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0020] With reference to FIG. 1 , a pneumatic drilling machine, generally referred to by the numeral 20 , and method according to a preferred embodiment of the present invention, is described. In general terms, the machine 20 illustrated in the figure is surrounded by a housing 22 and includes a conventional pneumatic motor 24 . The motor is connectable to an external source of compressed air 25 (not shown in FIG. 1 ) through a connector 26 . A tool holder spindle 28 held by the housing 22 is adapted to be rotatable about its axis A, and to move the tool back and forth along its axis A. A mechanism 30 for driving the spindle and for controlling the movement of the spindle 28 is located within the housing. Drilling tools can be mounted and removed from the spindle in a conventional manner. [0021] The drive mechanism 30 , which is schematically exemplified in FIGS. 2-5 , includes a conventional mechanism known as a positive feed drill. An external source of compressed air 25 supplies compressed air to the drive mechanism 30 via the connector 26 . Within the drilling machine housing, the compressed air is circulated, as described herein, through a series of ducts which collectively form a pneumatic circuit. FIGS. 2-5 exemplify additional features of the present invention, and, in the description below, the terms “lower,” “upper,” “horizontal,” “left,” and “right” relate to FIGS. 2-5 . [0022] In a preferred embodiment, the drive mechanism 30 includes a lower gear (or, drive gear) train 32 comprising gears 34 , 36 , 38 , 40 , and 42 intermeshing in series, and an upper gear (or, feed gear) train 44 comprising gears 46 , 48 , 50 , and 52 intermeshing in series. The spindle 28 passes through the end gears 42 and 52 of each gear train. The lower and upper gear trains may be stationary, or rotate in various modes, as described herein. [0023] In the idling mode, power is supplied via the motor 24 to lower gear 34 , which imparts power only to the lower gear train 32 . In this mode, the upper gear train 44 rotates only under frictional connection with the lower gear train 32 , so that lower and upper gear trains rotate at the same speeds, causing the spindle to rotate under power, but not causing the spindle to advance or retract along its axis A. [0024] In the feed, or advancing, mode, lower gear 34 is supplied with power from the motor 24 as before, but upper gear 46 is caused (as described herein below) to engage via conventional dog collar linkage to lower gear 36 , thus placing both upper and lower gear trains under power. The number of teeth of upper and lower gear trains are selected to differ by preferably one or two teeth, causing the upper (feed) gear 52 to rotate about the spindle 28 at a slightly faster speed than lower (drive) gear 42 . By conventional means, this difference in rotation speeds is harnessed to cause the spindle 28 to advance downwardly at a relatively slow speed through the upper end gear 52 and the lower end gear 42 , while simultaneously rotating clockwise. [0025] In the retraction mode, lower gear 34 is supplied with power from the motor as before, but upper coupling gear 46 is caused (as described herein below) to move upward to engage by conventional dog collar means a braking disc 54 which is fixed to the housing and unable to rotate. It will be appreciated that, under these conditions, the upper gear 44 train cannot rotate at all. It will be further appreciated that in this mode the lower gear train 32 will rotate faster than the upper gear train by a relatively large difference. By conventional means, this large difference in rotation speeds is harnessed to cause the spindle 28 to retract at a relatively rapid rate through the upper end feed gear 52 and the lower end drive gear 42 , while simultaneously rotating clockwise. [0026] A further aspect of the drive mechanism 30 is the supply valve 56 positioned between the external compressed air supply 25 and the motor 24 . The supply valve 56 includes a shaped slide 58 movable within a cylinder 60 . The top of the cylinder 60 may be connected by air duct 61 to a micro valve 63 that presents an exposed surface or button 62 for manually activating the micro valve 63 which, in turn, activates the supply valve 56 . The slide 58 is configured so that, upon downward displacement ( FIGS. 3-5 ), it will permit the passage of compressed air from the source 25 via duct 59 through the valve 56 to the motor 24 . At the lower end of the supply valve 56 is a shut-off piston 64 connected to the slide 58 . The shutoff piston 64 resides within a shut-off chamber 66 . A sufficient pressure in the shut-off chamber 66 is capable of lifting the shut-off piston 64 and slide 58 upwards to interrupt the supply of compressed air to the motor 24 . ( FIG. 2 ) [0027] Yet another aspect of the drive mechanism 30 is the coupling shaft 68 which is configured to rotate in, and slide through, lower coupling gear 36 and to rotate in, but to be translationally connected with, upper coupling gear 46 . Thus, any translational movement of the coupling shaft 68 will translationally carry upper gear 46 with it. A coupling spring 70 is positioned to bias the coupling shaft 68 downward. Adjacent the coupling shaft is an idler lock 72 , having an arm 74 configured to removably engage with an indent 76 in the coupling shaft 68 . A torsion spring 78 torsionally biases the idler lock 72 . Fixed above the upper gear 46 is the braking disc 54 fixed to the housing and unable to rotate, so that an upward movement of the coupling shaft 68 engages upper gear 46 with the braking disc 54 , a downward movement of the coupling shaft engages gear 46 with gear 36 . In an intermediate position, the coupling shaft 68 is free from connection with either the brake disc 54 or the lower gear 34 . Connected to the lower end of the coupling shaft 68 is a coupling piston 80 residing within a coupling chamber 82 . A sufficient pressure in the coupling chamber 82 is capable of lifting the coupling piston 80 and coupling shaft 68 against the bias of the spring 70 . [0028] Another aspect of the drive mechanism 30 is the control valve 85 that includes a shaped stem 86 sliding within a cylinder 88 . A supply of compressed air is brought directly from the compressed air source 25 to the control valve 85 by a duct 90 . The control cylinder 88 is connected via a duct 92 with the coupling chamber 82 , and via a duct 94 with the shut-off chamber 66 . The control valve 85 is configured to have two modes, corresponding with two vertical positions of the shaped stem 86 within the cylinder 88 . In a first mode, the stem 86 is in an upper position and configured to pneumatically connect the coupling chamber 82 with the shut-off chamber 66 via duct 92 and duct 94 , but prevent the supply of compressed air 25 to both the shut-off chamber and the control chamber, as exemplified in FIG. 2 . In a second mode, the stem 86 is in a lower position and permits compressed air to be fed from the compressed air source 25 to the coupling chamber 82 , but interrupts the pneumatic connection between the coupling chamber 82 and the shut-off chamber 66 , as exemplified in FIG. 5 . [0029] The vertical position of the stem 86 of the control valve 85 may be set by movement of the spindle 28 , as follows. An upper spindle nut 98 is attached to the spindle 28 so that downward movement of the spindle brings the upper spindle nut 98 in contact with an upper valve arm 100 to move the stem 86 downwards. A lower spindle nut 102 is attached to the spindle 28 so that upward movement of the spindle brings the lower spindle nut in contact with a lower valve arm 104 to move the stem upwards. [0030] A further aspect of the drive mechanism is that it includes a pneumatic counting device 106 , pneumatically connected with coupling chamber 82 via duct 108 . The counting device may be a commercially available counting device such as Part No. PM1421 by Ellis/Kuhnke Controls, of Atlantic Highlands, N.J. 07716. The counting device is adapted to count the number of drive cycles performed by the drilling machine so that service requirements on the machine may be performed as required. Each time compressed air is delivered to the coupling chamber 82 (as described herein below), the counting device will add one cycle to the total number of cycles counted. [0031] In use, the drilling machine 20 may be operated as follows. [0032] The drive mechanism is initially configured in a standby mode, as schematically represented in FIG. 2 . In standby mode, the supply valve 56 is closed in a first position, thus interrupting supply of compressed air 25 to the motor 24 . The coupling shaft is in an intermediate position, held in place by the arm 74 on the idler lock 72 . The control valve 85 is in an upper first position with the slide 86 interrupting supply of compressed air to the coupling chamber 82 . [0033] The standby mode may be followed by the idle mode, as schematically represented in FIG. 3 . The motor is activated by manually depressing the start button 62 . The momentary opening of the micro valve 63 directs an air signal above the slide 58 of the supply valve 56 via the duct 61 displacing the slide to open the supply valve, and thus opening the compressed air supply going to the motor 24 , to cause the motor to turn and supply power to lower gear 34 , and hence to the entire lower gear train 32 . At this stage the coupling shaft 68 is positioned in an intermediate position so that gear 46 is engaged with neither the brake disc 54 nor lower gear 36 . In this position the drive mechanism 30 is in the idle mode, with the spindle 28 under rotational or driving power from the lower gear train 32 , but not under translational or feeding power. [0034] The idle mode may be followed by the feed mode, as schematically represented in FIG. 4 . In order to engage the upper gear train 44 to advance the spindle 28 , the idler lock 72 may be turned sufficiently to allow the arm 74 to disengage from the indent 76 in the coupling shaft 68 . This will allow the coupling shaft 68 under the biasing action of the spring 70 to move down and engage the upper coupling gear 46 with the lower coupling gear 36 . The tool now enters the feed, or advancing, mode, with the spindle 28 rotating and being advanced slowly under power. The feed action of the spindle will continue until the upper spindle nut 98 reaches and pushes down on, the upper valve arm 100 to depress the stem 86 within the cylinder 88 of the control valve 85 , as exemplified in FIG. 5 , thus leading to the retraction mode, as detailed below. [0035] The feed mode may be followed by the retraction mode, as schematically represented in FIG. 5 . The downward movement of the control valve stem 86 allows compressed air to flow into the coupling chamber 82 , forcing up the coupling piston 80 and hence the coupling shaft 68 , thereby ending the spindle feed process by disengaging the upper coupling gear 46 from lower coupling gear 36 , and locking the upper gear 46 against the brake disc 54 of the upper housing. The immobilization of the upper gear train 44 will initiate the retraction phase (or return cycle) characterized by a fast return of the spindle (about 1 mm per revolution), until the lower spindle nut 102 reaches and elevates the lower valve arm 104 , returning the valve stem 86 to its first upper position, as exemplified in FIG. 2 , thereby to end the retraction mode, as set forth below. [0036] The return of the valve stem 86 to its first position firstly disconnects the compressed air supply 25 from the coupling chamber 82 ( FIG. 2 ), and, almost simultaneously, connects duct 94 with duct 92 , thus pneumatically connecting the coupling chamber 82 with the shut-off chamber 66 . It will be appreciated that when the stem 86 was in its second lower position, the pressure in duct 94 was around atmospheric pressure, but the pressure in the coupling chamber 82 was under compression from the source 25 , which may be in the region of 90 p.s.i. Thus, when the upward movement of the stem 86 disconnects the coupling chamber 82 from the compressed air supply 25 , but connects the coupling chamber 82 to the shut-off chamber 66 , the compressed air present in the coupling chamber 82 is at an elevated pressure (i.e. well above atmospheric pressure) and will rapidly discharge into the shut-off chamber 66 until the pressure in both chambers 82 and 66 and their related ducts is equalized. Furthermore, at the same time, the coupling spring 70 biases the coupling piston 80 downwards, adding to the escape of air from the coupling chamber 82 into the shut-off chamber 66 by expressing an additional volume, or 37 bolus,” of air (about 0.1 cu. inches) from the coupling chamber 82 . It will be appreciated that the resulting upward force applied to the shut-off piston 64 will lift the supply valve slide 58 to its upper first position ( FIG. 2 ) to cut connection of the main air supply 25 to the motor 24 , thus shutting off the motor 24 . The drive mechanism is now in standby phase, the same condition it was in prior to pressing button 62 . To start the whole cycle over, the user may press button 62 once again. [0037] It will be appreciated that the manner in which the supply valve 56 is closed, as described in the preferred embodiment, may be accomplished by transmitting a pneumatic signal directly to the supply valve via the pneumatic circuit within the housing, specifically by the ducts 92 , 94 . Thus, in a preferred embodiment, the force applied upon the valve 56 to move it to a closed position is a positive pneumatic force, i.e., a force not applied by a mechanical action upon the supply valve itself. Moreover, in another aspect, the source of the pneumatic signal may derive from a fixed quantity of air trapped at elevated pressure within a reservoir located in the drive mechanism. In a preferred embodiment, the reservoir may include the coupling chamber 82 , its supply duct 92 , and also may include a volume defined by the cycle counting device 106 and its supply duct 108 if present. The fixed quantity of air trapped at elevated pressure within a reservoir located in the drive mechanism may be distinguished over an effectively limitless supply of compressed air from the main source of compressed air 25 which is not trapped in the drive mechanism. [0038] A significant aspect of a preferred embodiment of the invention is that the ending position of the slide 86 of the control valve 85 at the end of a drilling cycle is the same as its starting position prior to activation of the drilling cycle, and that, at both the start and the end of a drilling cycle (as seen in FIG. 2 ), the main compressed air supply 25 to the motor 24 is closed by the supply valve 56 and the compressed air supply to the coupling chamber 82 is closed by the control valve 85 , thus giving rise to a completed cycle of operation in all respects. If, for example, the slide 86 connected the compressed air supply 25 with shut-off chamber 66 upon the upward movement of the slide 86 at the end of a drilling cycle, the compressed air has raised the slide 58 to turn off the motor 24 . However, it will be appreciated that compressed air would now be supplied to the shut-off chamber 66 at the start of a new drilling cycle, a condition which may prevent the slide 58 from being downwardly activated, with disruptive consequences. [0039] An additional aspect of the drilling machine is the emergency valve 110 with its activation button 112 . The valve 110 is also a micro valve, configured to direct compressed air from the source 25 direct to the shut-off chamber 66 of the supply valve 56 via a duct 114 . As will be appreciated, the compressed air in the shut-off chamber 66 will force the slide 58 of the supply valve upwards to interrupt air supply to the motor 24 . In case of an emergency, depressing the activation button 112 will activate the micro valve 110 which in turn will shut off the supply valve 56 and the motor 24 . A bleed hole in the shutoff chamber 66 allows for the decompression of the chamber 66 , thus allowing the supply valve 56 to be turned on again. [0040] A further significant feature of a preferred embodiment of the invention is that the cycle counter 106 is pneumatically connected to the coupling chamber 82 . This has the advantage that a driving cycle is only counted once the spindle has completed a feed phase, marked by the advance of the control valve 85 to its second position, upon the drive mechanism entering the retraction phase. Accordingly, if the emergency shutoff valve 110 is activated by pressing emergency button 112 in the middle of a feeding phase, an additional cycle will not necessarily be added to the counter when the motor is turned on again. Only upon the commencement of a retraction phase will the counter add one cycle to the total. It will be appreciated that this feature has an advantage over systems that add one cycle to the total every time the motor is switched on. In such machines, interrupted but recommenced drive cycles count as a full cycle upon each recommencement, thus biasing the total count to a higher level than actually carried out by the drilling machine, and leading to uneconomical servicing of the machine or replacing its accessories such as drill bits. [0041] Thus, the preferred embodiments of the invention provide for an inexpensive and reliable device and method for automatically controlling a drilling machine. The use of a pneumatic control over the supply valve 56 , which controls the supply of compressed air to the drive mechanism, eliminates the dangers present in the use of mechanical parts which tend to wear down during the lifetime of a drilling machine. Moreover, a pneumatic control system is typically easier to assemble than a mechanical control system, and eliminates much of the labor intensive operation of assembling the small mechanical pieces of a mechanical control system. [0042] While a particular form of the invention has been illustrated and described, it will also be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited except by the appended claims.
A pneumatic drilling machine is provided, comprising a pneumatic motor, a circuit for connecting the motor to a source of compressed air, a tool holder spindle, and a drive mechanism. The drive mechanism comprises a coupling shaft which can be moved to select a first mode of driving the spindle and a second method of driving the spindle. The mechanism has a driving cycle which comprises a stationary mode at the beginning and end of the cycle, and at least one phase for driving the spindle according to the first driving method, then a phase for driving the spindle according to the second driving method, then the stopping of the supply of air to the motor. A supply valve of the circuit is controlled pneumatically by the drive mechanism to interrupt the supply of compressed air to the motor at the end of the driving cycle.
1
RELATED APPLICATION This application claims the benefit of United States Provisional Application Serial No. 60/160,102, filed Oct. 18, 1999. BACKGROUND The present invention relates generally to a bracket for attachment to a movable window and connection to an automotive window lifting mechanism, and relates more specifically to a window bracket having at least one flexible beam which engages the window. In vehicles, and especially automobiles, it is highly desirable to have movable windows. With reference to automobiles, windows are displaceable upwardly and downwardly relative to a door assembly by use of a manual crank or an electrically-driven window lifting mechanism. Many window lifting mechanisms include a scissoring linkage which transfers motion from a manual crank or electric drive to a window connected to the window lifting mechanism. The scissoring linkage is used in order to limit the movement of the window in a generally vertical direction. A cross member is attached to the scissoring linkage to provide a support for the movable window. Such a window lifting mechanism is disclosed in U.S. Pat. No. 5,513,468, which is hereby incorporated herein by reference in its entirety. Mounting brackets or window lift brackets are often used to attach the movable window to the cross member attached to the scissoring linkage. These brackets generally are attached to a mounting edge of the window at two spaced apart locations and a portion of the bracket is attached to the window lifting cross member. Many prior art brackets present problems in a movable window assembly, are difficult to manufacture, and are relatively expensive. Some prior art brackets are manufactured from a stamped strip of metal which is deformed to a specified bracket configuration. These deformed metal components are subject to damage and failure as the result of corrosion thereby providing a weak link in the movable window assembly. With regard to the manufacturing of such prior art window lift brackets, many opportunities for complications and defects arise. Initially, a strip of metal is stamped or cut to a desired size. Next, the metal component is stamped, bored or drilled to provide through holes which will be used as described here and below. The stamped metal component is deformed to form a bracket having a generally “Y” shaped cross section. The deformed metal component must now be protected by painting, anodizing or other means to delay the corrosion process. Once protected, plastic mounted clips are positioned in a channel portion of the bracket and secured in the thru holes by use of a heat staking process. The base of the bracket is drilled for receiving a fastener which will be used to attach the bracket to the lift mechanism cross member. In applying such prior art lift brackets to a window, an adhesive is disposed in the channel portion of the lift bracket and the lift bracket is attached to the mounted edge of a movable window. The window, with two or more brackets positioned thereon, is subjected to a heat curing process in order to cure the adhesive. A heat curing adhesive is used in order to properly adhere the adhesive to the surfaces of the bracket and window. As may be understood from the description hereinabove, there are numerous opportunities for problems to arise in the manufacture of a window lift bracket as set forth by the prior art. For example, if the bracket is not properly formed, it may not properly fit on the window or function in the movable window assembly. In each step of the fabrication process a new operation, coating, or joining method is used, each presenting its own opportunity for problems. For example, as mentioned, clips must be used with the deformed metal bracket in order to prevent the bracket from scratching the window glass and the protective coating on the window. The plastic clips are an individual piece part which must be designed, purchased, and managed in the manufacturing system. The clips are typically produced by selectively cutting an extruded plastic strip. Each clip must be cut to a generally precise dimension thereby requiring an additional inspection step. The clips must also be heat staked to the metal bracket. The heat staking process deforms a portion of the plastic clip over an abutting portion of the metal bracket. If the plastic portion is not properly melted, it may not be securely held to the metal bracket which could result in a release of the window from the bracket under certain circumstances. Clearly, it is not desirable to have a release of the window from the bracket. Additionally, an adhesive is disposed in a channel portion of the metal bracket to secure the window to the bracket. The adhesive must be selected to attach or adhere to the metal bracket (or the protective surface of the metal bracket) and the window glass and/or coating. The numerous and diverse material properties involved can make selection of an appropriate adhesive somewhat difficult. Further, if the metal bracket begins to corrode, the corrosion could result in the adhesive detaching from the metal bracket. As may be clear, there are numerous problems associated with the manufacture and use of metal window lift brackets as currently used in the prior art. As such, it is important to find a window lift bracket which will overcome the problems associated with the prior art devices. A window lift bracket which overcomes many of the problems presented by some prior art window brackets can be found in U.S. Pat. No. 5,513,468, which has been incorporated herein in its entirety be reference hereinabove. The bracket which is disclosed in the '468 patent is also generally illustrated in FIG. 1 of the present application, as is designated with reference numeral 10 . The bracket 10 includes a base 12 which is configured for attachment to a window lifting mechanism (see FIG. 1 of the '468 patent), and spaced apart sidewalls 14 which extend from the base 12 and define a channel 16 which receives an edge of the window (see FIGS. 1, 6 and 7 of the '468 patent). Each of the sidewalls 14 includes alternating protrusions 17 and depressions 18 which define a convoluted surface. As described in the '468 patent, the convoluted surfaces increase the effective surface area of the inside surface of the sidewalls 14 , thereby increasing the contact surface between an adhesive applied to the convoluted surfaces and the window which is disposed in the channel 16 . As disclosed in the '468 patent, the bracket 10 also includes a groove 19 at the bottom of the channel 16 which provides even greater holding forces between the adhesive and the window. As disclosed in the '468 patent, the bracket 10 is preferably formed of a plastics material which allows the bracket to be integrally formed as a unitary, single-piece body. Such a configuration presents certain advantages, including certain manufacturing advantages. While the bracket 10 disclosed in the '468 patent and illustrated in FIG. 1 of the present application presents several advantages over many prior art window brackets, the bracket 10 also presents a disadvantage. Specifically, the bracket 10 is configured such that when the window is installed in the bracket 10 , and specifically in the channel 19 defined by the sidewalls 14 , an interference fit results between the sidewalls 14 and the window. The interference fit tends to create high stresses in the bottom of the channel 16 , which may cause the bracket 10 to fail. An embodiment of the present invention essentially provides an improvement to the bracket disclosed in the '468 patent. Hence, the embodiment provides many of the same advantages as does the bracket disclosed in the '468 patent, while being directed to overcome the noted disadvantage-namely, eliminating the high stress area which is present in the bottom of the channel of the bracket disclosed in the '468 patent. OBJECTS AND SUMMARY A general object of an embodiment of the present invention is to provide a window lift bracket which will securely attach to a window and a window lifting mechanism. Another object of an embodiment of the present invention is to provide a window lift bracket with a reduced stress area. A still further object of the present invention is to provide a window lift bracket which is efficiently manufactured and eliminates numerous manufacturing steps and the parts required to manufacture a bracket. Briefly, and in accordance with at least one of the foregoing, an embodiment of the present invention envisions a window lift bracket for attachment to a mounting edge of a movable window and which is connectable to a window lifting mechanism. The window lift bracket includes a base which is attachable to the window lifting mechanism and spaced apart portions extending from the base being positionable on either side of the movable window. The spaced apart portions define a channel therebetween. The window lift bracket includes at least one member, such as a flexible beam member, which is disposed generally in the channel for engaging the window when the window is disposed therein. Preferably, the engagement between the member and the window provides a reduced stress area at the bottom of the channel. Opposing surfaces of the spaced apart portions may provide convoluted surfaces, such as protrusions and depressions, which effectively increase the surface area to which the adhesive adheres, thereby improving the adhesion of the adhesive to the window bracket and the window. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an enlarged perspective view of a prior art window lift bracket, which is disclosed in U.S. Pat. No. 5,513,468; FIG. 2 is an enlarged perspective view of a portion of a window lift bracket, where the window lift bracket is in accordance with an embodiment of the present invention; FIG. 3 is a front elevational view of the window lift bracket shown in FIG. 2, showing the entire bracket; FIG. 4 is a top plan view of the window lift bracket shown in FIG. 3; FIG. 5 is a side elevational view of the window lift bracket shown in FIG. 3; FIG. 6 is cross-sectional view of the window lift bracket shown in FIG. 3, taken along line 6 — 6 of FIG. 2; FIG. 7 is a side elevational view similar to FIG. 5, but showing the window disposed in a channel defined by the bracket; FIG. 8 is a cross-sectional view similar to FIG. 6, but showing a window disposed in the channel defined by the bracket; 5 FIG. 9 is an enlargement of a top portion of FIG. 8, showing an adhesive disposed in the channel defined by the bracket; and FIG. 10 is an enlargement of a middle portion of FIG. 4, showing the window disposed in the channel defined by the bracket, and showing the engagement of two flexible beam members of the bracket with the window. DESCRIPTION While the invention may be susceptible to embodiment in different forms, there is shown in the drawings, and herein will be described in detail, an embodiment with the understanding that the present description is to be considered an exemplification of the principles of the invention and is not intended to limit the invention to that as illustrated and described herein. FIGS. 2-10 illustrate a window lift bracket 20 which is in accordance with an embodiment of the present invention. The window lift bracket 20 is similar to that which is disclosed in U.S. Pat. No. 5,513,468, which has been incorporated herein in its entirety be reference hereinabove. Like the bracket shown in FIG. 1 (and disclosed in the '468 patent), the bracket 20 illustrated in FIGS. 2-10 is configured for attachment to a window lifting mechanism 24 and a window 26 (see FIG. 3, for example), essentially providing a link between the window lifting mechanism 24 and the window 26 . The bracket 20 illustrated in FIGS. 2-10 of the present application preferably includes a base 28 and spaced apart means, such as generally parallel sidewalls 30 , which extend from the base 28 , thereby defining a channel 32 which receives an edge 34 of the window 26 . Preferably, the spaced apart means 30 provide convoluted surfaces which provide increased surface areas for an adhesive 36 to bond. Unlike the bracket 10 shown in FIG. 1 (and disclosed in the '468 patent), wherein an interference fit results between sidewalls 14 of the bracket 10 and the window when the window is disposed in the channel 16 between the sidewalls 14 , the bracket 20 illustrated in FIGS. 2-10 includes a plurality of flexible beam members 40 which extend from the base 28 and are disposed generally in the channel 32 . The flexible beam members 40 engage the window 26 when the window 26 is disposed in the channel 32 , and the engagement between the flexible beam members 40 and the window 26 works to localize resulting stress at the flexible beam members 40 , thereby reducing the stress which would otherwise be experienced at the bottom of the channel 32 , such as in the bracket 10 shown in FIG. 1 (and disclosed in the '468 patent). All of this will be described more fully later herein. As discussed above, preferably the window lift bracket 20 is configured to engage a window lifting mechanism 24 . Specifically, preferably the base 28 of the window lift bracket 20 includes one or more bores 42 for receiving corresponding fasteners 44 (shown in phantom in FIG. 3) which secure the base to the window lifting mechanism 24 , such as to a cross member of the window lifting mechanism 24 . While only a portion of the window lifting mechanism 24 is shown in FIG. 3, and the window lifting mechanism 24 is omitted from the rest of the FIGS. for clarity, a window lifting mechanism 24 which may be employed with the window lift bracket 20 is disclosed in U.S. Pat. No. 5,513,468 (see specifically FIG. 1 of the '468 patent), and the '468 patent has been incorporated herein in its entirety be reference hereinabove. As discussed above, the window lift bracket 20 is configured to receive an edge 34 of a window 26 and effectively provides a link between the window lifting mechanism 24 and the window 26 . Preferably, the window lift bracket 20 is configured to be securely engaged with an edge 34 of the window 26 , without scratching the window or a protective coating which is often applied to windows. As shown, the window lift bracket 20 includes spaced apart means 30 which are attached to and extend from the base 28 for attaching the bracket 20 to a window 26 . The spaced apart means 30 define a channel 32 therebetween in which the edge 34 of the window 26 is fitted Preferably, an inside surface 46 of the spaced apart means 30 provides a convoluted surface for adhesion to an adhesive 36 . The spaced apart means 30 are preferably formed as generally upstanding, spaced-apart sidewalls 30 which are attached to and extend from the base 28 . Inside facing surfaces 46 of the sidewalls 30 preferably include protrusions 50 which are shaped as ridges, and corresponding depressions 52 which are shaped as troughs. Preferably, the ridges 50 and troughs 52 are generally parallel to the direction of travel of the window 26 (arrow 56 in FIG. 3 generally depicts a preferred direction of travel of the window 26 ). The ridges 50 and troughs 52 define a convoluted inside surface. The convoluted surfaces preferably increase the effective surface area of the inside surface 46 of the sidewalls 30 , thereby increasing the contact surface between an adhesive 36 which is applied to the convoluted surfaces and to the window 26 . Preferably, the sidewalls 30 are spaced-apart such that when the window 26 is disposed in the channel 32 , a gap (identified by reference numeral 60 in FIG. 10) exists between the sidewalls 30 and the window 26 , and only the flexible beam members 40 contactably engage the window 26 . The flexible beam members 40 provide that the stress on the sidewalls 30 is localized on the flexible beam members 40 , and that the stress which would otherwise be experienced at the bottom of the channel 32 (i.e. proximate area 70 illustrated in FIG. 9) is reduced. For example, the bracket 10 shown in FIG. 1 (and disclosed in the '468 patent) is configured to provide an interference fit between the sidewalls 14 of the bracket 10 and a window disposed in the channel 16 . Such an interference fit provides a high stress area generally at the bottom of the channel (i.e. at area 15 shown in FIG. 1 ). In contrast, the bracket 20 illustrated in FIGS. 2-10 includes flexible beam members 40 which engage the window 26 , and a gap 60 (see FIG. 10) is preferably provided between the inside surfaces 46 of the sidewalls 30 and the window 26 . Hence, the stresses are localized on the flexible beam members 40 , and a high stress area is eliminated from the bottom of the channel 32 (i.e. at area 70 identified in FIG. 9 ). As shown in FIGS. 2, 5 , 6 and 9 , each of the flexible beam members 40 may include a hook portion 72 at an end 74 thereof, for contacting the window 26 which is disposed in the channel 32 . Preferably, the flexible beam members 40 are also configured to allow the free flow of adhesive 36 along the inside surfaces 46 of the sidewalls 30 , and the adhesive 36 does not leak from the bracket 20 . As shown in FIG. 9, the adhesive 36 is preferably disposed in the channel 32 for contact between the inside surfaces 46 of the sidewalls 30 and the window 26 . Preferably, the adhesive 36 is retained between the sidewalls 30 and the window 26 , and the convoluted surfaces provide increased surface area for improved adhesion. As shown, the adhesive 36 is also disposed between the spaced apart sidewalls 30 and the flexible beam members 40 . In order to provide even greater holding forces between the adhesive 36 , the bracket 20 and the window 26 , a groove 80 may be formed in the bracket 20 generally at the bottom of the channel 32 , between the sidewalls 30 for receiving the adhesive 36 therein. Preferably, the groove 80 generally runs the length of the bracket 20 to provide additional holding forces between the surface of the bracket 20 positioned proximate to the groove 80 , the adhesive 36 retained within the groove 80 , and the edge 34 of the window 26 . One type of adhesive which is used in the attachment of the present bracket 20 to a window 26 requires a heat curing process. As such, the adhesive 36 is applied between the window 26 and the bracket 20 forming bonds between the window 26 and the inside surfaces 46 of the sidewalls 30 and the groove 80 . The window 26 and one or more attached window lift brackets define a movable window assembly which is subjected to a heated environment to cure the adhesive 36 . In this regard, it is preferable to form the bracket 20 of a suitable plastics material which can withstand the temperature range required for heat curing the adhesive 36 . The bracket 20 is preferably formed of a plastics material which allows the bracket 20 to be integrally formed as unitary single piece body. A material such as injection molded glass filled nylon plastic may be used. Such material will provide the manufacturing benefits of plastic without compromising, and perhaps improving, the structural characteristics of the bracket 20 . Unitary forming of the bracket 20 eliminates numerous manufacturing steps and, perhaps, inspection steps required in some prior art brackets. Further, forming the bracket 20 of plastic eliminates the need for individually manufactured and assembled clips to prevent scratching the glass and protective coating of the window. As discussed above, the bracket 20 is preferably configured to be attached to a cross member of a window lifting mechanism 24 by one or more fasteners 44 which extend through bores 42 formed in the base 28 of the bracket 20 . Use of fasteners 44 to attach the bracket 20 to the window lifting mechanism 24 helps to simplify the installation process and further reduces the weight of the overall vehicle assembly. Preferably, the plastics material used in forming the bracket 20 will no t corrode, thereby eliminating corrosion failure which may occur in some prior art metal brackets. Additionally, providing that the bracket 20 is plastic eliminates the need for additional manufacturing steps such as coating of a metal bracket to delay the corrosion process. The plastics material greatly reduces the weight of the bracket 20 which may provide a noticeable cumulative effect since two brackets are often used per window which result in the use of eight brackets per vehicle thereby providing eight times the weight reduction per vehicle when comparing the plastic bracket to a prior art metal bracket. While a preferred embodiment of the present invention is shown and described, it is envisioned that those skilled in the art may devise various modifications of the present invention without departing from the spirit and scope of the appended claims. The invention is not intended to be limited by the foregoing disclosure.
A window lift bracket for attachment to a mounting edge of a movable window and which is connectable to a window lifting mechanism. The window lift bracket includes a base which is attachable to the window lifting mechanism and spaced apart portions extending from the base being positionable on either side of the movable window. The spaced apart portions define a channel therebetween. The window lift bracket includes at least one member, such as a flexible beam member, which is disposed generally in the channel for engaging the window when the window is disposed therein. Preferably, the engagement between the member and the window provides a reduced stress area at the bottom of the channel. Opposing surfaces of the spaced apart portions may provide convoluted surfaces, such as protrusions and depressions, which effectively increase the surface area to which the adhesive adheres, thereby improving the adhesion of the adhesive to the window bracket and the window.
4
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation of co-pending U.S. application Ser. No. 14/616,194, filed Feb. 6, 2015, which in turn is a continuation-in-part of and claims priority to U.S. application Ser. No. 13/626,986, filed Sep. 26, 2012 and issued Mar. 17, 2015 as U.S. Pat. No. 8,980,042, the contents of which are incorporated herein by reference in their entirety. FIELD OF THE INVENTION [0002] The present invention relates to carpet seam tape and methods for joining carpet. BACKGROUND [0003] When installing carpet, it is common for the room in which the carpet is being installed to have at least one dimension (length or width) that is greater than the length of a standard roll of carpet (which is typically twelve feet). In such a case, a single unitary segment of carpet from a roll cannot cover the entire floor of the room, and two or more segments must be pieced together. When two or more segments are pieced together, an edge of one segment is abutted against an edge of another segment, and these edges are joined (“seamed”) together using seam tape. [0004] FIGS. 1 and 2 illustrate top and cross-sectional views, respectively, of prior art seam tape. Prior art seam tape 10 comprises an elongated base layer 12 , scrim 14 , and an adhesive 16 (the adhesive is omitted from FIG. 1 for clarity). The base layer typically comprises paper or other relatively inelastic material. The scrim typically comprises woven threads and provides strength and additional inelasticity to the seam tape. The adhesive typically comprises a hot-melt thermoplastic adhesive applied to a large portion of the base layer. The scrim is embedded within the adhesive. [0005] When joining carpet edges together, the edge of one carpet segment is positioned to abut the edge of the other carpet segment. The seam tape is positioned under the abutting edges, and the adhesive is activated by applying heat to the top surface of the carpet above the seam tape. The heat melts the adhesive and the melted adhesive bonds to the underside of both carpet segments as the adhesive cures. [0006] After the carpet segments are positioned to cover the entire floor and the seams are joined using seam tape, the carpet is stretched at the outer edges and the outer edges are secured to the floor using tack strips. The stretching tightens the carpet to remove any slack and wrinkles. FIG. 3 illustrates what happens when the carpet is stretched in a direction transverse to the carpet seam (indicated by the arrows in FIG. 3 ). The top image of FIG. 3 illustrates the unstretched carpet. As the carpet is stretched and the two carpet segments 18 A, 18 B are pulled away from each other, the inelasticity of the seam tape 10 causes the seam to lift off the floor, resulting in an unsightly bulge in the carpet (illustrated in the bottom image of FIG. 3 ). This is called seam “peaking” or “profiling” and is highly undesirable. BRIEF SUMMARY [0007] In one embodiment of the invention, a method for joining two carpet segments, each carpet segment having an underside and at least one edge, comprises abutting one edge of one carpet segment with one edge of the other carpet segment, positioning a length of seam tape under the abutting edges, and activating the adhesive to secure the seam tape to the undersides of both carpet segments. The seam tape comprises an elongated base layer being resilient in a transverse direction, an intervening layer applied to the base layer, and an adhesive applied to the intervening layer. [0008] The adhesive may comprise a hot-melt thermoplastic adhesive. [0009] The base layer may comprise textile or fabric. The textile or fabric may comprise cotton and elastane. The textile or fabric may comprise denim and elastane. [0010] The adhesive may comprise (a) a unitary mass of adhesive, (b) a plurality of beads of adhesive, or (c) a plurality of spots of adhesive. [0011] The intervening layer may comprise (a) a unitary mass of intervening layer, (b) a plurality of beads of intervening layer, or (c) a plurality of spots of intervening layer. [0012] The intervening layer may comprise a sealant to inhibit the adhesive from seeping into pores of the base layer. [0013] The adhesive may comprise a first adhesive, and wherein the intervening layer comprises a second adhesive. The second adhesive may comprise a polymer adhesive. [0014] The seam tape may not comprise a scrim. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S) [0015] Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein: [0016] FIG. 1 is a top view of prior art seam tape. [0017] FIG. 2 is a cross-sectional view of the prior art seam tape of FIG. 1 along the indicated line. [0018] FIG. 3 illustrates carpet segments joined using the prior art seam tape of FIG. 1 . [0019] FIG. 4 is a top view of seam tape, in accordance with an embodiment of the present invention. [0020] FIG. 5 is a cross-sectional view of the seam tape of FIG. 4 . [0021] FIG. 6 illustrates carpet segments joined using the seam tape of FIG. 4 . [0022] FIG. 7 is a top view of seam tape, in accordance with an alternative embodiment of the present invention. [0023] FIG. 8 is a cross-sectional view of the seam tape of FIG. 7 . [0024] FIG. 9 is a cross-sectional view of seam tape, in accordance with an alternative embodiment of the present invention. DETAILED DESCRIPTION [0025] Embodiments of the invention provide the ability to securely join carpet segments while preventing seam peaking when the joined carpet is stretched. Referring now to FIGS. 4 and 5 , top and cross-sectional views are illustrated, respectively, of seam tape in accordance with an embodiment of the present invention. The seam tape 30 of embodiments of the invention comprises an elongated base layer 32 and an adhesive 36 applied to the base layer. Notably, the seam tape does not comprise a scrim. The elongated base layer may comprise any suitable material that is resilient (stretches and rebounds) in a transverse (perpendicular to the longitudinal axis) direction. For example, the elongated base layer may comprise a textile or fabric (including combinations of different textiles or fabrics), rubber, polymer (including combinations of different polymers), and combinations thereof. In one embodiment of the invention, the elongated base layer comprises a fabric that combines cotton (such as denim) and elastane (such as Lycra or Spandex). For example, the fabric that is used to make “stretch jeans” may be used for the base layer. Such a fabric may be, for example, 98% denim and 2% elastane or 95% denim and 5% elastane, although different amounts of denim and elastane may be used. Optionally, one or more additional materials may be combined with the cotton and elastane. For example, the elongated base layer may comprise a fabric that combines polyester with the cotton and elastane, such as a combination of 78% cotton denim, 18% polyester, and 4% elastane. The fabric may be dyed or undyed. The adhesive typically comprises a hot-melt thermoplastic adhesive. [0026] The material selected for the elongated base layer should be as resilient as the carpet to which the seam tape is to be secured, such as to not impede the carpet from stretching. However, it may also be desirable for the material to not be significantly more resilient than the carpet. Such a material should provide enough stretch to the seam tape to reduce the likelihood of seam peaking, but not so much stretch as to allow a gap to be visible at the seam. As different types of carpets may have different amounts of resiliency, it may be desirable to have different types of seam tapes, each with a different amount of resiliency to match a different type of carpet. Alternatively, it may be desirable to have a single type of seam tape that has sufficient resiliency to be used with a wide variety of different types of carpet. [0027] For purposes of this application, the terms “textile” and “fabric” are used interchangeably to refer to a flexible woven material comprising a network of natural or artificial fibers (often referred to as thread or yarn). Textiles are formed by weaving, knitting, crocheting, knotting, or pressing fibers together. For purposes of this application, the terms “textile” and “fabric” specifically exclude paper. [0028] FIG. 6 illustrates what happens when carpet that is joined using carpet seam tape 30 of embodiments of the invention is stretched in a direction transverse to the carpet seam (indicated by the arrows in FIG. 6 ). As the two carpet segments 38 A, 38 B are pulled away from each other, the elasticity of the seam tape 30 prevents the seam from lifting off the floor, thereby preventing seam peaking. It does this by allowing the stretch to “reach” the seam. That is, the portions of the carpet that are affixed to the seam tape (of embodiments of the invention) are able to stretch (along with the seam tape). In contrast, the prior art seam tape does not allow the portions of the carpet that are affixed to the prior art seam tape to stretch (because the prior art seam tape does not stretch). [0029] Referring now to FIGS. 7 and 8 , top and cross-sectional views are illustrated, respectively, of seam tape in accordance with an alternative embodiment of the present invention. The seam tape 50 of alternative embodiments of the invention comprises an elongated base layer 52 and an adhesive 56 applied to the base layer. As above, seam tape 50 does not comprise a scrim. Rather than a unitary mass of adhesive applied to the base layer, seam tape 50 comprises a plurality of “beads” of glue. The beads of glue are illustrated as being substantially parallel to the longitudinal axis of the seam tape and to each other, but other configurations may be used. The beads are illustrated as being continuous, but may be non-continuous beads or may even comprise individual “dots” or “spots” of adhesive. Such a non-unitary application of adhesive to the base layer may be desirable where a non-flexible (or insufficiently flexible) adhesive is used. Some types of adhesives, once cured, may be less flexible than other types of adhesives. For example, high melt glue is less flexible, once cured, than low melt glue. Using a non-unitary application of adhesive to the base layer when a less flexible adhesive is used prevents (or at least reduces) the adhesive from restricting the tape (and therefore the carpet) from stretching. [0030] While four beads of adhesive are illustrated in FIGS. 7 and 8 , the amount of adhesive in each bead and the spacing and number of the beads may vary, depending on the type of adhesive, the type of carpet, etc. It is desirable that the amount of adhesive and the spacing of the beads be selected such that the beads remain separate and do not run together when the seam tape is heated and the adhesive is melted. Since the use of such beads is typically limited to glues that are relatively less flexible, ensuring that the beads remain separate after melting helps maintain the continued resiliency of the seam tape. [0031] The carpet seam tape of embodiments of the invention offers many improvements over prior art seam tape. The carpet seam tape of embodiments of the invention lays flat despite stretching of the carpet because the elasticity of the seam tape allows the carpet to stretch. The carpet seam tape of embodiments of the invention is easier to manufacture and less expensive due at least to the lack of a scrim. The carpet seam tape of embodiments of the invention provides a bond that is better capable of withstanding repeated steam cleaning due to its use of fabric rather than paper as the base layer. [0032] When the carpet seam tape of embodiments of the invention is used to seam carpet, the edges of the carpet should be “seam sealed” as per standard carpet seaming practices established by the Carpet and Rug Institute. This seam sealing step further reduces the likelihood of peaking. It is anticipated that all other standard seaming techniques will work when the carpet seam tape of embodiments of the invention is used to seam carpet, and therefore should be used. [0033] In addition to joining carpet segments during installation of carpet, the carpet seam tape of embodiments of the invention may be used in a carpet mill to join the ends of carpet rolls to form larger carpet rolls. [0034] The adhesive may be applied directly to the base layer, as illustrated in FIGS. 4 and 5 , or the adhesive may be applied indirectly to the base layer. Referring now to FIG. 9 , a cross-sectional view of seam tape is illustrated in accordance with an alternative embodiment of the present invention. The carpet seam tape 60 of FIG. 9 comprises a base layer 62 (as described above), an intervening layer 64 applied to the base layer 62 , and an adhesive 66 (as described above, which may be, for example, hot melt adhesive) applied to the intervening layer 64 . In this regard, the adhesive is applied indirectly to the base layer. [0035] As described above, the elongated base layer 62 may be resilient in a transverse direction and may comprise textile or fabric, such as (a) cotton and elastane or (b) denim and elastane. [0036] The intervening layer may comprise a sealant to inhibit (partially or completely) the adhesive from seeping into pores or any similar openings in the base layer and/or melting through the base layer (which can happen with conventional seam tape if the seam tape is overheated during installation; if it happens, the seam tape may stick to the carpet padding, which is undesirable). [0037] In one embodiment of the invention, the intervening layer comprises an adhesive (typically a different adhesive than the hot melt adhesive) which functions as a sealant. Specifically, the intervening layer may comprise a polymer adhesive such as Roberts® 8015 Universal Carpet Seam Sealer from Q.E.P. Co., Inc. The intervening layer may fully cover the base layer, or partly cover the base layer (such that part or parts of the base layer are not covered by the intervening layer). If the intervening layer partly covers the base layer, it may be applied as (a) a unitary mass of intervening layer (similar to the application of the adhesive in FIG. 4 ), (b) a plurality of beads of intervening layer (similar to the application of the adhesive in FIG. 7 ), or (c) a plurality of spots of intervening layer. The adhesive may fully cover the intervening layer, or partly cover the intervening layer. The adhesive may be applied as (a) a unitary mass, (b) a plurality of beads, or (c) a plurality of spots. [0038] Using an intervening layer that inhibits the adhesive from seeping into pores or other openings of the base layer helps prevent the seam tape from sticking to the carpet padding, helps prevent the base layer from unraveling (particularly if the base layer is a fabric or textile), and helps keep the base layer resilient. [0039] After the intervening layer is applied to the base layer, the intervening layer should typically be allowed to dry or cure (partially or fully) before the adhesive is applied to the intervening layer to help prevent the adhesive from combining with the intervening layer. [0040] The embodiment of FIG. 9 may be used with a base layer that is not resilient in the transverse direction, or a base layer that is not resilient at all. [0041] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. [0042] The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
A method for joining two carpet segments, each carpet segment having an underside and at least one edge, comprises abutting one edge of one carpet segment with one edge of the other carpet segment, positioning a length of seam tape under the abutting edges, and activating the adhesive to secure the seam tape to the undersides of both carpet segments. The seam tape comprises an elongated base layer being resilient in a transverse direction, an intervening layer applied to the base layer, and an adhesive applied to the intervening layer.
2
CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a divisional application of U.S. patent application Ser. No. 13/760,556, filed on Feb. 6, 2013, which claims the benefit of Korean Patent Application No. 10-2012-0011798, filed on Feb. 6, 2012, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein in their entireties by reference. BACKGROUND The inventive concept relates to a sensor for sensing a signal, and, more particularly, to an image sensor for sensing object information and converting the sensed object information into an electrical signal and an image processing apparatus using the image sensor. An example of an image sensor is a complementary metal oxide semiconductor (CMOS) image sensor. The CMOS image sensor is a device for converting an optical image into an electrical signal, and may be applied to electronic products, such as a digital camera, a cellular phone, and the like. As electronic products become slimmer, research into minimization of the CMOS image sensor and reduction of power consumption is needed. SUMMARY The inventive concept may provide an image sensor for reducing a size of a product and power consumption thereof. The inventive concept may also provide an image processing apparatus using an image sensor for reducing a size of a product and power consumption thereof. According to an aspect of the inventive concept, there is provided an image sensor including: a column signal line connected to output terminals of a plurality of pixel sensors; a comparator circuit configured to output a signal corresponding to a comparison result of a signal output to the column signal line and a reference signal; an analog/digital conversion (ADC) circuit configured to convert an analog signal corresponding to an optical signal sensed by the pixel sensor selected from the plurality of pixel sensors connected to the column signal line into digital data based on the signal output from the comparator circuit; and a load circuit connected in series to the comparator circuit between the column signal line and a ground terminal, wherein the load circuit is configured as a common load device of the plurality of pixel sensors connected to the column signal line and the comparator circuit. The comparator circuit may include a transistor, wherein the reference signal is applied to a gate terminal of the transistor, the column signal line is connected to a first terminal of the transistor, and the load circuit is connected to a second terminal of the transistor. The transistor may include a PMOS transistor. The comparator circuit may include a transistor, a capacitor, and a switch, wherein the reference signal is applied to a first terminal of the capacitor, a gate terminal of the transistor and a first terminal of the switch are connected to a second terminal of the capacitor, the column signal line is connected to a first terminal of the transistor, and a second terminal of the switch and the load circuit are connected to a second terminal of the transistor. The switch may be turned on during a first section before a correlated double sampling (CDS) process is performed and may be turned off during sections other than the first section. The load circuit may include an active load circuit. The reference signal may include a signal having a ramp waveform. The ADC circuit may include: a counter circuit configured to generate the digital data as a counting value corresponding to a difference in a length of double sampling sections determined according to the signal output from the comparator circuit based on the CDS process. The counter circuit may generate the digital data by performing up-counting during one of the double sampling sections and performing down-counting during another double sampling section, or performing up-counting or down-counting during the double sampling sections and changing a digital data code of one of the double sampling sections through bit-inversion between the double sampling sections. The image sensor may further include an amplification circuit between an output terminal of the comparator circuit and the ADC circuit. The amplification circuit may include an inverter or an amplifier. Each of the plurality of pixel sensors may include: a photoelectric conversion device configured to generate charges corresponding to an incident light; and a signal transfer circuit configured to transfer an electrical signal corresponding to the charges generated by the photoelectric conversion device to the column signal line. The signal transfer circuit may include: a first transistor connected between the photoelectric conversion device and the first node and configured to transmit the charges accumulated in the photoelectric conversion device to the first node according to a first driving signal; a second transistor connected between the first node and a power voltage and configured to reset the charges charged in the first node according to a second driving signal; a third transistor connected between the first node and a second node and configured to transfer a signal sensed by the first node to the second node; and a fourth transistor connected between the second node and the column signal line and configured to transfer a signal of the second node to the column signal line according to a third driving signal. According to another aspect of the inventive concept, there is provided an image processing apparatus including: an image sensor configured to convert an incident image signal into an electrical signal; and a processor configured to control an operation of the image sensor and post-processing a signal output from the image sensor, wherein the image sensor includes: a column signal line connected to output terminals of a plurality of pixel sensors; a comparator circuit configured to output a signal corresponding to a comparison result of a signal output to the column signal line and a reference signal; an analog/digital conversion (ADC) circuit configured to convert an analog signal corresponding to an optical signal sensed by the pixel sensor selected from the plurality of pixel sensors connected to the column signal line into digital data based on the signal output from the comparator circuit; and a load circuit connected in series to the comparator circuit between the column signal line and a ground terminal, wherein the load circuit is configured to operate as a common load device of the plurality of pixel sensors connected to the column signal line and the comparator circuit. The comparator circuit may include a transistor, wherein a reference signal having a ramp waveform is applied to a gate terminal of the transistor, the column signal line is connected to a first terminal of the transistor, and the load circuit is connected to a second terminal of the transistor. According to another aspect of the inventive concept, an image sensor comprises a column signal line connected to output terminals of a plurality of pixel sensors and configured to generate a column signal line output signal, a comparator circuit configured to output a comparison result signal corresponding to a comparison of the column signal line output signal and a reference signal, and a load circuit connected to the comparator circuit between the column signal line and a ground terminal and configured as a common load device of the plurality of pixel sensors connected to the column signal line and the comparator circuit. The comparator circuit comprises a transistor, a gate terminal of the transistor receives the reference signal, the column signal line is connected to a first terminal of the transistor, and the load circuit is connected to a second terminal of the transistor. The transistor may comprise a PMOS transistor. The comparator circuit may comprise a transistor, a capacitor, and a switch, a first terminal of the capacitor receives the reference signal, a gate terminal of the transistor and a first terminal of the switch are connected to a second terminal of the capacitor, the column signal line is connected to a first terminal of the transistor, and a second terminal of the switch and the load circuit are connected to a second terminal of the transistor. The switch may be in a turned on state during a first section before a correlated double sampling (CDS) process is performed and may be in a turned off during sections other than the first section. BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments of the inventive concept will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings in which: FIG. 1 is a block diagram of an image sensor, according to an embodiment of the inventive concept; FIGS. 2A through 2C are exemplary circuit diagrams of pixel sensors of FIG. 1 ; FIG. 3 is a circuit diagram of a comparator circuit connected to one column signal line of a pixel sensor of FIG. 1 , according to an embodiment of the inventive concept; FIG. 4 is a circuit diagram of a comparator circuit connected to one column signal line of a pixel sensor of FIG. 1 , according to another embodiment of the inventive concept; FIG. 5 is a circuit diagram of an amplification circuit added to a comparator circuit connected to one column signal line of the pixel sensor of FIG. 3 , according to an embodiment of the inventive concept; FIGS. 6A and 6B are circuit diagrams of the amplification circuit of FIG. 5 , according to embodiments of the inventive concept; FIG. 7 is a circuit diagram of an amplification circuit added to a comparator circuit connected to one column signal line of the pixel sensor of FIG. 4 , according to another embodiment of the inventive concept; FIGS. 8A and 8B are circuit diagrams of the amplification circuit of FIG. 7 , according to embodiments of the inventive concept; FIG. 9 is a circuit diagram of a load circuit of FIG. 1 , according to an embodiment of the inventive concept; FIG. 10 is a circuit diagram of a load circuit of FIG. 1 , according to another embodiment of the inventive concept; FIG. 11 is a timing diagram of main signals generated by an image sensor, according to an embodiment of the inventive concept; FIG. 12 is a timing diagram of main signals generated by an image sensor, according to another embodiment of the inventive concept; and FIG. 13 is a block diagram of an image processing apparatus according to embodiments of the inventive concept. DETAILED DESCRIPTION OF THE EMBODIMENTS Hereinafter, the inventive concept will be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the inventive concept are shown. The present inventive concept may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those of ordinary skill in the art. As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the inventive concept to particular modes of practice, and it is to be appreciated that all changes, equivalents, and substitutes that do not depart from the spirit and technical scope of the inventive concept are encompassed in the inventive concept. It will be understood that when an element or layer is referred to as being “on,” “connected to” or “coupled with” another element or layer, it can be directly on, connected or coupled with the other element or layer or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly connected to” or “directly coupled with” another element or layer, there are no intervening elements or layers present. In the drawings, like reference numerals denote like elements and the sizes or thicknesses of elements may be exaggerated for clarity of explanation. The terms used in the present specification are merely used to describe particular embodiments, and are not intended to limit the inventive concept. An expression used in the singular encompasses the expression in the plural, unless it has a clearly different meaning in the context. In the present specification, it is to be understood that the terms such as “including” or “having,” etc., are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof disclosed in the specification, and are not intended to preclude the possibility that one or more other features, numbers, steps, actions, components, parts, or combinations thereof may exist or may be added. Unless defined differently, all terms used in the description including technical and scientific terms have the same meaning as generally understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and this specification and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. FIG. 1 is a block diagram of an image sensor 100 , according to an embodiment of the inventive concept. Referring to FIG. 1 , the image sensor 100 includes a pixel sensor array 10 , a comparator circuit block 20 , an analog/digital conversion (ADC) circuit block 30 , a load circuit block 40 , a buffer memory block 50 , a timing controller TCON 60 , a row driver 70 , and a ramp signal generator 80 . The pixel sensor array 10 includes a plurality of pixel sensors P 11 that are respectively connected to a plurality of column signal lines 12 - 1 ˜ 12 -m in a matrix shape. The comparator circuit block 20 includes a plurality of comparator circuits C 21 that are respectively connected to the column signal lines 12 - 1 ˜ 12 -m. The ADC circuit block 30 includes a plurality of ADC circuits 31 . The ADC circuit block 30 includes at least one of the ADCs 31 for each of the column signal lines 12 - 1 ˜ 12 -m. The load circuit block 40 includes a plurality of load circuits L 41 . The load circuit block 40 includes the single common load circuit L 41 for each of the column signal lines 12 - 1 ˜ 12 -m. The detailed construction and operation of the image sensor 100 , according to some embodiments of the inventive concept, will now be described below. The pixel sensor array 10 is briefly referred to as a pixel array. The pixel sensor array 10 includes the plurality of pixel sensors P 11 . The pixel sensors P 11 may include a plurality of color pixel sensors, for example, at least one red pixel sensor, at least one green pixel sensor, and at least one blue pixel sensor. If the image sensor 100 is implemented as a 3D image sensor, the pixel sensors P 11 may further include at least one depth pixel sensor in addition to the color pixel sensors. The depth pixel sensor may generate optical charges corresponding to wavelengths of an infrared region. The pixel sensor array 10 may include the plurality of column signal lines 12 - 1 ˜ 12 -m (m is a natural number). The pixel sensors P 11 that are arranged in a column direction may be respectively connected to the column signal lines 12 - 1 ˜ 12 -m. FIGS. 2A through 2C are exemplary circuit diagrams of the pixel sensors P 11 of FIG. 1 . Referring to FIG. 2A , a pixel sensor 11 a according to an embodiment of the inventive concept may be implemented as one photoelectric conversion device PD and four transistors M 1 ˜M 4 . The photoelectric conversion device PD that is an optical sensing device may be implemented as a photo diode, a photo transistor, a photo gate, or a pinned photo diode. The photoelectric conversion device PD is connected between a floating diffusion node FD and a ground terminal and generates charges corresponding to an incident optical signal. The transistor M 2 is connected between a power voltage terminal VDD and the floating diffusion node FD and functions to emit charges stored in the floating diffusion node FD in response to a driving signal RG. The transistor M 1 is connected between an output terminal of the power voltage terminal VDD and the floating diffusion node FD and functions to transmit the optical charges generated by the photoelectric conversion device PD to the floating diffusion node FD in response to another driving signal TG. The transistor M 3 functions as a source follower buffer amplifier and may perform a buffering operation in response to the charges stored in the floating diffusion node FD. A drain terminal of the transistor M 4 is connected to a source terminal of the transistor M 3 , and a source terminal thereof is connected to a node P of the column signal line 12 -i. Another driving signal SL is applied to a gate terminal of the transistor M 4 . Accordingly, the transistor M 4 may output a pixel signal PIX_OUT output from the transistor M 3 to the column signal line 12 -i in response to the driving signal SL. Referring to FIG. 2B , a pixel sensor 11 b according to another embodiment of the inventive concept may be implemented as the photoelectric conversion device PD and the three transistors M 2 ˜M 4 . Referring to FIGS. 2A and 2B , the pixel sensor 11 b of FIG. 2B has a structure in which the transistor M 1 functioning as a transmission transistor is deleted. Referring to FIG. 2C , a pixel sensor 11 c according to another embodiment of the inventive concept may be implemented as the photoelectric conversion device PD and five transistors M 1 ˜M 5 . The driving signal TG for controlling an operation of the transistor M 1 functioning as the transmission transistor is supplied to a gate of the transistor M 1 through the transistor M 5 that is turned on/off in response to the driving signal SL. Referring to FIG. 1 , the timing controller 60 generates control signals necessary for selecting the pixel sensors P 11 or outputting image signals sensed by the pixel sensors P 11 . The timing controller 60 may control generation timing of a ramp signal necessary for performing a correlated double sampling (CDS) process and control output of data stored in the buffer memory block 50 . The row driver 70 outputs a plurality of driving signals necessary for controlling photoelectric conversion operations of the pixel sensors P 11 arranged in a row direction to the pixel sensor array 10 in response to the control signals. In this regard, the plurality of driving signals may include, for example, the driving signals RG, TG, and SL of FIG. 11 . The plurality of driving signals may further include, for example, a driving signal AZP of FIG. 12 . The driving signal AZP will be described in more detail below. The ramp signal generator 80 generates a ramp signal RAMP in response to the control signals and outputs the ramp signal RAMP to the comparator circuit block 20 . As shown in FIG. 11 or 12 , the ramp signal generator 80 generates a signal having one ramp waveform before a pulse of the driving signal TO is generated, and generates a signal having one ramp waveform after the pulse of the driving signal TG is generated so as to perform CDS. The comparator circuits 21 are respectively connected to the column signal lines 12 - 1 12 -m. Various embodiments of the comparator circuit 21 will be described with reference to FIGS. 3 and 4 below. FIG. 3 is a circuit diagram of a comparator circuit 21 a connected to one column signal line 12 -i of the pixel sensor 11 of FIG. 1 , according to an embodiment of the inventive concept. The image sensor 100 including the comparator circuit 21 a of FIG. 3 may generate, for example, the driving signals SL, RG, and TG at the timings of FIG. 11 . Referring to FIG. 3 , the comparator circuit 21 a may be implemented as a transistor M 6 . For example, the transistor M 6 may be implemented as a PMOS transistor. The ramp signal RAMP output from the ramp signal generator 80 is applied to a gate terminal of the transistor M 6 , the column signal line 12 -i is connected to a source terminal of the transistor M 6 , and a first terminal of the load circuit 41 is connected to a drain terminal of the transistor M 6 . A second terminal of the load circuit 41 is connected to a ground terminal. An output terminal of the pixel sensor 11 is connected to the node P of the column signal line 12 -i. A signal COMP_OUT output from a node Q disposed in a signal line that is connected to the first terminal of the load circuit 41 and the drain terminal of the transistor M 6 is applied to the ADC circuit 31 . Referring to FIGS. 2A to 2C , in a case where the transistor M 4 is turned on by the driving signal SL applied to the pixel sensors 11 a to 11 c , an output signal of the source follower transistor M 3 is applied to the column signal line 12 -i through the node P. The source follower transistor M 3 needs a load circuit. The transistor M 6 constituting the comparator circuit 21 a also needs a load circuit. Referring to FIG. 3 , the load circuit 41 has a circuit structure in which the load circuit 41 is connected in series to the comparator circuit 21 a between the column signal line 12 -i and the ground terminal. Accordingly, the load circuit 41 operates as a load device of a pixel sensor connected to the column signal line 12 -i, and operates as a load device of the comparator circuit 21 a . In other words, the load circuit 41 operates as a common load device of the source follower transistor M 3 included in the pixel sensor 11 and the transistor M 6 constituting the comparator circuit 21 a. In this regard, the load circuit 41 may be implemented as an active load circuit. An example of the active load circuit is shown in FIG. 9 . Referring to FIG. 9 , an active load circuit 41 a may be implemented as a transistor M 7 . For example, the transistor M 7 may be implemented as an NMOS transistor. More specifically, a drain terminal of the transistor M 7 is connected to the node Q, a source terminal of the transistor M 7 is connected to a ground terminal, and a load bias voltage (or current) is applied to a gate terminal of the transistor M 7 . A drain-source current of the transistor M 7 varies with the load bias voltage (or current). That is, the transistor M 7 enables a load value between the node Q and the ground terminal to vary with the load bias voltage (or current). Accordingly, the transistor M 7 operates as an active load. FIG. 10 shows a detailed example of an active load circuit 41 b including a circuit for generating a load bias. Referring to FIG. 10 , for example, transistors M 7 and M 8 may be implemented as NMOS transistors. More specifically, a drain terminal of the transistor M 7 is connected to the node Q, a source terminal of the transistor M 7 is connected to a ground terminal, and a gate terminal of the transistor M 7 is connected to a node R. A gate terminal and a drain terminal of the transistor M 8 are connected to the node R, and a source terminal of the transistor M 8 is connected to the ground terminal. A first terminal of a current source I 1 is connected to a power voltage terminal, and a second terminal thereof is connected to the node R. A gate-source voltage of the transistor M 7 is the same as a gate-source voltage of the transistor M 8 , and thus a drain-source current of the transistor M 7 is the same as a drain-source current of the transistor M 8 . That is, the transistor M 7 operates a current mirror circuit. Accordingly, the drain-source current of the transistor M 7 varies with a variation of a current value of the current source I 1 . The transistor M 7 enables a load value between the node Q and the ground terminal to vary with the current value of the current source I 1 . Accordingly, the transistor M 7 operates as an active load. Referring to FIG. 3 , it is assumed that the pixel sensor 11 is implemented as, for example, the circuit of FIG. 2A , and the driving signals SL, RG, and TG are generated at the timings of FIG. 11 . It is also assumed that the ramp signal generator 80 generates the ramp signal RAMP at the timing of FIG. 11 . Then, a voltage of the floating diffusion node FD of FIG. 2A is as shown in FIG. 11 . The output signal PIX_OUT of the pixel sensor 11 disposed in the node P of the column signal line 12 -i has a waveform shown in FIG. 11 . Referring to FIG. 3 , if the ramp signal RAMP shown in FIG. 11 is applied to the gate terminal of the transistor M 6 of the comparator circuit M 6 , the node Q connected to the drain terminal of the transistor M 6 generates the output signal COMP_OUT of the comparator circuit 21 a . The PMOS transistor M 6 is turned on if a voltage applied to the gate terminal of the PMOS transistor M 6 is lower than a voltage obtained by subtracting a threshold voltage Vth from a voltage applied to the source terminal thereof, and is turned off if the voltage applied to the gate terminal of the PMOS transistor M 6 is not lower than the obtained voltage. Accordingly, as shown in FIG. 11 , the output signal COMP_OUT of the comparator circuit 21 a is in a logic high state HIGH in a case where a voltage of the ramp signal RAMP applied to the gate terminal of the transistor M 6 is lower than a voltage obtained by subtracting the threshold voltage Vth from a voltage of the pixel signal PIX_OUT applied to the drain terminal of the transistor M 6 , and is in a logic low state LOW if the voltage of the ramp signal RAMP applied to the gate terminal of the transistor M 6 is not lower than the obtained voltage. That is, it may be understood that the transistor M 6 operates as a comparator circuit for comparing the ramp signal RAMP with the output signal PIX_OUT of the pixel sensor 11 . The above-described output signal COMP_OUT of the comparator circuit 21 a is applied to the ADC circuits 31 . Referring to FIG. 1 , the ADC circuits 31 may be implemented as, for example, counter circuits for generating digital data with respect to a corresponding pixel as a counting value corresponding to a difference in a length between double sampling sections determined according to the output signal COMP_OUT of the comparator signal 21 based on a CDS process. For example, referring to FIG. 11 , before a pulse of the driving signal TG is generated, the ramp signal generator 80 starts a up-counting operation at a time T 1 at which a signal having a ramp waveform is generated, and stops the up-counting operation at a time T 2 at which the output signal COMP_OUT is in a logic high state. After the pulse of the driving signal TG is generated, the ramp signal generator 80 starts a down-counting operation at a time T 3 at which the signal having the ramp waveform is generated, and stops the down-counting operation at a time T 4 at which the output signal COMP_OUT is in the logic high state. In this way, the digital data may be generated by operating the counter circuits as described above. For another example, referring to FIG. 11 , before the pulse of the driving signal TG is generated, the ramp signal generator 80 starts the down-counting operation at the time T 1 at which the signal having the ramp waveform is generated, and stops the down-counting operation at the time T 2 at which the output signal COMP_OUT is in the logic high state. After the pulse of the driving signal TG is generated, the ramp signal generator 80 starts the up-counting operation at the time T 3 at which the signal having the ramp waveform is generated, and stops the up-counting operation at the time T 4 at which the output signal COMP_OUT is in the logic high state. In this way, the digital data may be generated by operating the counter circuits as described above. For another example, referring to FIG. 11 , the digital data may be generated with respect to a corresponding pixel by performing the up- or down-counting operation on the two sampling sections T 1 -T 2 and T 3 -T 4 of the double sampling section, and changing a digital data code of one of the two sampling sections through bit inversion between the two sampling sections. The counter circuits that implement the ADC circuits 31 may be reset, for example, at a time at which a pulse of the driving signal RF is generated. Referring to FIG. 1 , a plurality of pieces of pixel data generated by the ADC circuits 31 included in the ADC circuit block 30 are stored in the buffer memory block 50 . The pixel data stored in the buffer memory block 50 may be output to an image processor (not shown) under control of the timing controller 60 . FIG. 4 is a circuit diagram of a comparator circuit 21 b connected to the column signal line 12 -i of the pixel sensor 11 of FIG. 1 , according to another embodiment of the inventive concept. The image sensor 100 including the comparator circuit 21 b of FIG. 4 may generate the driving signals SL, RG, TG, and AZP, for example, at the timing shown in FIG. 12 . Referring to FIG. 4 , the comparator circuit 21 b may be implemented as the transistor M 6 , a capacitor C 1 , and a switch SW 1 . For example, the transistor M 6 may be a PMOS transistor. The gate terminal of the transistor M 6 is connected to a node T, the source terminal of the transistor M 6 is connected to the node P of the column signal line 12 -i, and the drain terminal of the transistor M 6 is connected to the node Q. A first terminal of the switch SW 1 is connected to the node T, a second terminal thereof is connected to the node Q, and the driving signal AZP is applied to a control terminal of the switch SW 1 . A first terminal of the capacitor C 1 is connected to the node T, and the ramp signal RAMP output from the ramp signal generator 80 is applied to a second terminal of the capacitor C 1 . In this regard, the driving signal AZP is generated before, for example, a CDS process is performed. For example, as shown in FIG. 12 , before the ramp signal generator 80 generates a signal having a ramp waveform, the row driver 70 may generate the driving signal AZP under control of the timing controller 60 . A first terminal of the load circuit 41 is connected to the node Q, and a second terminal thereof is connected to a ground terminal. An output terminal of the pixel sensor 11 is connected to the node P of the column signal line 12 -i. The pixel sensor 11 connected to the node P may be implemented as, for example, the circuits shown in FIGS. 2A to 2C . The pixel sensor 11 and the load circuit 41 are described in detail with reference to FIG. 3 , and, thus, redundant descriptions thereof will not be repeated here. As described with reference to FIG. 3 , the load circuit 41 of FIG. 4 operates as a common load device of the source follower transistor M 3 included in the pixel sensor 11 and the transistor M 6 constituting the comparator circuit 21 b. The comparator circuit 21 b of FIG. 4 further includes the capacitor C 1 and the switch SW 1 compared to the comparator circuit 21 of FIG. 3 . Referring to FIG. 4 , the capacitor C 1 and the switch SW 1 function to remove an offset of the transistor M 6 constituting the comparator circuit 21 b . That is, the switch SW 1 is turned on during a section in which the driving signal AZP is in a logic high state HIGH. A voltage reflecting an offset of a threshold voltage of the transistor M 6 is applied to both terminals of the capacitor C 1 during the section in which the switch SW 1 is turned on. Thereafter, if the switch SW 1 is turned off, the voltage reflecting the offset of the threshold voltage of the transistor M 6 is applied to both terminals of the capacitor C 1 , and, thus, the offset of the transistor M 6 is removed. FIG. 5 is a circuit diagram of an amplification circuit 22 added to the comparator circuit 21 a connected to one column signal line of the pixel sensor 11 of FIG. 3 , according to an embodiment of the inventive concept. The pixel sensor 11 , the comparator circuit 21 a , and the load circuit 41 of FIG. 5 are described in detail with reference to FIG. 3 , and, thus, redundant descriptions thereof will not be repeated here. Referring to FIG. 5 , an input terminal of the amplification circuit 22 is connected to the node Q corresponding to an output terminal of the comparator circuit 21 a , and an output terminal of the amplification circuit 22 is connected to the ADC circuits 31 . Accordingly, an output signal COMP_OUT 1 of the comparator circuit 21 a output to the node Q is amplified by the amplification circuit 22 . A signal COMP_OUT 2 amplified by the amplification circuit 22 is applied to the ADC circuits 31 . FIGS. 6A and 6B are circuit diagrams of the amplification circuit 22 of FIG. 5 , according to embodiments of the inventive concept. Referring to FIG. 6A , the amplification circuit 22 may be implemented as, for example, an amplifier 22 a , such as an operational amplifier OP AMP. A first input terminal of the amplifier 22 a is connected to the node Q corresponding to the output terminal of the comparator circuit 21 a , and a reference voltage REF is applied to a second input terminal of the amplifier 22 a . For example, the first input terminal of the amplifier 22 a is set as a positive terminal+, and the second input terminal of the amplifier 22 a may be set as a negative terminal −. For another example, the first input terminal of the amplifier 22 a is set as the negative terminal −, and the second input terminal of the amplifier 22 a may be set as the positive terminal +. The output terminal of the amplifier 22 a is connected to the ADC circuits 31 . Referring to FIG. 6B , the amplification circuit 22 may be implemented as, for example, an inverter 22 b . An input terminal of the inverter 22 b is connected to the node Q corresponding to the output terminal of the comparator circuit 21 a , and an output terminal of the inverter 22 b is connected to the ADC circuits 31 . FIG. 7 is a circuit diagram of the amplification circuit 22 added to the comparator circuit 21 b connected to one column signal line of the pixel sensor 11 of FIG. 4 , according to another embodiment of the inventive concept. The pixel sensor 11 , the comparator circuit 21 b , and the load circuit 41 of FIG. 7 are described in detail with reference to FIG. 4 , and, thus, redundant descriptions thereof will not be repeated here. Referring to FIG. 7 , an input terminal of the amplification circuit 22 is connected to the node Q corresponding to an output terminal of the comparator circuit 21 b , and an output terminal of the amplification circuit 22 is connected to the ADC circuits 31 . Accordingly, the output signal COMP_OUT 1 of the comparator circuit 21 b output to the node Q is amplified by the amplification circuit 22 . The signal COMP_OUT 2 amplified by the amplification circuit 22 is applied to the ADC circuits 31 . FIGS. 8A and 8B are circuit diagrams of the amplification circuit of FIG. 7 , according to embodiments of the inventive concept. Referring to FIG. 8A , the amplification circuit 22 may be implemented as, for example, the amplifier 22 a , such as the operational amplifier OP AMP. A first input terminal of the amplifier 22 a is connected to the node Q corresponding to the output terminal of the comparator circuit 21 b , and the reference voltage REF is applied to a second input terminal of the amplifier 22 a . For example, the first input terminal of the amplifier 22 a is set as a positive terminal +, and the second input terminal of the amplifier 22 a may be set as a negative terminal −. For another example, the first input terminal of the amplifier 22 a is set as the negative terminal −, and the second input terminal of the amplifier 22 a may be set as the positive terminal +. The output terminal of the amplifier 22 a is connected to the ADC circuits 31 . Referring to FIG. 8B , the amplification circuit 22 may be implemented as, for example, the inverter 22 b . An input terminal of the inverter 22 b is connected to the node Q corresponding to the output terminal of the comparator circuit 21 b , and an output terminal of the inverter 22 b is connected to the ADC circuits 31 . FIG. 13 is a block diagram of an image processing apparatus 1000 according to embodiments of the inventive concept. For example, the image processing apparatus 1000 may be included in a computer apparatus, a camera apparatus, a cellular phone apparatus, a scanner apparatus, a navigation apparatus, a security system, and the like. Referring to FIG. 13 , the image processing apparatus 1000 may include the image sensor 100 , a processor 200 , a non-volatile memory device 300 , a random access memory (RAM) 400 , an input/output device I/O 500 , and a bus 600 . The image sensor 100 of FIG. 1 may be applied to the image sensor 100 of FIG. 13 . The embodiments of the image sensor 100 of FIGS. 2 through 10 may be applied to the image sensor 100 of FIG. 13 . The processor 200 controls an operation of the image sensor 100 and performs signal post-processing on a signal output from the image sensor 100 . The processor 200 may transmit or receive data to or from elements connected through the bus 600 . The non-volatile memory device 300 may store image data on which post-processing is performed by the processor 200 or a program and data necessary for controlling the image processing apparatus 1000 . The non-volatile memory device 300 may be implemented as a non-volatile semiconductor memory device, for example, phase change RAM (FRAM), ferroelectric RAM (FRAM), magnetic RAM (MRAM), and the like. The RAM 400 may temporarily store data used in the image processing apparatus 1000 . An input device included in the input/output device 500 may be implemented as a keyboard, a mouse, a keypad, and the like, and an output device included therein may be implemented as a display, a printer, and the like. While the inventive concept has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the following claims.
An image sensor senses object information and converts the sensed object information into an electrical signal. An image processing apparatus uses the image sensor. The image sensor includes a column signal line connected to output terminals of a plurality of pixel sensors, a comparator circuit configured to output a signal corresponding to a comparison result of a signal output to the column signal line and a reference signal, an ADC circuit configured to convert an analog signal corresponding to an optical signal sensed by the pixel sensor selected from the plurality of pixel sensors connected to the column signal line into digital data based on the signal output from the comparator circuit and, a load circuit connected in series to the comparator circuit between the column signal line and a ground terminal, wherein the load circuit is configured as a common load device of the plurality of pixel sensors connected to the column signal line and the comparator circuit.
7
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the closure of large vessels which may operate under pressure and at high temperature. 2. Description of the Prior Art The most common method for mounting doors, covers, or other closure devices on large vessels which operate under pressure and at high temperature has been by bolting them to flanges on the vessel opening. Sealing, where required, is usually by use of various gaskets or O-rings. High temperature or pressure vessel closures are typically held in place by numerous bolts or studs and nuts. Removal and replacement of the bolted cover is a time-consuming operation. Removal of the bolts or nuts must generally be done by operators on site and thus it is sometimes necessary to wait for the vessel to cool before the closure can be removed. Another method sometimes used to remove such a vessel cover involves the placement of some type of strong back or frame over the back of the closure and attaching the frame to the vessel, thereby pressing the closure itself onto the opening. Such frames can be hinged or otherwise attached to reduce the number of bolts or other attachment devices necessary to hold the closure on the vessel opening. This method requires the sacrifice of some of the rigidity and sealing ability found in the aforementioned bolted flange system. Numerous cycles of operation can cause the cover itself to become warped or cause the sealing devices used to deteriorate so that a successful design must allow for these increased tolerances. Where the temperatures and pressures encountered will allow their use, inflatable seals are sometimes incorporated into either of these types of vessel closure designs in order to accommodate the warping and deterioration that will take place. A device disclosed in U.S. Pat. No. 3,819,479 exhibits inflatable seals which can aid in sealing between the vessel flange and the closure plug and the flange of the plug. Some of these seals can also be inflated in order to lift the plug itself and allow its movement. This design incorporates a variation of the bolted flange with the plug assembly being bolted in place by use of a collar. The device disclosed in U.S. Pat. No. 871,421 exhibits an inflatable tube which exerts a force against a door and a door frame to seal the door against the vessel. The door is held in place by a separate locking device. The inflatable tube here is used to position the door for sealing by other devices rather than performing the sealing function itself. The invention disclosed in U.S. Pat. No. 3,632,303 exhibits a pressure hose which can be pressurized to exert force via a lever bar to force the closure against the seal. The attachment of the closure to the vessel is achieved by a variation of the normal bolting method. Local operation by hand is essential in attaching the closure to the vessel. The invention disclosed in U.S. Pat. No. 3,500,584 exhibits an inflatable seal which positions the closure against another seal with attachment of the closure being by means of a bolted apparatus. These and similar devices all suffer from the disadvantage of requiring local hand operation to attach or remove the closure and sometimes they sacrifice the strength of a bolted flange in order to reduce removal time, resulting in warpage or seal failure. U.S. Pat. No. 4,820,384 disclosed a remotely operable apparatus for installing and removing a vessel cover from a large vessel. Specially shaped connector pins align the cover with the opening and attach the cover to a mounting rim around the opening of the vessel. An incrementally rotating ring secures the cover to the connector pins, then an actuator which expands under fluid pressure is used to force the cover into its final position firmly against the vessel opening. A second rotating ring wedges the cover in its final position for the duration of the operating cycle of the vessel. The installing and removing operations can be performed remotely, resulting in a high-strength closure which can be quickly removed and replaced. SUMMARY OF THE PRESENT INVENTION The cover positioner assembly is a remotely operable apparatus for installing and removing a vessel cover from a vessel. The cover positioner assembly can be used with any vessel having a mounting rim around the vessel opening. The cover positioner assembly includes a cover sized to fit against the mounting rim of the vessel. Specially designed connector pins mount to the mounting rim and secure the cover to the mounting rim. A rotating lock ring secures the connector pins to the cover positioner assembly and a force actuator expands under fluid pressure to force the cover into sealing engagement with the mounting rim. A ramp ring rotates to secure and lock the cover in the sealed position and the pressure in the force actuator is released for the duration of the operating cycle of the vessel. A ramp ring safety lock apparatus prevents the accidental rotation of the ramp ring and the breaking of the seal between the cover and the mounting rim of the vessel. A quick-acting pipe connector assembly is also disclosed for making or breaking a quick pipe connection to the vessel cover. The quick-acting pipe connector assembly can be used to join two ends of pipe. A flange is mounted on the end of one pipe and the quick-acting pipe connector assembly includes a pipe end fitting sized to fit against the pipe flange. A force ring mounts to the pipe end fitting and specially designed connector pins mount to the force ring and secure the force ring to the flange. A rotating lock ring secures the connector pins to the flange and a force actuator expands under fluid pressure to force the pipe end fitting into sealing engagement with the flange. A ramp ring rotates to secure and lock the force ring in the sealed position for the duration of the pipe connection and the pressure in the force actuator is released. BRIEF DESCRIPTION OF THE DRAWINGS In order to more fully understand the drawings used in the detailed description of the present invention, a brief description of each drawing follows: FIG. 1 is an elevation view of the remotely operable vessel cover positioner of the present invention illustrating the cover assembly in a lowered position on a dolly and showing the dolly transporting the cover assembly in phantom; FIG. 2 is a plan view taken along line 2--2 in FIG. 1; FIG. 3 is a partial plan view taken along line 3--3 in FIG. 1; FIG. 4 is a partial cross-sectional elevation view showing the cover assembly in a raised position with the connector pins in a retracted position; FIG. 5 is a partial cross-sectional elevation view showing the cover assembly in a raised position with the connector pins in an extended position; FIG. 6 is a partial cross-sectional elevation view showing the upper and lower ramp rings in a disengaged position; FIG. 7 is a partial cross-sectional elevation view showing the upper and lower ramp rings in an engaged position; FIG. 8 is a cross-sectional elevation view of a ramp safety lock apparatus in an unlocked and retracted position; FIG. 9 is a cross-sectional elevation view of the ramp safety lock apparatus in a locked position; FIG. 10 is a cross-sectional elevation view of the ramp safety lock apparatus showing the lock in the process of being unlocked; FIG. 11 is a view taken along line 11--11 in FIG. 10; FIG. 12 is a cross-sectional view of a quick acting pipe connector assembly of the present invention; and FIG. 13 is a partial plan view of the lock ring showing the details of the keyhole openings. DETAILED DESCRIPTION OF THE INVENTION The invention can readily be described as it is used on a typical coke oven or other vertical vessel with an opening on the bottom. Referring to FIG. 1, the vessel with which the invention is used is generally indicated as V. Such a vessel V would typically be relatively large and have a vertical axis and legs or other supporting structure not shown in the figure. A cover positioner assembly, generally depicted as C in FIG. 1, and including a cover 10, is generally attached to an opening in the vessel V which is normally a round opening of large diameter. The means of attachment is by attaching the cover 10 to a mounting rim, in this case a flange 5, which surrounds the opening, and which has circumferentially spaced holes 5a as shown in FIG. 4. The holes 5a in the vessel flange 5 extend through the flange 5 and include a lower bore 5b having a diameter greater than an upper bore 5c for reasons which will be explained below. The vessel V is charged with a quantity of raw material and then heated and possibly maintained at an elevated pressure in performing the desired process, such as making coke. After the process is performed, the product is discharged by removing the cover 10 from the opening. A cart or dolly, generally designated as 100 in FIG. 1, is used to handle and transport the cover 10. This cart 100 can take various forms, but it will typically have a framework which includes legs 100a and wheels 100b which can roll on a track as illustrated or directly on the floor. The cart 100 includes a platform or other supporting surface 100c upon which the cover assembly C comes to rest after removal from the vessel V. The platform 100c includes a recessed portion (not shown) for receiving inlet piping, generally designated as P in FIG. 1. The inlet piping P is connected at one end to the cover 10 and a second end connects to a quick acting pipe connector assembly 200 which will be more fully described below. Referring to FIGS. 1 and 2, a plurality of cover lift cylinder assemblies 120 are mounted to the flange 5 of the vessel V with vessel lift cylinder brackets 122. Preferably, at least three such vessel lift cylinder assemblies 120 are equally spaced around the perimeter of the vessel V. Preferably, a single control (not shown) synchronously controls the plurality of cylinder assemblies 120. As shown in FIGS. 1 and 3, a corresponding set of cover lift cylinder brackets 124 are mounted to the cover assembly C. The cover lift cylinder brackets 124 include a slot 124a which receives an end portion 120a of the cover lift cylinder assemblies 120. The cover lift cylinder assemblies 120 are used to raise the cover assembly C to the flange 5 of the vessel and to lower the cover assembly C from the flange 5 to the platform 100c of the cart 100. In order to look more closely at the cover positioner assembly C, refer to FIGS. 4 and 5, where it will be seen that the cover 10 mates with the vessel flange 5 with the necessary seal being provided by a gasket 15. The cover 10 in the preferred embodiment is a circular disc having a generally flat upper surface 11 including a downwardly tapered outer portion 11a. The downwardly tapered outer portion 11a includes a plurality of circumferentially spaced holes 12 corresponding to the circumferentially spaced holes 5a of the vessel flange 5. A generally flat lower surface 13 of the cover 10 includes annular recesses 13a, 13b machined into the lower surface 13 of the cover 10 to provide a location for a force actuator 40 which will be more fully described later. A third annular recess 13c is machined on the outer periphery of the cover 10 just inside the circumferentially spaced holes 12 to provide a location for a plurality of upper ramps 50. The plurality of upper ramps 50, which can be seen in more detail in FIGS. 6 and 7, are wedge-shaped arcuate sections having a substantially flat upper surface 50a which bears against the third annular recess 13c of the cover 10 and a slanted planar lower surface 50b which interacts with a corresponding slanted planar upper surface 52b of a lower ramp 52. The upper ramp 50 includes step portions 50c, 50d at opposite ends of the upper ramps 50 which overlap with step portions 50d, 50c respectively of adjoining upper ramps 50. Each upper ramp 50 also includes a blind bore 50e opening in the upper surface 50a which receives a stab post 54 extending downwardly from the third annular recess 13c of the cover 10. A through bore 50f extends through the upper ramp 50 from the upper surface 50a to a lower cutout section 50g. A ramp connecting bolt 55 is inserted through the through bore 50f and threadably engages a threaded hole 13d in the cover 10 to removably fasten the upper ramp 50 to the cover 10. The upper ramp 50 is thus held in place with the ramp connecting bolt 55, the stab post 54, and the overlapping step portions 50c and 50d . The cutout section 50g provides adequate clearance for the connecting bolt head 55a to avoid obstruction with the lower ramp 52, as will be further described below. Still referring to FIGS. 6 and 7, the plurality of lower ramps 52 are similar to the upper ramps 50 and are wedge-shaped arcuate sections having a substantially flat lower surface 52a which bears against a lower ramp ring 56. The lower ramps 52 have a slanted planar upper surface 52b which interacts with the corresponding slanted planar surface 50b of the upper ramp 50. The lower ramp 52 includes step portions 52c, 52d at opposite ends of the lower ramps 52 which overlap with step portions 52d, 52c, respectively, of adjoining lower ramps 52. Each lower ramp includes a blind bore 52e opening in the lower surface 52a which receives a stab post 58 extending upwardly from the lower ramp ring 56. A through bore 52f extends through the lower ramp 52 from the lower surface 52a to an upper cutout section 52g. A lower ramp connecting bolt 59 is inserted through the through bore 52f and threadably engages a threaded hole 56a in the lower ramp ring 56 to removably fasten the lower ramp 52 to the lower ramp ring 56. The lower ramp 52 is held in place with the ramp connecting bolt 59, the stab post 58, and the overlapping step portions 52c and 52d. The cutout section 52g provides adequate clearance for the connecting bolt head 59a to avoid obstruction with the upper ramp 50. As shown in FIG. 1, the upper ramps 50 are mounted to the cover 10 and are joined end to end in an overlapping relationship to form a complete circle around the outer periphery of the force actuator 40 and within the periphery of the plurality of circumferentially spaced holes 12 of the cover 10. The lower ramps 52 are mounted to the lower ramp ring 56 and are similarly joined end to end forming a complete circle substantially the same size as formed by the upper ramps 50 such that the slanted planar surfaces 50b, 52b interact and cooperatively contact one another when engaged as will be described below. Referring to FIGS. 4 and 5, the cover 10 rests indirectly upon a force ring 20 which is an annular structure having an annular support flange 20a around the internal periphery of the force ring 20. The annular support flange 20a includes a plurality of spaced holes 20b extending therethrough which correspond to a plurality of spaced threaded holes 13e in the cover 10. A force ring retaining bolt 22 having a shoulder 22a is inserted through the hole 20b in the support flange 20a and threadably engages with the hole 13e. The retaining bolt 22 is advanced into the threaded hole 13e until the shoulder 22a abuts the lower surface 13 of the cover 10. The retaining bolt 22 has a length between the shoulder 22a and the bolt head that is slightly greater than the thickness of the support flange 20a so that the force ring 20 is loosely attached to the cover 10 with the force ring retaining bolts 22. A generally flat upper surface 21 of the force ring 20 includes annular recesses 21a, 21b machined into the upper surface 21 in opposing relationship to the annular recesses 13a, 13b, respectively, of the cover 10 to house inner annular ring 40a and outer annular ring 40b of the force actuator 40. The inner annular ring 40a has a tubular cross section and is positioned in the combined annular recesses 13a and 21a. The outer annular ring 40b has a tubular cross section and is positioned in the combined annular recesses 13b and 21b. The rings 40a, 40b are connected to one another by an inflation membrane 40c which joins the rings 40a and 40b and lies flatly between the lower surface 13 of the cover 10 and the upper surface 21 of the force ring 20 in the space between the rings 40a and 40b. In the preferred embodiment, the inner and outer annular rings 40a and 40 b, respectively, and the inflation membrane 40c are made of metal, preferably stainless steel. An inner filler bar 41a and an outer filler bar 41b are positioned inside the inner and outer annular rings 40a and 40b, respectively. The filler bars 41a, 41b, are round steel bars forming a circle which are placed in the annular rings 40a, 40b, to reduce the amount of fluid needed to pressurize the force actuator 40. Fluid pressure is introduced to the inflation membrane 40c by pressure tube 40d through force ring 20 and thence the inflation membrane 40c to the rings 40a, 40b. A quick connect coupling 40e attached to the end of the pressure tube 40d detachably connects with a mating coupling 40f which is in communication with a pressure source (not shown). The fluid may be either a gas or a hydraulic-type liquid. The inflation membrane 40c will expand sufficiently upon inflation by pressurized fluid to raise the cover 10 with respect to the connector pins 60 as more fully described below. Referring to FIG. 5, the annular recess 21b is machined on the periphery of the force ring 20 and has a depth sufficient to allow the lower ramp ring 56 to rest on the lower face of the annular recess 21b without interfering with outer annular ring 40b. The outer periphery of the annular recess 21b includes a plurality of circumferentially spaced holes 20c which align with the plurality of spaced holes 12 in the cover 10. Referring to FIGS. 4 and 5, the ramp ring 56 is a flat ring having a smooth lower surface 56b which is permitted to slide on the lower surface of the annular recess 21b of the force ring 20. The ramp ring 56 has a substantially flat upper surface 56c having an outer periphery recess 56d for receiving the plurality of lower ramps 52. The ramp ring 56 includes a plurality of orifices 56e extending from the upper surface 56c to an annular recess 56f formed in the lower surface 56b of the ramp ring 56. The annular recess 56f is in fluid communication with a plurality of purge tubes 21d extending through the force ring 20 to the lower surface of the force ring 20. The purge tubes 21d are in fluid communication with an annular purging channel 23 attached to the lower surface of the force ring 20. A purging fluid inlet tube 23a feeds into the purging channel 23. The force actuator 40 can be purged or flushed with a purging fluid, such as water, by filling the purging channel 23 with fluid via the inlet tube 23a and continuing to fill so that the fluid fills the plurality of purge tubes 21d, then the annular recess 56f and the orifices 56e before filling the area around the force actuator 40. The fluid is allowed to drain between the upper and lower ramps 50, 52 and via a drain tube 21c in fluid communication with the annular recess 21a. As shown in FIGS. 1, 2, and 3, the ramp ring 56 includes a pair of slotted ramp ring ears 57 attached to the perimeter of the ramp ring 56 and extending beyond the outer perimeter of the cover 10 and force ring 20. A ramp ring lever 66 is pivotally connected to a ramp ring lever pivot arm 67 which is firmly secured to the outer perimeter of the cover 10. As can be seen in FIG. 1, the ramp ring lever 66 has a lower end 66a which extends through the slotted ramp ring ear 57. The ramp ring lever 66 has an upper end 66b which is received by ramp ring rotation means 70 mounted via cylinder bracket 70a. The ramp ring rotation means 70 includes a pivotably mounted hydraulic cylinder assembly 70b oriented tangentially with respect to the cover 10. The end of an extending ram 70c of the hydraulic cylinder assembly 70b includes a slotted receiver 70d which receives and engages the upper end 66b of the ramp ring lever 66. As shown in FIG. 1, as the cover assembly C is raised to the mounting rim 5, the upper end 66b of the ramp ring lever 66 is slightly forward of the slotted receiver 70d. As the ram 70c is extended, the pivotably mounted cylinder assembly 70b allows the cylinder assembly 70b to pivot upwards as the slotted receiver 70d engages the upper end 66b of the ramp ring lever 66. A cylinder assembly stop 70e is attached to the flange 5 to limit the downward movement of the cylinder assembly 70b. An identical ramp ring lever 66 assembly with ramp ring rotation means 70 is also provided on the opposite site of the cover 10 to facilitate the rotation of the ramp ring 56 during the final positioning of the cover positioner assembly C as will be explained below. Referring to FIGS. 1, 3, 4, and 13, lock ring 30 is an annular ring having a plurality of circumferentially spaced holes 30a which align with the holes 20c in the force ring 20. The lock ring 30 is mounted for rotation in a recessed annular portion 20d in the lower surface of the force ring 20. The lock ring 30 rests on a lock ring support plate 32 which is attached by support plate bolts 32a to the force ring 20. The lock ring 30 engages and locks a plurality of connector pin assemblies 60 which extend through the plurality of circumferentially spaced holes in the flange 5, the cover 10, and the force ring 20. Each connector pin 60 has threads 60a on one end onto which nuts 60b are threaded. On the end of connector pin 60 distal from the threads 60a is head 60c. In the preferred embodiment, the end of the head 60c is hexagonal shaped to allow a standard wrench to be used to prevent rotation during the adjustment of the nuts 60b. The connector pin 60 includes a shoulder 60d near the head 60c for radially aligning the connector pins 60 in the hole 20c in the force ring 20. As shown in FIG. 13, the lock ring 30 has keyhole shaped openings 30a which have large diameter l and small diameter s. Large diameter l is slightly larger than the diameter of the connector pin head 60c and small diameter s is smaller than the diameter of connector pin head 60c but slightly larger than the diameter of the shank of the connector pin 60. As shown in FIGS. 1, 2, and 3, the lock ring 30 includes a pair of slotted lock ring ears 31 attached to the perimeter of the lock ring 30 and extending beyond the outer perimeter of the cover 10 and force ring 20. A lock ring lever 62 is pivotally connected to a lock ring lever pivot arm 63 which is firmly secured to the outer perimeter of the cover 10. As can be seen in FIG. 1, the lock ring lever 62 has a lower end 62a which extends through the slotted lock ring ear 31. The lock ring lever 62 has an upper end 62b which is received by lock ring rotation means 80 mounted via cylinder bracket 70a. The lock ring rotation means 80 includes a pivotably mounted hydraulic cylinder assembly 80b oriented tangentially with respect to the cover 10. The end of an extending ram 80c of the hydraulic cylinder assembly 80b includes a slotted receiver 80d which receives and engages the upper end 62b of the lock ring lever 62. As shown in FIG. 1, as the cover assembly C is raised to the mounting rim 5, the upper end 62b of the lock ring lever 62 is slightly forward of the slotted receiver 80d. As the ram 80c is extended, the pivotably mounted cylinder assembly 80b allows the cylinder assembly 80b to pivot upwards as the slotted receiver 80d engages the upper end of 62b of the lock ring lever 62. A cylinder assembly stop 80e is attached to the flange 5 to limit the downward movement of the cylinder assembly 80b. An identical lock ring lever 62 assembly with lock ring rotation means 80 is also provided on the opposite side of the cover 10 to facilitate the rotation of the lock ring 30 during the initial positioning of the cover positioner assembly C as will be explained below. Referring to FIGS. 4 and 5, an interference plate 30b is connected to the lock ring 30. The interference plate 30b extends downwardly as shown in FIGS. 4 and 5 to a position in front of or to the side of a quick connect coupling 40e depending on the position of the lock ring 30 for reasons which will be explained below. Referring to FIG. 5, the connector pins 60 include a longitudinal blind bore 60e in the threaded end of the connector pins 60 for receiving a first end of a lift rod 60f. As shown in FIGS. 1, 2, and 5, a pin lift ring 86 is an annular ring having a plurality of circumferentially spaced holes 86a in spaced relationship to the plurality of spaced holes 5a in the flange 5. The spaced holes 86a in the pin lift ring 86 extend over the upper end of the lift rods 60f. The upper end of the lift rods 60f receive a cap 60g which attaches to the lift rods 60f. The cap 60g may be attached by various means but is shown in FIGS. 4 and 5 to be attached with a pin 60h extending through the cap 60g and the lift rod 60f. A plurality of lift ring lifting cables 88 are connected to the periphery of the lift ring 86 as shown in FIGS. 1, 4, and 5. Preferably, there are at least three lifting cables 88 at equal spacings around the circumference of the vessel V although only one is shown in FIG. 1 for clarity purposes. As shown in FIG. 1, an upper end of each lifting cable is connected to a lift ring hydraulic cylinder 89 which is mounted to the vessel V. The stroke of the lift ring hydraulic cylinder 89 raises and lowers the pin lift ring 86 which in turn raises and lowers the plurality of connector pins 60. As shown in FIG. 1, a lift ring pulley assembly 88a is attached to the vessel V at a location such that the lifting cable 88 is maintained in a substantially vertical position between the pin lift ring 86 and the pulley assembly 88a. This configuration enables the connector pins 60 and the pin lifting ring 86 to be vertically raised and lowered without misalignment. FIGS. 8, 9, 10, and 11 show a ramp safety lock apparatus 90 having a housing 90a which has an enlarged cavity 90b in the mid portion of the housing 90a. The housing 90a has a first end 90c with a bore 90d extending through the first end 90c to the cavity 90b and finally through a second end 90e of the housing 90a. As shown in FIGS. 1 and 3, the second end 90e of the housing 90a is pivotably connected with a fastener 98a to a lifting support member 98 which is securely mounted to the periphery of the force ring 20. A pair of bushings 90f are fitted within the bores 90d, and a pair of packing glands 90g are threadably engaged with the bores 90d at the first and second ends 90c, 90e of the housing 90a. A connector rod 92 is pivotably connected at a first end 92a to the ramp ring 56 with a ramp ring pivot pin 56g. The connector rod 92 includes a second end 92b which slidably extends through the bore 90d in the first end 90c of the housing 90a. The second end 92b of the connector rod 92 is pivotably connected to a gripper 94 via a gripper pin 94a which is inserted through a gripper opening 94b and a hole in the second end 92b of the connector rod 92. In the preferred embodiment as shown in FIGS. 8-10, 10, the opening 94b is oval in shape with the long axis of the oval being substantially vertical for reasons to be explained below. The gripper 94 includes an inwardly tapered recess 94c in an end facing the second end 90e of the housing 90a. The inwardly tapered recess 94c receives a tapered end 96a of a plunger rod 96 which extends through the bore 90d in the second end 90e of the housing 90a. The distal end of the plunger rod 96 includes a handle 96b for inserting and withdrawing the plunger rod 96 in the housing 90a. The gripper 94 includes an upper ridge 94d on the upper face of the gripper 94 and a plurality of teeth 94e on the lower face of the gripper 94. A lower surface 90h of the cavity 90b includes a plurality of teeth 90i capable of engaging the teeth 94e of the gripper 94. Gravity will cause the gripper teeth 94e to engage the housing teeth 90i as shown in FIG. 9. The configuration of the teeth 90i and 94e and the pivot connection of the gripper 94 allows the gripper teeth 94e to travel along the housing teeth 90i in a direction towards the first end 90c of the housing 90a as the connector rod 92 is withdrawing from the housing 90a. Also, as shown in FIG. 9, a centerline 96' of the plunger rod 96 is slightly offset above a centerline 94' of the tapered recess 94c when the teeth 90i, 94e are engaged; however, when the plunger rod 96 is inserted in the housing 90a to a point where the tapered end 96a enters the tapered recess 94c of the gripper 94 and is fully received by the tapered recess 94c, the gripper 94 pivots about the gripper pin 94a and raises to a position where the teeth 90i, 94e are no longer engaged as shown in FIG. 10. Thus, so long as the plunger rod 96 maintains the gripper teeth 94e in the raised position, the connector rod 92 is permitted to slide into the housing 90a. The significance of this ramp safety lock apparatus 90 will be explained in the operation of the preferred embodiment which follows. Referring to FIGS. 1 and 12, a quick-acting pipe connector assembly 200 is shown attached to an end of the inlet piping P. The quick-acting pipe connector assembly 200 is structurally very similar to the cover positioner assembly C described above. Thus, elements that are structurally similar will be identified by the same name with a different reference numeral and it may be necessary to refer to some of the drawings pertaining to the cover positioner assembly C to more fully understand the structural features of the corresponding elements of the quick-acting pipe connector assembly 200. The end of the inlet piping P includes a flange 202 having a plurality of circumferentially spaced holes 204. A lock ring 230, similar to the lock ring 30 discussed above, is an annular ring having a plurality of circumferentially spaced keyshaped openings 230a which align with the holes 204 in the flange 202. The key-shaped openings are similar to the openings 30a in the lock ring 30 as shown in FIG. 13. The lock ring 230 is mounted for rotation at a rear face 202a of the flange 202 and is held in place with a lock ring support plate 232 which is welded to the flange 202. Referring to FIG. 12, the mating pipe P' includes a threaded end fitting 210 having a smooth, flat end 210a that mates with the piping flange 202 with the necessary seal being provided by a gasket 212. A force ring 214 is an annular structure comprising a fixed force ring 216 and a movable force ring 218. The fixed force ring 216 includes an internally threaded opening 216a which engages the threaded end fitting 210 of the mating pipe P'. The force ring 214 includes a plurality of circumferentially spaced holes 214a extending through the fixed and movable force rings 216, 218 which correspond to the plurality of spaced holes 204 in the flange 202. The lock ring 230 engages and locks a plurality of connector pin assemblies 260 which extend through the plurality of circumferentially spaced holes 214a, 204, and 230a in the force ring 214, flange 204, and the lock ring 230, respectively. Each connector pin 260 has threads 260a on one end onto which a nut 260b is threaded. On the end of connector pin 260 distal from the threads 260a is head 260c. The connector pin 260 includes a shoulder 260d near the head 260c for radially aligning the connector pins 260 in the hole 214a in the force ring 214. Referring to FIG. 12, the connector pins 260 include a longitudinal threaded bore 260e in the threaded end of the connector pins 260 for receiving a threaded end of a lift screw 260f. A lift ring 286 has a plurality of circumferentially spaced holes in spaced relationship to the plurality of spaced holes 214a in the force ring 214. The spaced holes 286a in the lift ring 286 align with the threaded bores 260e in the connector pins 260 and the lift screws 260f secure the lift ring 286 to the ends of the connector pins 260. The lift ring 286 includes a pair of handles 286a for removing or inserting the connector pins 260 through the flange holes 204. The fixed and moveable force rings 216 and 218 are held together with a plurality of guide bolts 222 having a threaded end portion 222a. The guide bolts 222 are inserted through a guide bolt bore 218c in the moveable force ring 218 and then threadably engage with a threaded bore 216c in the fixed force ring 216. The guide bolt 222 includes a shoulder 222b located slightly beyond the outer face of the moveable force ring 218. The shoulder 222b limits the travel of the moveable force ring 218 from the fixed force ring 216. The guide bolt 222 also includes an extending portion 222c which extends through guide bolt openings 286b in the lift ring 286. The guide bolt extending portions 222c serve to maintain the connector pins 260 in alignment with the holes when the connector pins 260 are retracted. The fixed force ring 216 includes a generally flat mating surface 216a having an annular recess 216b machined into the mating surface 216a. The movable force ring 218 also includes a generally flat mating surface 218a having an annular recess 218b. The annular recesses 216b, 218b are in opposing relationship to one another and provide a location for an inner annular ring 240a of a force actuator 240. An outer annular ring 240b is positioned outside of the mating surfaces 216a, 218a, enclosed by a pair of annular outer shields 242a and 242b attached to the fixed and movable force rings 216 and 218 respectively. The rings 240a, 240b are connected to one another by an inflation membrane 240c which joins the rings 240a and 240b and lies flatly between the mating surfaces 216a and 218a of the fixed and moveable force rings 216 and 218, respectively, in the space between the rings 240a and 240b. In the preferred embodiment, the inner and outer annular rings 240a and 240b, respectively, and the inflation membrane 240c are made of metal, preferably stainless steel. An inner filler bar 241a and an outer filler bar 241b are positioned inside the inner and outer annular rings 240a and 240b, respectively. The filler bars 241a, 241b are round steel bars forming a circle which are placed in the annular rings 240a, 240b, to reduce the amount of fluid needed to pressurize the force actuator 240. Fluid pressure is introduced to the inflation membrane 240c by pressure tube 240d through fixed force ring 216 and thence the inflation membrane 240c to the rings 240a, 240b. The fluid may be either a gas or a hydraulic-type liquid. The inflation membrane 240c will expand sufficiently upon inflation by pressurized fluid to position the end face 210a of the pipe end fitting 210 firmly against the gasket 212 as more fully described below. The inner periphery of the annular recess 216b of the fixed force ring 216 provides a location for a plurality of fixed ramps 250 which are similarly shaped and attached to the fixed force ring 216 as the upper ramps 50 are to the cover 10 as previously described. The inner periphery of the annular recess 218b of the moveable force ring 218 provides a location for a plurality of moveable ramps 252 which are similarly shaped and attached to a ramp ring 256 as the lower ramps 52 are to ramp ring 56 as previously described. The ramp ring 256 has a handle 257 attached to the ramp ring 256 for rotating the ramp ring 256 and the moveable ramps 252 as will be explained below. Operation of the Invention The operation of the preferred embodiment will now be described. As seen in FIG. 1, a cart 100 can be used to move the cover positioner assembly C into general alignment with the vessel opening. The end portions 120a of the cover lift cylinder assemblies 120 are downwardly extended and the connector pins 60 are in the raised position as the cart 100 approaches with the cover positioner assembly C as shown in FIG. 1. The slots 124 of the cover lift cylinder brackets 124 receive the downwardly extending end portions 120a. The cover lift cylinder assemblies 120 then raise the cover positioner assembly C into contact with the vessel flange 5 and maintain alignment of the holes 5a in the vessel flange 5 with the corresponding holes 12 in the vessel cover 10. As seen in FIG. 4, the vessel cover 10 contacts the gasket 15 at the perimeter of the opening. After the cover positioner assembly C has been raised to the flange 5, the upper ends 62b and 66b of the lock ring lever 62 and the ramp ring lever 66, respectively, are received by the slotted receivers 80d and 70d of the lock ring rotation means 80 and the ramp ring rotation means 70, respectively, by extending the respective cylinder rams 80c and 70c. The lift ring hydraulic cylinder 89 is then activated to lower the pin lift ring 86 which allows the connector pins 60 to pass through the aligned corresponding holes 12, 20c, and 30a in the cover 10, force ring 20, and the lock ring 30, respectively. The connector pin 60 is attached to the vessel flange 5 by the nuts 60b with the axial alignment being maintained in the holes by the shoulder 60d and the connector pin head 60c. As shown in FIG. 5, the nuts 60b are located so that when the nuts 60b come to rest against the flange 5, the portion of the connector pin 60 between the head 60c and the shoulder 60d will be positioned in the hole 30a of the lock ring 30. As shown in FIG. 4, as the connector pin 60 is being lowered, the keyhole shaped opening 30a of the lock ring 30 is oriented so that the large diameter l is aligned to allow the head 60c to pass through the opening 30 a. The hydraulic cylinder assembly 80b of the lock ring rotation means 80 then rotates the lock ring 30 so that the small diameter s of the opening 30a is positioned between the pin head 60c and the shoulder 60d as shown in FIG. 5. This operation locks the connector pin head 60c below the lock ring 30 which in turn supports the force ring 20. As shown in FIG. 4, when the lock ring 30 is in its unlocked position, the interference plate 30b is positioned in front of the quick connect coupling 40e to prevent the premature inflation of the force actuator 40. As the lock ring is rotated to the locked position as shown in FIG. 5, the interference plate 30b is rotated to the side of the quick connect coupling 40e, thus permitting the mating coupling 40f to be connected to the coupling 40e. After the lock ring 30 is rotated into its locking position with respect to the connector pin head 60c and the pressure source connection is made, fluid pressure is applied via the pressure tube 40d to the force actuator 40. This pressurizes the inflation membrane 40c and both the inner annular ring 40a and the outer annular ring 40b. When under pressure as shown in FIG. 5, the inflation membrane 40c and the rings 40a and 40b expand, reacting against the force ring 20, which is held in place by the lock ring 30 and the connector pins 60, and the cover 10. The resulting force against the cover 10 presses it firmly against the gasket 15. In order to prevent permanent deformation of the rings 40a and 40b, the travel of the cover 10 is limited by the force ring retaining bolt 22 threadably engaging the cover 10. Expansion of the inflation membrane 40c and annular rings 40a and 40b serves to substantially uniformly prestress the connector pins 60 to desired magnitude as a group, which also serves to prestress the cover 10. The advantage of prestressing, as is known in the art, is to serve to load the connector pins 60 and the cover 10 so as to maintain a desired pre-load even under the stress of operation. Referring to FIG. 6, it can be seen that prior to the inflation of the force actuator 40, the upper ramps 50 attached to the cover 10 are disengaged but in contact with the lower ramps 52 attached to the ramp ring 56 and each upper ring 50 is positioned substantially above the corresponding lower ring 50. After the lock ring 30 is rotated into place and after the force actuator 40 is pressurized to raise the cover 10 into sealing engagement with the gasket 15, a small gap forms between the upper ramps 50 and the lower ramps 52. The hydraulic cylinder assembly 70b of the ramp ring rotation means 70 then rotates the ramp ring 56 and the connected lower ramps 52 so that the small gap between the upper and lower ramps 50 and 52 is eliminated. The ramp ring 56 is rotated until the lower ramps 52 firmly contact the upper ramps 50 on the cover 10 as shown in FIG. 7. The angle of inclination of these ramps 50, 52 is sufficiently shallow so that friction between the ramps 50 and 52 of the cover 10 and the ramp ring 56 prevents the relative rotation of either part during vessel operation. Referring to FIG. 8, the ramp safety lock apparatus 90 is initially in the unlocked and retracted position prior to the ramp ring 56 being rotated to firmly engage the upper and lower ramps 50 and 52. As the ramp ring 56 is rotated by the ramp ring rotation means 70, the connector rod 92 is pulled in a direction away from the housing 90a of the ramp safety lock apparatus 90 which in turn drags the pivotably mounted gripper 94 along the teeth 90i of the housing 90a as shown in FIG. 9. The teeth 94e of the gripper 94 engage the teeth 90i which prevents the ramp ring 56 from accidently being rotated to disengage the ramps 50 and 52 during operation of the vessel. If the ramp ring rotation means 70 attempts to disengagingly rotate the ramp ring 56 while the ramp safety lock apparatus 90 is locked, the connector rod 92 will forcibly attempt to enter into the housing 90a and the gripper 94 will oppose the insertion of the connector rod 92. The force applied to the gripper 94 by the connector rod 92 causes the upper ridge 94d to rise due to the oval shape of the opening 94b and bear against the upper surface of the cavity 90b while the gripper teeth 94e are engaged with the housing teeth 90i. Thus, the gripper 94 binds in the cavity 90b and locks the ramp ring 56. This insures that ramp ring 56 will not be disengagingly rotated unless the ramp safety lock apparatus 90 has been unlocked. After the ramp ring 56 is rotated into place, the force actuator 40 is depressurized, allowing the inflation membrane 40c and the rings 40a and 40b to return to their original shape. The cover positioner assembly C remains in this condition until removal is required. The quick-acting pipe connector assembly 200 is connected by positioning the flange 202 with the gasket 212 adjacent the flat end 210a of the pipe end fitting 210. This will be accomplished as the cover positioner assembly C is being raised to the flange 5 of the vessel V. The lift ring 286 is forced towards the force ring 240 causing the heads 260c of the connector pins 260 to pass through the holes 204 in the flange 202 and the openings 230a in the lock ring 230. The lock ring 230 is then rotated so that the small diameter portion of the opening 230a located between the head 260c and shoulder 260d. After the lock ring 230 is rotated into its locking position with respect to the connector pin head 260c, fluid pressure is applied via the pressure tube 240d to the force actuator 240. This pressurizes the inflation membrane 240c and both the inner annular ring 240a and the outer annular ring 240b. When under pressure, the inflation membrane 240c and the rings 240a and 240b expand, reacting against the fixed force ring 216, which is held in place by the threaded connection to the pipe end fitting 210, and the moveable force ring 218. The resulting force against the moveable force ring 218 causes it to apply force to the connector pins 260 via the nuts 260b which in turn stesses the connector pins 260 which are secured to the flange 202 by the lock ring 230. The final result is that the pipe end fitting 210 firmly seals with the gasket 212 and the flange 202 of the pipe P. In order to prevent permanent deformation of the rings 240a and 240b, the travel of the moveable force ring 218 is limited by the guide bolt 222 threadably engaging the fixed force ring 216. After the force actuator 240 is pressurized to form the seal between the pipe end fitting 210 and the flange 202 with the gasket 212, the ramp ring 256 and the connected moveable ramps 252 are rotated via the handle 257 until the moveable ramps 252 firmly contact the fixed ramps 250 on the fixed force ring 216. After the ramp ring 256 is rotated into place, the force actuator 240 is depressurized, allowing the inflation membrane 240c and the rings 240a and 240b to return to their original shape. The quick-acting pipe connector assembly 200 remains in this condition until removal is required. To remove the quick-acting pipe connector assembly 200, the force actuator 240 is first pressurized and then the ramp ring 256 is rotated until the moveable ramps 252 disengage the fixed ramps 250. The force actuator 240 is then depressurized and the lock ring 230 is rotated until the connector pin heads 260c can pass through. At this point, the lift ring 286 is pulled away from the force ring 214 which withdraws all of the connector pins 260 from the flange 202 to a retracted position behind the plane of the flat end 210a of the pipe fitting 210 so that the pipe P and flange 202 can be lowered directly without having to be moved in a direction along the length of the pipe P. To remove the cover positioner assembly C, the force actuator 40 is first pressurized and then the ramp safety lock apparatus 90 is unlocked by inserting the plunger rod 96 into the housing 90a to a point at which the plunger rod 96 enters the tapered recess 94c and forces the gripper to pivot upwardly to fully seat the tapered end 96a of the plunger rod 96. As the plunger 94 upwardly pivots, the gripper teeth 94e disengage with the housing teeth 90i which allows the connector rod 92 to enter into the housing 90a as the ramp ring 56 is rotated by the ramp ring rotation means 70 as sequentially shown in FIGS. 9 and 8. The ramp ring 56 is rotated until the lower ramps 52 no longer contact the upper ramps 50. The force actuator 40 is then depressurized and the lock ring 30 is rotated until the connector pin heads 60c can pass through. At this point, the lift cylinder assemblies 120 lower the cover positioner assembly C to the cart D. These removal and replacement operations can be performed manually, however, the greatest utility of the invention can be achieved by using power devices such as pneumatic or hydraulic cylinders as shown in FIG. 1. The quick-acting pipe connector assembly 200 could also utilize pneumatic or hydraulic cylinders to operate the ramp and lock rings. This will allow the entire operation to be conducted in remote which can be desirable when the vessel is at a comparatively high temperature. Although shown as being manually unlocked, the ramp safety lock apparatus 90 could also be remotely operated. The cover positioner assembly C of this invention allows opening and closing of heavy vessel covers without exposing personnel to the dangers of vessel contents which may be at dangerous pressure and temperature or which may be toxic. The foregoing disclosure and description of the invention are illustrative and explanatory thereof, and various changes in the size, shape, and materials, as well as in the details of the illustrated construction may be made without departing from the spirit of the invention.
A remotely operable vessel cover assembly used with a vessel. The cover assembly has a mounting rim secured to the vessel surrounding a circular opening and a circular cover to fit against the mounting rim. A force ring having a plurality of openings is attached to the cover. Connector pins are attached to and extend from the mounting rim and through a plurality of holes in the cover and the force ring. A lock ring is rotatably attached to the force ring and locks the extending heads of the connector pins to the force ring to restrain the cover in an initial position. A force actuator, disposed between the force ring and the cover, expands under fluid pressure to react against the cover forcing the cover against the mounting rim. Upper and lower ramps are connected to the periphery of the cover and a ramp ring respectively. The ramp ring, rotatably supported between the force ring and the cover, has lower ramps positioned to match upper ramps on the cover. The rotation of the ramp ring relative to the cover holds the cover against the mounting rim. A safety lock assembly is connected to the ramp ring to prevent unintended releasing rotation of said ramp ring relative to the cover.
5
This is a continuation of application Ser. No. 09/733,629 filed Dec. 7, 2000, abandoned which application is hereby incorporated by reference in its entirety. CROSS-REFERENCE TO RELATED APPLICATIONS This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-351902, filed Dec. 10, 1999, the entire contents of which are incorporated herein by reference. BACKGROUND OF THE INVENTION The present invention relates to semiconductor devices, and more particularly to a TAB type ball grid array semiconductor device. FIG. 1A is a plan view showing a conventional TAB type, FIG. 1B is a sectional view taken along the line 1 B— 1 B of FIG. 1 A. FIG. 1C is a sectional view taken along the line 1 C— 1 C of FIG. 1 A. As shown in FIG. 1A through 1C , a Cu pattern 2 comprising copper (Cu) is formed on the surface of a polyimide tape (an insulating base) 1 . The Cu pattern 2 is formed by allowing, for example, a copper foil to adhere to the polyimide tape 1 , for example, with an adhesive agent and etching the Cu foil by using as a mask a resist layer having a pattern corresponding to, for example, the Cu pattern 2 . On the surface of the polyimide tape 1 , a solder resist layer 3 is formed, and this solder resist layer 3 is covered at least except for a wire bonding portion 2 WB, and a ball pad portion 2 BP. On the rear surface of the polyimide tape 1 , an adhesive agent layer 4 is formed. A protection tape 5 is allowed to adhere to the adhesive agent layer 4 . A semiconductor chip 6 is mounted on the TAB tape and is allowed to adhere to the TAB tape via the adhesive agent layer 4 . In allowing the semiconductor chip 6 to adhere to the TAB tape, as shown in FIG. 2A , the semiconductor chip 6 is picked up from the wafer-chip tray of the mounting device, and the semiconductor chip 6 is placed on a lower mold 22 of a pressurizing device. Next, as shown in FIG. 2B , after the position of the TAB tape having the protection tape 5 peeled off and the position the semiconductor chip 6 is corrected, an upper mold 23 is allowed to come down so that the chip 6 is bonded onto the TAB tape. However, with the conventional TAB tape, as shown in FIG. 1B , 1 C or FIG. 2B , an uneven configuration is generated on the surface where the Cu pattern 2 is formed with the presence and absence of the Cu pattern 2 . A concave portion 20 is a portion where no Cu pattern 2 is formed. A convex portion 21 is a portion where the Cu pattern 2 is formed. Therefore, when the chip 6 is heat pressurized to the TAB tape, the pressure is concentrated on the convex portion 21 as shown in FIG. 2C with the result that the pressure is applied to the concave portion 22 with greater difficulty. A difference in this pressure distribution generates a difference in the adherence force between the TAB tape and the chip 6 which will lead to the peeling off of the TAB tape from the chip 6 later. Furthermore, with the conventional TAB tape, as shown in FIG. 3 A and FIG. 3B , there arises an intersection angle θ between the solder resist layer 3 and the wire bonding portion 2 WB is less than 90 degrees. Consequently, when the solder resist is printed on the TAB tape, a disuniformity is generated in the flow of the paste-like solder resist in the Cu pattern 2 particularly in the vicinity of the wire bonding portion 2 WB, so that bubbles 24 are easily involved in the solder resist layer 3 . When bubbles are generated in the solder resist layer 3 , and between the solder resist layer 3 and the polyimide tape 1 . Water infiltrates into the bubbles from the outside so that the Cu pattern 2 is eroded with the lapse of time. BRIEF SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. A first object of the invention is to provide a semiconductor device having a reduced difference in adherence force between an insulating base and a chip, and a stable adherence. Furthermore, a second object of the invention is to provide a semiconductor device which suppresses the generation of bubbles and which has a high reliability against the erosion of a conductive pattern. In order to attain the first object of the invention, according to a first aspect of the present invention, there is provided a semiconductor device comprising: a semiconductor chip having a pad; an insulating base which adheres to the semiconductor chip; a conductive pattern formed on the insulating base, the conductive pattern including a bonding portion connected to the pad of the semiconductor chip, a pad portion connected to an outside electrode, and a wiring portion connecting the bonding portion and the pad portion; and an electrically floating island-like portion formed on the insulating base. According to the semiconductor device having the above structure, the uneven configuration can be alleviated which results from the presence and absence of the conductive layer by providing the electrically floating island-like portion on the insulating base. Consequently, the difference in the pressure distribution can be alleviated as compared with the conventional example, so that a difference in the adherence force between the insulating base and the chip can be reduced. Consequently, a semiconductor device having a stable adherence force can be obtained. In order to attain a first object of the invention, according to a second aspect of the invention, there is provided a semiconductor device comprising: a semiconductor chip having a pad; an insulating base which adheres to the semiconductor chip; and a conductive pattern formed on the insulating base, the conductive pattern including a bonding portion connected to the pad of the semiconductor chip, a pad portion connected to an outside electrode, and a wiring portion connecting the bonding portion and the pad portion and having a tend portion with a different width. According to the semiconductor device having the above structure, the uneven configuration resulting from the presence and absence of the conductive pattern can be alleviated by providing the extended portion mutually different width on the wiring portion of the conductive pattern. Consequently, in the same manner as the first aspect of the invention, the difference in the pressure distribution can be alleviated as compared with the conventional example with the result that the adherence force between the tape and the chip can be reduced. Thus, the semiconductor device having a stable adherence can be obtained. In order to attain the second object, according to a third aspect of the present invention, there is provided a semiconductor device comprising: a semiconductor chip; an insulating base which adheres onto the semiconductor chip; a conductive pattern formed on the insulating base, the conductive pattern including a bonding portion connected to the pad of the semiconductor chip, a pad portion connected to an outside electrode, and a wiring portion connecting the bonding portion and the pad portion; and a covering layer which covers the conductive pattern formed on the insulating base at least except for the bonding portion and the pad portion; wherein an intersection angle between the edge of the covering layer and the bonding portion is 90 degrees or more. According to the semiconductor device having the above structure, the covering layer less involves bubbles on the conductive pattern particularly in the vicinity of the bonding portion at the time of forming the covering layer by setting an intersection angle between the covering layer and the terminal portion to 90 degrees or more. Consequently, a semiconductor device which suppresses the generation of bubbles and which has a high reliability against the corrosion of the conductive pattern can be obtained. Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention. FIG. 1A is a plan view showing a conventional TAB tape. FIG. 1B is a sectional view taken along the line 1 B— 1 B of FIG. 1 A. FIG. 1C is a sectional view taken along the line 1 C— 1 C of FIG. 1 A. FIGS. 2A , 2 B and 2 C are sectional views showing a heat pressurizing step respectively. FIG. 3A is a plan view showing a conventional TAB tape. FIG. 3B is a sectional view taken along the line 3 B— 3 B of FIG. 3 A. FIG. 4A is a plan view showing a semiconductor device according to a first embodiment of the present invention. FIG. 4B is a sectional view taken along the line 4 B- 4 b of FIG. 4 A. FIG. 4C is a sectional view showing the state after the completion of the device. FIGS. 5A , 5 B, 5 C and 5 D are sectional views showing a method for manufacturing the semiconductor device according to the present invention respectively. FIG. 6A is a plan view showing a first basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 6B is a sectional view taken along the line 6 B— 6 B of FIG. 6 A. FIG. 6C is a sectional view taken along the line 6 C— 6 C of FIG. 5 A. FIGS. 7A , 7 B and 7 C are sectional views showing the heat pressurizing step respectively. FIGS. 8A , 8 B, 8 C and 8 D are plan views showing basic patterns of an island-like portion respectively. FIG. 9A is a plan view showing a second basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 9B is a sectional view taken along the line 9 B— 9 B of FIG. 9 A. FIG. 9C is a sectional view taken along the line 9 C— 9 C of FIG. 9 A. FIGS. 10A , 10 B, and 10 C are sectional views showing the heat pressurizing step respectively. FIGS. 11A , 11 B, 11 C and 11 D are plan views showing basic patterns of an expanded portion respectively. FIG. 12A is a plan view showing a third basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 12B is a sectional view taken along the line 12 B— 12 B of FIG. 12 A. FIGS. 13A and 13B are plan views showing a printing step respectively. FIGS. 14A and 14 b are plan views showing basic patterns of a bonding portion respectively. FIG. 15 is a plan view showing a semiconductor device according to a reference example of the present invention. FIG. 16 is a plan view showing a semiconductor device according to a second embodiment of the present invention. FIG. 17 is a plan view showing a semiconductor device according to a third embodiment of the present invention. FIG. 18 is a plan view showing a semiconductor device according to a fourth embodiment of the present invention. FIG. 19 is a plan view showing a semiconductor device according to a fifth embodiment of the present invention. FIG. 20 is a plan view showing a semiconductor device according to the present invention. FIG. 21 is a plan view showing a semiconductor device according to a sixth embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, embodiments of the present invention will be explained by referring to the drawings. In the explanation, common portions are denoted by common reference numerals over all the drawings. (First Embodiment) FIG. 4A is a plan view showing a semiconductor device according to a first embodiment of the present invention. FIG. 4B is a sectional view taken along the line 4 B— 4 B of FIG. 4 A. As shown in FIGS. 4A and 4B , a Cu pattern (a conductive pattern) 2 comprising copper (Cu) is formed on the surface of a polyimide (an insulating base) 1 . The Cu pattern 2 includes a wire bonding portion 2 WB, a ball pad portion 2 BP, and a wiring portion 2 WR. The ball pad portion 2 BP is arranged in a matrix-like configuration on a pad area 12 set approximately in the center of the polyimide tape 1 . The wiring portion 2 WR connects the wire bonding portion 2 WB and the ball pad portion 2 BP. On the main surface of the polyimide tape 1 , a solder resist layer (covering layer) 3 is formed. The solder resist layer 3 covers the Cu pattern 2 at least except for the wire bonding portion 2 WB, and the ball pad portion 2 BP. The polyimide tape 1 has an open hole 8 to which a pad 7 of a semiconductor chip 6 is exposed. The wire bonding portion 2 WB is connected to the pad 7 which is exposed to the hole 8 via a bonding wire 9 comprising, for example, gold (Au). On the rear surface of the polyimide tape 1 , an adhesive layer 4 is formed, and the polyimide tape 1 is connected to the semiconductor chip 6 via the adhesive layer 4 . An example of the adhesive agent of the layer 4 is an acryl-epoxy resin adhesive. In addition, a silicone resin adhesive or the like can be used. FIG. 4C is a sectional view showing a state after the completion of the semiconductor device. On the open hole 8 , a shield resin 10 is formed for shielding the bonding wire 9 and the pad 7 from the outside. Furthermore, on the ball pad portion 2 BP, for example, a solder bump (also referred to as a solder ball) 11 comprising solder is formed. The solder bump 11 constitutes an outside electrode of the semiconductor chip 6 . An example of the thickness of the polyimide tape 1 in this state is about 0.075 mm±0.008 mm. An example of thickness of the adhesive agent layer 4 is 0.05 mm±0.01 mm. An example of the thickness of the chip 6 is 0.38 mm±0.02 mm. Furthermore, a solder bump 11 ′ formed on the peripheral area 13 on the outside of the pad area 12 is referred to as an option ball, and has a function of heightening the mechanical strength of the TAB type ball grid array semiconductor device. The solder bump (the option ball) 11 ′ is formed on the option pad portion 2 BP′, and the option pad portion 2 BP′ is formed on the peripheral area 13 . FIGS. 5A , 5 B, 5 C and 5 D are sectional views showing a method for manufacturing the semiconductor device according to the present invention. In the beginning, as shown in FIG. 5A , there is prepared the polyimide tape 1 on which the Cu pattern 2 is formed. Next, as shown in FIG. 5B , a screen 51 having a window 50 corresponding to the solder resist layer formation pattern is allowed to come close to the Cu pattern 2 . Next, a squeegee 52 is allowed to move in a direction shown by an arrow so that a paste-like solder resist 53 is printed on the tape 1 via the screen 51 thereby forming the solder resist layer 3 . As a consequence, the TAB tape is completed. Next, as shown in FIG. 5C , the semiconductor chip 6 is placed on a lower mold 22 . Next, after the position of the TAB tape having the protection tape 5 peeled off and the position of the chip 6 are corrected, an upper mold 23 is allowed to come down so that the TAB tape is heat pressurized to the chip 6 . As a consequence, the chip 6 is adhered to the TAB tape. Next, as shown in FIG. 5D , the wire bonding portion 2 WB of the Cu pattern 2 is connected to the pad 7 of the chip 6 with the bonding wire 9 . Next, the bonding wire 9 and the pad 7 are shielded with resin 10 , and a solder bump 11 is formed on the ball pad portion 2 BP with the result that the semiconductor device according to the present invention is completed. The semiconductor device according to the first embodiment of the semiconductor device includes mainly three elements. The elements will be explained in order hereinafter. (First Element) FIG. 6A is a plan view showing a first basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 6B is a sectional view taken along the line 6 B— 6 B of FIG. 6 A. FIG. 6C is a sectional view taken along the line 6 C— 6 C of FIG. 6 A. The Cu pattern 2 in the first embodiment has, as shown in FIGS. 6A through 6C , an electrically floating island-like portion 2 IL in addition to the wire bonding portion 2 WB, the ball pad portion 2 BP, the wiring portion 2 WR. The island-like portion 2 IL is arranged between the wiring portions 2 WR or ball pad portions 2 BP. The Cu pattern 2 has the island-like portion 2 IL so that the area of a convex portion 21 increases and the uneven configuration resulting from the presence and the absence of the Cu pattern 2 can be alleviated. As a consequence, at the time of the heat pressurizing step shown in FIGS. 7A through 7C , a difference in the pressure distribution applied to the chip 6 can be alleviated as compared, for example, with the conventional example shown in FIG. 2 C. As a consequence, the adherence force between the TAB tape and the chip 6 can be made small with the result that a semiconductor device having a stable adherence can be obtained. It is preferable that a region for arranging the island-like portion 2 IL is arranged along the peripheral area 13 at least outside of the pad area 12 , namely along the peripheral portion of the chip 6 . In the peripheral portion of the chip 6 , an adherence with the TAB tape is heightened by arranging the island-like portion 2 IL in the peripheral area 13 in this manner, a stronger pressure endurance can be obtained against the separation. FIGS. 8A , 8 B, 8 C and 8 D are plan views showing basic patterns of the island-like portion respectively. By the way, when the Cu pattern 2 has an island-like portion 2 IL, it is feared that the parasitic capacity of the wiring portion 2 WR increases, and the electric characteristic of the wiring portion 2 WR, particularly, the RCL characteristic is affected. This influence can be minimized by changing the design of the island-like portion 2 IL into a stripe pattern shown in FIG. 8B , a checker pattern shown in FIG. 8C and a lattice-like (matrix-like) pattern shown in FIG. 8D , instead of a planer pattern shown in FIG. 8 A. For example, patterns shown in FIGS. 8B through 8D have a gap therebetween. For the portion of this gap, for example, the parasitic capacity of the wiring portion 2 WR can be reduced so that the electric characteristic of the wiring portion 2 WR, particularly, the influence upon the RCL characteristic can be minimized. Furthermore, by changing the design of the island-like portion 2 IL, the electric characteristic of the wiring portion 2 WR can be adjusted. (Second Element) FIG. 9A is a plan view showing a second basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 9B is a sectional view taken along the line 9 B— 9 B of FIG. 9 A. FIG. 9C is a sectional view taken along the line 9 C— 9 C of FIG. 9 A. The Cu pattern 2 in the first embodiment has, as shown in FIG. 9A through 9C , has a tend portion 2 WRW having a widened width at least on a portion of the wiring portion 2 WR. The tend portion 2 WRW reduces a gap D between the wiring portions 2 WRW and the ball pad portions 2 BP. The Cu pattern 2 has a tend portion 2 WRW so that the area of the convex portion 21 can be increased in the same manner as the case in which the island-like portion 2 IL is provided. Consequently, at the time of heat pressurizing step shown in FIGS. 10A through 10C , a difference in the pressure distribution applied to the chip 6 can be alleviated as compared with conventional example shown in FIG. 2 C. Consequently, a difference in the adherence between the TAB tape and the chip 6 can be made small with the result that a semiconductor device having a stable adherence can be obtained. Preferably, a portion for providing the tend portion 2 WRW is arranged at least along an outside peripheral area 13 of a pad area 12 , namely along the peripheral portion of the chip 6 . Furthermore, the tend portion 2 WRW can be obtained by expanding, for example, the width of the wiring portion 2 WR with the result that there is an advantage that the tend portion 2 WRW can be easily provided on a portion where the island-like portion 2 IL can be provided with difficulty, and the wiring density is high. In the case where the expanded portion 2 WRW is provided on a portion where the wiring density is dense, a large tend portion 2 WRW is required, and the capacity of the wiring portion 2 WR largely increases. The island-like portion 2 IL and the tend portion 2 WRW may be respectively provided appropriately in consideration of the electric characteristic of the semiconductor device. One example of an appropriate arrangement is such that, as shown in FIG. 4A , the island-like portion 2 IL is provided in the peripheral portion 13 where the wiring density is relatively rough, and the tend portion 2 WRW is provided on a pad area 12 where the wiring density is relatively dense. FIGS. 11A , 11 B, 11 C and 11 D are plan views showing basic patterns of the expanded portion respectively. The configuration of the basic patterns of the tend portion 2 WRW is, as shown in FIG. 11A , a fin-like configuration which projects either to one side or both sides of the wiring portion 2 WRW, or the fin-like configuration which is expanded of the wiring portion. The expanded portion 2 WRW having a fin-like configuration is provided on route of the wiring portion 2 WR so as to reduce a gap D between adjacent wiring portion 2 WR as shown in FIG. 11 A. Otherwise, as shown in FIG. 11B , the fin-like configuration is provided so as to extend between separate Cu patterns 2 so that a gap between the ball pad portions of these separate Cu pattern 2 is reduced. Otherwise, as shown in FIG. 11C , the fin-like expanded portion 2 WRW is provided so as to reduce the gap between the wiring portions 2 WR. Furthermore, the fin-like tend portion 2 WRW may be provided at the end of the wiring portion 2 WR as shown in FIG. 11 D. As the hardness of such tend portion 2 WRW and the Cu pattern 2 including the island-like portion 2 IL, Vickers hardness of 170 HV is preferable. Setting the hardness to such level is based on the viewpoint of suppressing the collapse of the Cu pattern 2 . Besides, one example of the tend portion 2 WRW according to the present invention, and the wiring density in the case where the Cu pattern 2 including the island-like portion 2 IL is provided is Cu pattern area/tape area=68.5%. The conventional wiring density is Cu pattern area/tape area=45.7%. From this viewpoint, when the wiring density (Cu pattern area/tape area) exceeds the wiring density=45.7%, the adherence is heightened as compared with the conventional device. (Third Element) FIG. 12A is a plan view showing a third basic pattern of the TAB tape provided in the semiconductor device according to the present invention. FIG. 12B is a sectional view taken along the line 12 B— 12 B of FIG. 12 A. With respect to the Cu pattern 2 according to the first embodiment, as shown in FIGS. 12A and 12B , an intersection angle θ between the wire bonding portion 2 WB and an edge of the solder resist layer 3 is maintained at 90 degrees or more. The bubbles are hardly involved at the time of printing in the Cu pattern 2 in the vicinity of the wire bonding portion 2 WB as compared with the conventional example in which a portion is generated which has an intersection angle of 90 degrees or less shown in FIG. 3A by maintaining the intersection angle θ of 90 degrees. As a result of the fact that the bubbles are involved with difficulty, the bubbles are generated with difficulty in the solder resist layer 3 and between the solder resist layer 3 and the polyimide tape 1 so that the situation of the corrosion of the Cu pattern 2 is suppressed with the lapse of time. As a consequence, a semiconductor device having a high reliability against the erosion of the conductive pattern can be obtained. FIGS. 13A and 13B are plan views showing an example of a step of printing a solder resist onto the tape 1 having the above Cu pattern 2 . As shown in FIG. 13A , a screen 51 having a window 50 corresponding to the solder resist layer formation pattern is allowed to come close to the Cu pattern 2 . Next, as shown in FIG. 13B , the squeegee 52 is moved along the direction of an arrow in FIG. 13 B. Specifically, the squeegee 52 is moved from the wire bonding portion 2 WB to the wiring port ion 2 WR, with the result that the paste-like solder resist layer 53 is printed on the tape 1 via the window 50 of the screen 51 . As a consequence, the solder resist layer 3 is formed where bubbles are generated with difficulty. FIGS. 14A and 14B are plan views showing the basic patterns of the bonding portion respectively. The Cu pattern 2 shown in FIG. 14A is a case in which the intersection angle θ is maintained at 90 degrees. The Cu pattern 2 shown in FIG. 14B is a case in which intersection angle θ is maintained at 90 degrees or more. In the case where the intersection angle θ is maintained at 90 degrees or more, the configuration of the wire bonding portion 2 WB may be formed in a tapered configuration toward the end. Next, another embodiment of the present invention will be explained. (Second Embodiment) FIG. 15 is a plan view showing a semiconductor device according to a reference example of the present invention. FIG. 16 is a plan view showing a semiconductor device according to a second embodiment of the present invention. As shown in FIG. 16 , the semiconductor device according to the second embodiment is an example in which an island-like portion 2 IL is further provided on the Cu pattern 2 in the reference example shown in FIG. 15 . The island-like portion 2 IL of the embodiment is provided outside of the pad area 12 , namely, in the peripheral area 13 . Incidentally, the second embodiment is an example in which the option pad 2 BP′ shown in the first embodiment is not provided. (Third Embodiment) FIG. 17 is a plan view showing a semiconductor device according to a third embodiment of the present invention. As shown in FIG. 17 , the semiconductor device according to the third embodiment is an example in which the tend area 2 WRW is further provided outside of the pad area 12 , namely, on the Cu pattern 2 of the reference example. The tend portion 2 WRW of the embodiment is provided outside of the pad area 12 , namely the peripheral area 13 . (Fourth Embodiment) FIG. 18 is a plan view showing a semiconductor device according to a fourth embodiment of the present invention. As shown in FIG. 18 , the semiconductor device according to the fourth embodiment of the present invention is an example in which the island-like portion 2 IL and the tend portion 2 WRW are further provided respectively on the Cu pattern 2 of the reference example shown in FIG. 15 . The island-like portion 2 IL and the tend portion 2 WRW are provided respectively on the outside of the pad area 12 , namely in the peripheral area 13 . (Fifth Embodiment) FIG. 19 is a plan view showing a semiconductor device according to a fifth embodiment of the present invention. As shown in FIG. 19 , the semiconductor device according to the fifth embodiment of the present invention is an example in which the tend portion 2 WRW is provided on the Cu pattern 2 of the reference example shown in FIG. 15 . And, at the same time, the tend portion 2 WRW is provided in the pad area 12 , and the peripheral area 13 respectively. In particular, in the fifth embodiment, the expanded portion 2 WRW is provided over the while pad area 12 and the peripheral area 13 . (Sixth Embodiment) FIG. 20 is a plan view showing a semiconductor device according to the present invention. FIG. 21 is a plan view showing the semiconductor device according to the sixth embodiment of the present invention. Incidentally, FIGS. 20 and 21 are plan views showing the semiconductor device as seen from the side of the chip 6 not from the side of the tape 1 . As shown in FIG. 20 , when the semiconductor devices according to the first to the fifth embodiments are observed from the side of the chip 6 , the shield resin 10 is present only on the periphery of the open hole 8 of the tape 1 . In the sixth embodiment, as shown in FIG. 21 , the shielded resin 10 is allowed to present on the whole periphery of the chip 6 so that the adherence of the chip 6 and the tape 1 can be further stabilized. In the above description, the present invention has been explained with respect to the first to the sixth embodiments of the present invention. The present invention is not restricted thereto, and the invention can be modified in various ways within the scope of not departing from the gist of the invention. For example, as a conductive pattern 2 , copper (Cu) is given, copper can be replaced with copper alloy or other conductive material. Furthermore, in the case where copper is replaced with copper alloy or other conductive material, preferably, the hardness may be at least 170 HV or more. Furthermore, as a pad arrangement of the semiconductor chip, an example is shown wherein the pad is arranged on the periphery of the chip, and on the center of the chip. The pad arrangement is provided either on the periphery of the chip or in the center of thee chip. Furthermore, as a semiconductor product formed in the semiconductor chip, products which requires a compact package such as a SRAM, FLAS, H-EEPROM, DRAM, mixedly mounted DRAM, CPU or the like are particularly preferable. Furthermore, the first to the sixth embodiments can be practiced as a single entity. However, the embodiments can be practiced by a combination of the embodiments in various manners. As has been described above, according to the present invention, a semiconductor device can be provided which has a reduced difference in adherence force between the tape and the chip, and which has a stable adherence. Furthermore, a semiconductor device can be provided which suppresses the generation of bubbles and which has a high reliability against the erosion of the conductive pattern. Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
There is disclosed a TAB style BGA type semiconductor device. This semiconductor device comprises a semiconductor chip on which an integrated circuit is formed, and a polyimide tape which has a conductive pattern and which is allowed to adhere to the semiconductor chip. The conductive pattern includes a bonding portion connected to the pad of the semiconductor chip, a pad portion connected to the outside electrode, and an electrically floating island-like portion in addition to a wiring portion for connecting the bonding portion and the pad portion.
7
This is a continuation of application Ser. No. 190,237 filed Sept. 24, 1980, now U.S. Pat. No. 4,318,356 dated Mar. 9, 1982. BACKGROUND OF THE INVENTION 1. Field of the Invention The invention concerns a device for the formation of a seam along at least a portion of the edges of a piece of material, particularly for stitching around the edges of an essentially polygonal piece of material, comprising a sewing machine and a table to support the material during the sewing process. 2. Description of the Prior Art In order to stitch a piece of material around successive edges, a trouser pattern for example, one may have an operator insert the piece into the sewing machine, pass it through the sewing machine along one edge, turn it about the needle tip at the end of the edge, and pass it through the sewing machine along the successive edge, etc. This procedure is relatively time-consuming. Another familiar method is to use two sewing machines with parallel sewing directions, in order to sew two parallel edges of a piece of material. After passing through the first machine, the material is shifted parallel to itself by use of a transporter and introduced into the second sewing machine, which it passes in the opposite direction, for example. This procedure is not only very elaborate in terms of the required machines, but also demands a large installation area. The expenditure increases accordingly, if three or more edges of a piece of material have to be stitched. SUMMARY OF THE INVENTION The invention is directed to a reasonably inexpensive apparatus for sewing or stitching a seam along several successive edges of a piece of material, which is operable in a small installation area, with little operating effort, and at high operating speed. According to the invention, the sewing machine apparatus is mounted so that it can turn about an axis of rotation that is essentially vertical with respect to the table surface and which passes through the point where the sewing machine needle passes through the table surface. A feed device is provided to feed the material essentially parallel with the respective sewing direction and a control device is provided to control the sewing apparatus drive, the feed device, and a rotary drive to turn the sewing apparatus about its rotary axis according to the desired course of the seam. With the apparatus according to the invention, the initially stated problems are solved in a surprisingly simple manner, since it is much easier to turn the sewing apparatus about a fixed axis than to automatically orient pieces of material which differ in their form and makeup in such a manner that their adjacent edges pass through the sewing apparatus, parallel to the sewing direction. To allow rotation of the sewing apparatus, the latter is preferably mounted on a rotary frame that is mounted beneath the table top and is moveable by means of the rotary drive. In order to obtain a flush table surface nonetheless, it is recommended that the sewing apparatus be mounted in a turntable that is flush with the table surface. In order to obtain a contiguous seam in the transition from one edge of the piece of material to another edge of the piece of material, the sewing apparatus drive is suitably controlled in such a manner that the needle remains in the material when the sewing apparatus is turned about its axis of rotation. This allows relative rotation between the material and the sewing apparatus, but also prevents a shift of the material with respect to the sewing apparatus. The control device preferably features a scanning device that reacts to the successive edge of the piece of material in the sewing direction, along which the next seam is to be produced, after rotation of the sewing apparatus, along which the previous seam is to be continued. This type of control has the advantage that it can be used with any shape of material sections, i.e. it is independent of the respective lengths of the edges to be stitched about, or of their enclosed angle. The control device is preferably so configured that both the disconnection of the sewing apparatus drive and the connection of the rotary drive, as well as the disconnection of the rotary drive and the reconnection of the sewing apparatus drive are controlled by the same edge of the material. This may, for example, be accomplished by having each successive edge pass the scanning device, as the piece of material passes through the sewing apparatus, along a first edge, shortly before the needle reaches the end of the first edge. The sewing apparatus drive is then disconnected in the above manner with a certain delay, so that the needle remains in the material. When the sewing apparatus is then turned about its rotary axis with respect to the material, which remains immobile on the table surface, the scanning device again encounters the second edge of the material and then causes the rotary drive to be disconnected and the sewing apparatus drive to be connected. Reliable and precise scanning can be obtained, when the scanning device contains at least one optical scanning element that turns together with the sewing apparatus and which reacts to optical differences between the material the the surface of the turntable and/or an active or passive luminescent element attached to it. Such as optical scanning element may be a photoelectric transmitter and receiver arrangement, for example, which acts in conjunction with a reflective foil, mounted on the turntable, with the reflective foil being either exposed or covered by the edge of the material that slides over it, to trigger a signal in the photoelectric transmitter and receiver arrangement. The scanning device preferably comprises two scanning elements that are spaced successively in the feed direction and ahead of the sewing location, with the scanning element that is further from the sewing location controlling the speed of the sewing apparatus drive, and the scanning element, that is closer to the sewing location, controlling the connection and disconnection of the sewing apparatus drive and of the rotary drive. Prior to stopping the sewing apparatus drive when used very high speed sewing apparatuses, it is best to reduce the sewing speed first, since it is otherwise practically impossible to stop the sewing apparatus drive in such a way that the sewing needle remains in the material. In order to enable feeding and removing the pieces of material at the same points at all times, the apparatus is designed so that it can assume at lease one intermediate position, defined by the position of that edge of the piece of material on the table along which the next seam is to be formed, between a defined starting position and a defined end position. The defined starting position and end position make it possible to connect automatic feed and clearing machines, for example. In the case of trouser parts, that are to be stitched along three sides, for example, one may provide that the starting position and the end position of the sewing apparatus are 180°, opposite to one another and correspond to the essentially parallel longitudinal edges of the trouser pattern, while the intermediate position is determined by the scanning device. A clamping device may be provided to hold the material on the table top during the rotation of the sewing appparatus. The piece of material is then held by the sewing needle, but this is not sufficient, especially in the case of heavy and long pieces that hang over the table top. Such a clamping device may simply be configured as a plunger that can be radially lowered onto the table surface outside of the turntable, to hold the material on the immobile part of the table top during the rotation of the sewing apparatus and the turntable. In order to assure perfect transport of the material on the table top, without distortion and bunching, the feed device may comprise a driven feed roll that is connected with the sewing apparatus and that can be adjusted up and down with respect to the table top, by being supported at a lateral distance from the sewing location, by a shaft that is parallel with the table surface and at right angles to the feed direction, in addition to the sewing apparatus transport. During the sewing process the feed roll is lowered onto the material and assures that the material is not only advanced along the edge that is passing through the sewing apparatus. In order to assure synchronous transport of the material by the sewing apparatus and the feed roll, the latter may be suitably connected with the sewing apparatus drive, via an infinitely variable gearing. The adjustment of the feed roll relative to the table surface may be controlled, as function of the rotary movement of the sewing apparatus, such that the feed roll is lifted from the table surface during the rotary movement of the sewing apparatus. In order to obtain penetration of the sewing apparatus needle at a defined distance from the respective distance from the respective fabric edge, the feed device may comprise a guide bar, placed ahead of the sewing location in the transport direction, and be essentially parallel with the feed direction, as well as at least one guide roll that is mounted to rotate on a nearly horizontal shaft at a lateral distance from the guide bar ahead of the sewing location, obliquely to the feed direction. Thus, the guide roll, rolling on the material, guides the material against the guide bar. A further guide roll is preferably mounted ahead of the first guide roll in the feed direction, to work together with a driven counter roll, that is mounted in the table top, tangentially with the table surface, and to actively guide the piece of material against the guide bar. In order to prevent the material from bunching up behind the sewing location, the table is preferably configured such that the table edges that run obliquely to the sewing direction of the sewing apparatus in its starting or end position, come together in the direction away from the sewing apparatus. When the sewing apparatus is in its starting or end position, this edge configuration creates tension in the material, hanging over the table edges, which pulls the material away from the sewing apparatus, out of the sewing invention. Since the position of the piece of material after the sewing process is not defined in the intermediate position of the sewing apparatus, as orienting device is expediently provided, to orient the piece of material relative to the sewing apparatus in its end position. This orienting device may be configured as a swivel arm that is mounted to turn about an essentially vertical axis, at a slight distance below the table top and which can be turned from a first position, in which it is aligned parallel with a table edge that is oblique to the sewing direction, outside the table top, to a second position, in which it essentially lies beneath the table top. During its transition into the first position, the swivel arm meets the piece of material, hanging over the edge of the table, and aligns it, so that it enters correctly into the sewing apparatus in its end position. The novel features of the invention are set forth with particularity in the appended claims. The invention will best be understood from the following description when read in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a partial schematic frontal view of the system in accordance with the present invention; FIG. 2 is a lateral view of the system shown in FIG. 1, from the direction of the arrow A in FIG. 1, with some of the parts, shown in FIG. 1, having been left out for the sake of clarity; FIG. 3 is a simplified plan of the system, shown in FIG. 1, with the sewing machine in the starting position; FIG. 4 is an illustration corresponding to FIG. 1, with the sewing apparatus in an intermediate position; FIG. 5 is an illustration corresponding to FIGS. 3 and 4, with the sewing apparatus in its end position; FIG. 6 is a view of the scanning device and the adjustable guide roll by themselves, in the direction of the arrow B in FIG. 3; and FIG. 7 is a lateral view of the stacking device in the direction of the arrow C in FIG. 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1 to 7 illustrate a system to stitch or new seams about the edges of a fabric pattern. Although the invention will be described in connection with stitching around three edges of a trouser pattern, it is clearly not intended to be limited thereto. In FIGS. 1 and 2, numeral 10 represents a table with a frame 12 and a table top 14. A rotary frame 20 is mounted to turn about a vertical axis 22 in a bearing 18, attached to a brace 16 of the frame 12. The rotary frame 20 is essentially U-shaped and rests with one leg 24 of the U on a shaft 26, which passes through the bearing 18. A chain sprocket 28 is firmly attached to the lower end of the shaft 26 and is driven by an electric motor 30 via a pinion gear 34 on its output shaft and a drive chain 36 which connects the pinion gear 34 with the chain sprocket 28. By use of the electric motor 30, the rotary frame 20 can thus be turned about the axis 22. A sewing apparatus 40 is mounted on the upper leg 38 of the U of the rotary frame 20. Since the invention is being described in connection with a conventional simple needle sewing apparatus, the sewing apparatus 40 is being shown in block form, without detailed description. The sewing apparatus 40 is driven by an electric motor 42, which is mounted on the rotary frame 20, via a drive belt 44, which connects a pulley 46 on the output shaft of the electric motor 42 with a roller 48 on the input shaft of the sewing apparatus 40. The sewing apparatus 40 passes through the table top 14 in such a manner that the stitch plate of the sewing apparatus 40, which is not labeled, is flush with the table surface. The part of the table top that surrounds the sewing apparatus 40 is configured as turntable 50 (see FIGS. 3 to 5), separated from the rest of the table top 14 by a circular gap or opening 52. The sewing apparatus 40 is mounted on the rotary frame 20 in such a manner that the axis 22 passes through the point where the needle 54 of the sewing apparatus 40 passes into the surface of the table. This means that the sewing apparatus 40 essentially turns about the tip of the needle when the rotary frame turns. For transport of the material, during the sewing process, a feed roll 56 is provided, apart from the usual transport device, built into the sewing apparatus 40, which is supported by a horizontal shaft 60 (See FIG. 2) at right angles to the sewing direction, attached to an articulated arm 58. The articulated arm 58 is articulated about a shaft 62 that is parallel to the shaft 60. Shaft 62 is mounted on a vertical rod 64, which, in turn, is mounted to a support 66, that runs at right angles to the sewing direction and is in turn rigidly connected with the sewing apparatus 40. The articulated arm 58 can be adjusted with a pneumatic piston-cylinder arrangement 68, whose piston rod 70 attaches to the end of the articulated arm 58 that is closer to the feed roll 56, and whose cylinder 72 is supported against the upper end of the rod 64. By use of the piston-cylinder arrangement 68 the feed roll 56 can be moved between a raised position, shown in FIGS. 1 and 2, and the lowered position in which it rests on the material that lies on the table top 14. The feed roll 56 is driven synchronously with the sewing speed by the sewing apparatus 40. The drive mechanism for the feed roll 56 comprises an infinitely variable gearing 74, mounted on a support 73, whose input shaft is driven via a pulley 76 which is attached to it and a drive belt 78 driven by the roll 48 of the sewing apparatus drive. The drive shaft of the gearing 74 drives a roller 82 that is mounted to turn on the lower end of the rod 64, coaxially with the shaft 62, via a universal shaft. Via a belt 84, the roller 82 drives a roller 86 that is mounted coaxially with the feed roll 56 and is rigidly connected with it. In FIG. 1 a frame 88 is shown. It is mounted on the table top 14 to support one or more sewing thread bobbins 90, from which the sewing thread is passed to the sewing apparatus via a first thread guide 92 and a second thread guide 94. When routing the thread, particularly several threads, one must take care that the threads do not twist about some part or about one another when the sewing apparatus 40 is turned 180°, resulting in interference. Apart from that, thread delivery may be accomplished in the conventional manner. Since the stability of the table top 14 is reduced by the cutting out of the turntable 50 in its center area, supports 96 are mounted on the upper U leg 38 of the rotary frame 20 in an area between the vertical posts of the frame 12, in order to support the table top. They contact the bottom of the table top 14 via gliding heads 98 and support it in an area close to the opening 52. In order to assure correct entry of the material 100 (See FIG. 3) into the proper sewing location of the sewing apparatus 40, a feed-in element 102 is mounted ahead of the sewing location in the feed direction. It comprises a guide bar 104 that is curved about a vertical axis and guides the edge of the entering material, and a cover plate 106 (See FIG. 7) that is parallel with the table top 14. Plate 106 is mounted at a distance from the table top 14 that roughly corresponds to the fabric thickness, in order to smooth the entering fabric. A guide roll 108 is supported in a slot of the cover plate 106, so that it turns freely and that the center plane that stands perpendicularly on its shaft points toward the sewing needle, forming an acute angle with the sewing direction. The guide roll 108 is turned by the entering fabric and causes the fabric to be moved against the guide bar 104. The guide roll 108, with the cover plate 106, is height adjustable in a manner not illustrated, so that it can be raised prior to the rotation of the sewing apparatus 40. Apart from the guide roll 108 another guide roll 110 (See FIG. 2) is provided, which is essentially free to rotate in parallel with the guide roll 108 and is supported on one arm of the elbow lever 112 (See FIG. 6). The elbow lever 112 is in turn articulated about a shaft 114 that is parallel to the sewing direction and mounted on a carrier 116. A support 118 is connected with the carrier 116 which serves to mount a pneumatic piston-cylinder arrangement 120. The piston rod 122 attaches to the other arm of the elbow lever 122, while the cylinder 125 of the piston-cylinder arrangement 120 is supported against the support 118. The in-and-out movement of the piston rod 122 adjusts the elbow lever 112, so that the guide roll 110 can be lowered onto the table top 14, or lifted from the latter. In its lowered position, the guide roll acts together with the drive roll 126, which is mounted beneath the table top, and is connected with a drive that is not illustrated. It emerges slightly through a slot 128 in the table top 14 with its peripheral surface. Thus, the guide roll 110 and the drive roll 126 cause the entering material to be guided against the guide bar 104 with its edge. The carrier 116 also holds two photoelectric transmitter and receiver arrangements 130 and 132 (See FIG. 3) which are arranged successively in the feed direction, and function together with reflective strips 134 and 136 respectively. The strips are fastened to the turntable, so that they produce a signal when the respective reflective strip is exposed or covered by a piece of fabric. The function of the photoelectric transmitter and receiver arrangements 130, 132 will be discussed in greater detail below. The transmitter and receiver arrangements 130 and 132 may contain a light source each, for example, whose light is reflected by the respective reflective strips and received by a photo cell or other photoelectric converter for processing. The carrier 116 (See FIG. 6) is mounted to a vertical support 118, which can be rotated about its longitudinal axis, so that the guide roll 110, together with its adjustment device, and the photoelectric transmitter and receiver arrangements 130 and 132 can be turned counterclockwise from their lowered position, shown in FIG. 3, so that one gains free access to the feed-in part 102. The function of the device according to the invention will be explained in greater detail below, with particular reference to FIGS. 3 to 5. FIG. 3 shows the sewing apparatus 40 in its defined starting position. In this position the piece of fabric material 100 e.g. trouser pattern which is to be stitched round its two longitudinal edges 138 and 140, as well as one lateral edge 142, is placed against the guide bar 104 with its edge 138 and introduced into the sewing location. Then the sewing apparatus drive is connected, which simultaneously lowers the feed roll 56 onto the fabric 100. The fabric 100 then passes through the sewing apparatus, while the edge 138 is stitched. The passage of the fabric material can be further facilitated by providing air jets in the turntable, (which are not illustrated) and through which compressed air is blown, so that the fabric material travels on an air cushion. The fabric material 100 moves until the edge 142 passes over the reflective strip, associated with the photoelectric transmitter and receiver arrangement 132. When the photo cell of this transmitter and receiver arrangement received light, the sewing apparatus drive is set to a slow speed. Shortly thereafter, the edge 142 passes over the reflective strip 130, which is associated with the transmitter and receiver arrangement 130, and which lies closer to the needle 54. A signal from this transmitter and receiver arrangement 130 causes the sewing apparatus drive to be disconnected after a delay and the food roll 56 is raised. The delay is so timed that the fabric material 100 is stopped at a slight distance of the needle 54 from the edge 142, with the needle 54 remaining in the fabric 100. At the same time the fabric material 100 is clamped to the table top 14 by a plunger 144 (See FIG. 1). The plunger 144 is connected to a carrier 146, that is firmly connected with the support frame 88 and is configured as a pneumatic piston-cylinder arrangement. The outward movement of the piston rod 148 causes the fabric material 100 to be clamped between the free end of the piston rod 148 and the table top 14, so that it cannot slip from the table top during the following rotation of the sewing apparatus 40. As a function of a signal produced by the transmitter-receiver arrangement, the rotation of the sewing apparatus 40 about the axis 22 is controlled, as are the other switching processes, by a control device which is housed in the control box 150, shown in FIG. 1. The sewing apparatus 40 is rotated clockwise (with reference to the illustrations in FIGS. 3 to 5), until the edge 142 of the unmoved fabric material 100 covers the reflective strip 134 and thus again causes a signal to be produced in the photoelectric transmitter and receiver arrangement 130. The sewing apparatus 40 is in the intermediate position illustrated in FIG. 4. In this position the rotational drive for the rotary frame 20 is disconnected, following the produced signal, the feed roll 56 is lowered onto the table top 14, and the sewing apparatus drive is again connected. The fabric material 100 is transported through the sewing apparatus in the direction of its edge 142, until the edge 140 of the fabric 100 glides over the reflective strip 136 and then the reflective strip 134, again triggering the above described control processes. In the special version described here, the sewing apparatus 40 is then rotated into its end position, illustrated in FIG. 5, in which it is turned exactly 180° with respect to its starting position. This end position is therefore independent of the course of the edges of the piece of fabric. It is of course possible to provide other intermediate positions for differently formed pieces of fabric, determined by the course of the edges of the fabric alone. When the end position is reached, the feed roll 56 is again lowered onto the table top 14 and the sewing apparatus drive is connected, whereupon the fabric material 100 passes through the sewing apparatus with its edge 140. When the end of edge 140 is reached, which is again determined by the photoelectric transmitter and receiver arrangements or scanning elements, the thread is bartacked onto the fabric and cut. Then the fabric material 100 is stacked by a stacking unit that is generally designated as 152 and which will be described in greater detail in connection with FIG. 7 below. As can be seen from FIGS. 3 to 5, the table edges, that essentially run obliquely with respect to the sewing direction of the sewing apparatus in its starting and end positions, are slanted to come together in a direction away from the sewing apparatus. The reason for this is that a tension away from the sewing location is to be produced on the fabric passing through the sewing apparatus. When the piece of fabric 100 passes through the sewing apparatus in its position, as illustrated in FIG. 3, for example, it drops over the table edge labeled 154 on the table top 14. The slant of this table edge 154 exerts a tension to the left, as seen in FIG. 3, on the piece of fabric 100, which pulls it away from the sewing location. This prevents the fabric from accumulating behind the sewing location and possibly bunching up. Depending on the course of the edge 142, the piece of fabric 100 is moved over the table top 14 in different directions, after stitching about of the first edge 138. It may happen that the piece of fabric 100 may remain hanging over the table edge 154 after the second edge has been stitched round. This is an unfavorable starting position for stitching up the third edge 140, since the sewing apparatus is in its end position, in which it is turned 180° from its starting position, regardless of the respective edge course. Hence the fabric pattern 100 is expediently aligned so that it now hangs over the table edge section, designated by 156 in FIG. 3. This alignment is accomplished with a swivel arm 158, which is arranged to turn about a vertical shaft 160 on the underside of the table top 14. The swivel arm 158 can be moved from a first position, drawn in solid, resp. broken lines in FIG. 3, and a second position, drawn in dot-dashed lines, in which the swivel arm is essentially parallel with the table edge 156, by use of a pneumatic piston-cylinder arrangement 162, which attaches to a table-mounted holder 166 with its cylinder 164 and to a short lever end 170 of the swivel arm 158 with its piston rod 168. This pulls the fabric pattern 100 away from the table edge 175 to the table edge 156 and orients it in the desired manner. The stacking mechanism 152 comprises a horizontal carrying rod 174 that is essentially parallel with the table edge and which is labeled by 172 in FIG. 3, and is fastened to a stand 176. At the lower end of the stand 176, an articulated yoke 178 is shown. It is mounted on a swiveling shaft, that is parallel to the carrying rod 172, having a leg 180 that lies in a vertical plane with the stand 176 and is articulated with it, and a leg 182 that is parallel with the carrying rod 147. The length of the leg 180 is so dimensioned that the leg 182 essentially comes to lie immediately next to the carrying rod 174 when the yoke 178 is swiveled against the stand 176. The yoke 178 is spring loaded in the direction of the stand 176 by a spring 184, which attaches to the stand 176 on one end and to a lever 186 that is firmly attached to the yoke 178 on the other end. Also articulated to the stand 176 by a shaft that is parallel to the swiveling shaft of the yoke 178 is a double arm lever, whose one lever arm 188 rests against the leg 180 of the yoke 178 via a roller 190 attached to its free end, and the free end of its other lever arm 192 is connected with the free end of a piston rod 194 of a pneumatic piston-cylinder arrangement 196, whose cylinder 198 is against the stand 176. When the piston rod 194 is moved out, the double arm lever is moved counterclockwise in FIG. 7, which makes it possible to swivel the yoke 178 against the carrying rod 174 or the stand 176 under the tension of the spring 184. As should be realized from FIG. 7, the leg 182 of the yoke 178 is beneath the table top 14 when the stacking unit 152 is in its rest position, so that a piece of fabric hanging over the table top 14 falls between the carrying rod 174 and the leg 182 of the yoke 178. If the yoke 178 is then moved toward the carrying rod 174, it pulls the piece of fabric from the table top 14 and flips it over the carrying rod 174 because of its rapid movement, so that it hangs over the carrying rod 174, in the position illustrated in FIG. 7. In order to make it possible to stack many pieces of fabric precisely, one above the other, a flat double arm lever 200 (See FIG. 3) is articulated about a vertical swiveling shaft 202 on the underside of the table top 14, near the table edge 172, which can be moved between the positions drawn in solid and broken lines respectively, in FIG. 3, by use of a pneumatic piston-cylinder arrangement 204. The piston-cylinder arrangement 204 is supported against a table mounted holder 208 with its cylinder 206 and against the lever 200 with its piston rod 210. The movement of the lever 200 orients the piece of fabric so that it hangs over an edge that is parallel with the carrying rod 174 resp. the yoke leg 182. Note that the piece of fabric is clamped onto the turntable 50 by a plunger after leaving the sewing location and during alignment, until stacking takes place. The plunger is formed by a pneumatic piston-cylinder arrangement 212 that is mounted on the carrier 66. Its piston rod 214 clamps the piece of fabric against the turntable 50 with its free end in its extended position. The above described device makes it possible, for example, to stitch a trouser pattern about on three edges and to deposit it on a stack, after placing it on the table, using a single process on a single sewing apparatus, without further intervention of the operator. After the return of the sewing apparatus into its starting position, the operator need only place a new pattern piece onto the table and guide it to the sewing location. It should be apparent that with the present devices several edges of other than a trouser pattern may be stitched and handled as herebefore described. Although particular embodiments of the invention have been described and illustrated herein, it is recognized that modifications and variations may occur to those skilled in the art, and consequently, it is intended that the claims be interpreted to cover such modifications and equivalents.
The arrangement comprises a sewing apparatus which is partially supported below a material-supporting table and which partially extends through an opening above the table surface. Control means are provided to control the operation of the sewing apparatus as well as to feed the material to be sewn along each direction in which a seam is to be formed. Sensing means are provided to sense the fact that a seam has been completed. Also, means are provided which clamp the material to the table after each seam is sewn. The control means further include means to rotate the sewing apparatus and align it in such a way that when the material is again fed to the sewing apparatus, the latter sews a successive seam along a different selected direction.
3
The present application claims the benefit of priority from U.S. Provisional Application No. 60/199,765, filed Apr. 26, 2000. FIELD OF THE INVENTION The present invention relates generally to a non-human host model for human tumors. More particularly, this invention relates to a hon-human host model implanted with a human tumor obtained from a human host and utilized for assessing the chemosensitivity of the implanted human tumor to an anti-tumor agent. BACKGROUND OF THE INVENTION The lack of clinically relevant tumor models of different human cancers is a major obstacle in the development of new and effective treatments for cancer especially for treatment of individual patients. Although heterotransplants of certain human tumors have been successfully grown in non-human host subjects such as nude mice, such heterotransplants have never been appropriately been explored for prediction of in vivo chemosensitivity to anti-tumor agents. Most potential anti-tumor agents discovered and tested in clinical trials are rarely approved for use in treatment of cancer. Typically, the majority of the potential anti-tumor agents tested are abandoned for lack of anti-tumor activity during Phase II clinical studies rather than intolerable and/or unpredictable toxicity. Some of the current in vitro anti-tumor agent screening systems utilized by the National Institute of Health and the pharmaceutical industry involve the use of human tumor cell lines derived from multiple sequential in vitro subcultures generated from human tumor explants. Such cell lines are well characterized from a molecular standpoint and are useful in identifying molecular determinants of in vitro sensitivity and/or confirming putative molecular mechanisms of action for the compounds of the anti-tumor agents being screened. Such screening systems have limited usefulness because most human tumors comprise accumulated genetic and molecular abnormalities which produces a high degree of phenotypic heterogeneity. Thus, the relevance of such screening systems for predicting in vivo clinical activity remains to be established. New anti-tumor agents are routinely screened in vivo using human tumor xenografts which are grown subcutaneously in non-human host subjects such as nude mice. Typically, clinical trials of new anti-tumor agents measure tumor growth inhibition rather than tumor shrinkage as an indicator of anti-tumor activity. Such xenografts do not exhibit the heterogenous population of tumor cells which are representative of the human tumor from which they are derived. Furthermore, the vascularity and stroma of such xenografts are exclusively of murine origin. Generally, such xenografts have been selected to suit the putative molecular mechanism of the anti-tumor agent tested. This approach focuses on the proof of principle as to the in vivo model rather than accessing or screening the anti-tumor agent using a panel of clinically relevant and predictive models. If panels of in vivo experimental tumor models clinically representative of each major human cancer type were available, the selection criteria for pursuing the clinical development of novel anti-tumor agents would be stricter but the likelihood of identifying useful anti-tumor agents for particular tumors would be much higher. These would reduce the cost and patient resources required for anti-tumor agent development. Similarly, if individualized models of human cancer were developed, such models would facilitate the process of selecting the optimal therapy for a particular patient's tumor. In vitro sensitivity tests using tumor cells derived from fresh tumor specimens have been known and used extensively. Such tests are typically more useful in confirming a tumor's resistance to anti-tumor agents which have been previously known to show little activity against a particular tumor rather than selecting the most active anti-tumor agent. In addition, in vitro assay systems can not account for the in vivo pharmacological determinants of anti-tumor activity. SUMMARY OF THE INVENTION The present invention is generally directed to a method of evaluating the chemosensitivity of a tumor to an anti-tumor agent in vivo. The method comprises generally of extracting a portion of a tumor from a human host and inserting it into a non-human host subject such as a nude immunodeficient mouse. The implanted tumor is permitted to grow to a minumum preseslected size to form a test tumor. Once the tumor reaches the prerequisite size, an amount of an anti-tumor agent is administered to the non-human host subject sufficient to determine whether the anti-tumor agent is effective in treating the test tumor. The test tumor is then examined to determine the anti-tumor activity of the anti-tumor agent. The present invention is also directed to a method of treating a patient suffering from the presence of a tumor is also contemplated. In particular, one aspect of the present invention is directed to a method of evaluating the chemosensitivity of a tumor to an anti-tumor agent in vivo, comprising: a) extracting a portion of a tumor from a human host; b) inserting the portion of the tumor into a first non-human host subject; c) growing the tumor portion in the first non-human host subject to a minimum preselected size to form a test tumor; d) administering an amount of an anti-tumor agent into the first non-human host subject sufficient to determine whether the anti-tumor agent is effective in treating the test tumor; and e) assessing the anti-tumor activity of the anti-tumor agent on the test tumor. Another aspect of the present invention is directed to a method of treating a patient suffering from the presence of a tumor, comprising: a) extracting at least one portion of the tumor from the patient; b) inserting the portion of the tumor into a first non-human host subject; c) growing the tumor portion in the first non-human host subject to a preselected minimum size to form a test tumor; d) administering an amount of an anti-tumor agent into the first non-human host subject sufficient to determine whether the anti-tumor agent is effective in treating the test tumor; e) assessing the anti-tumor activity of the anti-tumor agent; and, if positive f) administering an effective amount of the anti-tumor agent to said patient. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a set of photomicrographs showing the morphological appearances of two of the transplanted tumors, squamous carcinoma (A), and adenocarcinoma (B) and their respective first successful implants in nude mice, (C) and (D). DETAILED DESCRIPTION OF THE INVENTION The present invention is generally directed to a hon-human host model implanted with a human tumor obtained from a human host utilized for assessing the chemosensitivity of the implanted human tumor to anti-tumor agents created in a manner that provides a system of screening anti-tumor agents for anti-tumor activity and of selecting the most optimal cancer treatment for a patient. This invention deals with the use of heterotransplants of human tumors in nude mice both to screen and select new therapies for different tumors in general and to select the best therapy for the presence of tumor in individual patients. Many types of human tumors can be grown subcutaneously in immunodeficient mice. The morphological and kinetic characteristics of tumors change with each subsequent passage or generation of tumor implanted mice. Accordingly, it is important to use tumors from the early passages to test their response to different anti-tumor agents. The determinants of successful heterotransplantation are not known and generally, successful heterotransplantation is associated with poor clinical prognosis. The potential use of first and second heterotransplants of tumors as tumor models of potential clinical relevance to predict the anti-tumor activity of different anti-tumor agents and/or to select the most optimal treatment for an individual patient has not been explored before. To prove this concept, a large panel of second passage human non-small cell lung cancer (NSCLC) heterotransplants had been developed and molecularly characterized for studying the sensitivity to paclitaxel, an anti-tumor agent. One hundred consecutive resected NSCLC tumors were heterotransplanted subcutaneously into nude mice. It will be understood that the present invention may comprise insertion or transplantation of tumors into the non-human host subject through other modes including, but not limited to, intravenous injection, intraperitoneal implantation, and implantation of the tumor directly into a solid organ. The in vivo sensitivity to paclitaxel was studied in 34 successfully grown heterotransplants. The paclitaxel was intravenously administered to each mouse at a dosage rate of 60 mg/kg every 3 weeks. Treatment was initiated when the tumors reached a size of about 5 mm in diameter and strict standard clinical criteria (>50% tumor shrinkage) were used to define the tumor response. The heterotransplants were morphologically very similar to the original tumors. The response rate to paclitaxel was 21% (95% Cl 9-38%) which is equivalent to that reported in Phase II studies in patients with advanced NSCLC treated with paclitaxel alone. Tumor heterotransplants are thus proposed as relevant models to evaluate new potential anti-tumor agents for treatment of different cancers and to predict clinical response in individual patients. It is noted that the type of tumor utilized for evaluating chemosensitivity to anti-tumor agents comprises a range of cancers including, but not limited to, colon, head and neck, brain, melanoma, sarcoma, breast, ovarian, prostate, kidney and stomach cancers. The results suggest that the heterotransplant models may be used to predict the response of human tumors to different agents and therefore help in the selection of the most optimal cancer therapy for individual patients. It will be understood that the chemosensitivity assay of the present invention may be used to screen a range of anti-tumor agents including, but not limited to, gemcitabine, taxotere, cisplatinum, carboplatinum, irinotecan, topotecan, adriamycin, and atoposide. EXAMPLE 1 Patients and Tumors Between December 1995 and February 1998, 100 fresh NSCLC tumor samples were obtained from the Pathology Department of th University of Texas M. D. Anderson Cancer Center. These samples were taken from 100 consecutive patients who underwent surgical resection for Stage I to IIIA primary NSCLC. None of these patients had undergone preoperative radiation therapy or preoperative chemotherapy. Referring to Table 1, the take rate is shown for 100 heterotransplanted tumors. TABLE 1 Human NSCLC Heterotransplants Take Rate by Histology (n = 100) Histology Number Successful Growth/(%) p-value Adenocarcinoma 44 13 (30%) <0.05 Squamous 32 24 (75%) <0.05 Bronchioalveolar 13  3 (23%) <0.05 Large Cell Undifferentiated 9  5 (55%) Neuroendocrine 1  1 (100%) Sarcomatoid 1 0 (0%) Total: 100 46 (46%) The overall tumor take rate was 46% (95% Cl=36%−56%). The take rate was significantly higher (p<0.05) for squamous cell carcinomas (75%, 95% Cl 57%-89%) than for adenocarcinomas (30%, 95% Cl=17%-45%) and bronchioalveolar carcinomas (23%, 95% Cl=0%−54%). Large cell undifferentiated carcinoma had an intermediate take rate (5/9, 55%). Tumor take rate was independent of the implantation site of the tumor in the mouse. In 10 cases, the tumor initially appeared to have taken but spontaneously disappeared. These cases are considered temporary growths and thus not counted in the calculation of the successful take rate. Tumor Implantation in Nude Mice The fresh tumor samples were cut into 2-3 mm 3 pieces in sterile saline. Three or four pieces of non-necrotic tissue were injected subcutaneously into the lower back and anterior chest of 6 to 8 week old female Nu/Nu mice using a biomedical stainless steel implant needle and maintained under standardized conventional conditions. Animals transplanted with NSCLC tumors were checked for tumor growth over a 36 week period. Tumor formation measuring at least 5 mm in diameter was considered a positive take. Tumor formation was confirmed histologically in all cases. Temporary growth was defined as tumor formation followed by spontaneous regression before reaching a diameter of 5 mm. All other incidences were considered no growth. The histological morphology of all successfully heterotransplanted tumors were compared with that of the resected tumors. There were no significant morphological differences between the tumors resected from the patients and the initial successful implants although the median mitotic index was slightly higher in the heterotransplants (9±6) than in the resected tumors (5±4). Referring to FIG. 1, a set of photographic representations are provided to show the morphology of two of the transplanted tumors with A representing squamous carcinoma and B representing adenocarcinoma and their successfully grown first implants, C and D, respectively. The median time from the day of implantation from human to mouse to the day the tumor reached 1 cm in diameter was about 11 weeks (range 4-24 weeks) and the median weight doubling time which corresponds to a 20% increase in diameter was 18 days (range 11-40 days). These values are longer than those observed with commonly used NSCLC xenografts and much closer to those of human NSCLC which strongly suggests that the heterotransplanted tumors are accurate representatives of the original human tumors. All successfully heterotransplanted tumors were subsequently transplanted several times. Changes in doubling time and mitotic index between the second and third passage were minimal in a group of 21 heterotransplants that were analyzed (doubling time 18±10 days for second passage tumors and 17±10 days for third passage tumors) (mitotic index was 10.9±6.6 for second passage tumors and 12.0±6.3 with p<0.05). Paclitaxel Treatment and Assessment of Response The therapeutic experiments were designed as a standard Phase II clinical study with a target response rate of 20%, the only difference being that the tumor response was assessed as the average of two animals rather than in a single subject as in the case of a human Phase II trial. The tumor grown after implantation from human to mouse was resected and cut into pieces following the same procedure used for the original tumor sample as previously described above, and transplanted subcutaneously into several animals. Tumors from the first mouse to mouse passage were allowed to grow until reaching 5 mm in diameter, at which time the animals were split into two groups: 1) control group—no treatment; and 2) treated group. The treated group was administered 60 mg/kg paclitaxel intravenously as a bolus in the tail vein. Tumor measurements were performed twice a week and the tumor volume was calculated using the formula, a×b 2 /2 (a=longest diameter and b=shortest diameter). Partial tumor response was defined as an average reduction in the tumor volume of at least 50% in the animals of the treated group compared to the tumor volume measured in animals of the control group. Complete tumor response was defined as complete disappearance of the palpable tumor in both animals of the control group. Referring to Table 2, the tumor response to paclitaxel is shown. TABLE 2 Human NSCLC Heterotransplants Response to Paclitaxel Tumor Response/(%) Treatment Number Partial Complete First mouse to mouse passage Squamous carcinoma 20 4 (20%) 0 Adenocarcinoma 11 1 (9%)  0 Undifferentiated carcinoma 2 1 Neuroendocrine carcinoma 1 1 TOTAL 34 7 (21%) 0 (0%) First mouse to mouse passage After first dose 16 4 (24%) 0 After second dose 16 1 (6%)  3 (18%) Second mouse to mouse passage First passage 21 5 (24%) 0 Second passage 21 6 (29%) 0 Out of the total of 34 heterotransplants tested on the first mouse to mouse passage, 7 partial responses defined as a ≧50% reduction in tumor weight were observed after one single dose of paclitaxel for an overall response rate of 21% (95% Cl=9%-38%). There were no discrepancies in tumor response between the two animals in which the response was assessed. Since changes in tumor weight require smaller changes in tumor measurements, all partial responses were reevaluated using the standard clinical criteria of ≧50% in the product of the two largest diameters. All 7 partial responses were partial responses independently of the criteria used. In 16 cases, the animals in the treatment group were again treated with a second dose of paclitaxel on the 21 st day to assess the effect of a second dose of therapy. A second dose of paclitaxel given on the 21 st day did not change the overall response rate observed with the single dose. However, the second dose resulted in the conversion of several partial responses into complete responses. In a total of 16 heterotransplants studied, there were {fraction (4/16)} (25%, 95% Cl-7%-52%) partial responses after one dose. Three of these converted into complete response after two doses. None of the 12 heterotransplants that did not respond with one dose achieved a partial response after the second dose. The therapeutic experiments were also performed in 21 cases using the second mouse to mouse transplants to assess whether sequential passaging alters the chemosensitivity to paclitaxel. In the 21 heterotransplants tested both on first and second mouse to mouse passages, the response rate were 24% (95% Cl: 8%-47%) and 29% (95% Cl: 11%-52%), respectively. These results demonstrate that heterotransplants of NSCLC have an in vivo sensitivity to paclitaxel which is similar to that observed in clinical studies using paclitaxel alone in chemotherapy naive NSCLC patients. The reported overall response rate to a single agent paclitaxel in four Phase II studies that enrolled a total of 160 previously untreated patients with NSCLC is 24% (10, 21, 24, and 38%). The response rate in our series of 34 NSCLC heterotransplants was 21% (95% Cl: 9%-38%), which is essentially identical. These findings and the morphological similarity between the transplants and the original tumors strongly suggest their potential use to predict chemosensitivity. The heterotransplantability of human NSCLC tumors in nude or SCID mice has been the subject of several studies. The take rate of 47% observed in our study is very similar to the take rate reported by these studies and is significantly higher than that reported for other common solid tumors. In particular, the take rate of hormone-dependent tumors such as breast and prostate cancer is typically about 10%. Except for histology, the tumor determinants of successful heterotransplantability remain undefined. Identification of determinants of transplantability is critical for increasing the take rate which would facilitate the general use of these models in predicting chemosensitivity in individual patients. We have analyzed the relationship between tumor response and several baseline and post-therapy molecular markers that have been shown to play a role in paclitaxel sensitivity. The results are mostly confirmatory of previous studies of sensitivity to paclitaxel in different preclinical tumor systems and therefore constitute further evidence of the potential biological and clinical relevance of these tumors. The possibility of using panels of human NSCLC heterotransplants to perform Phase II-like studies with new potential anti-tumor agents potentially effective against NSCLC has not been explored before. Ideally, tumors harvested from first mouse to mouse passages should be used which is possible since tumor fragments from a successful first take preserved frozen in 10% DMSO retain their ability to grow when re-implanted. Orthotopic implantation is possible and would allow determining tumor responses by non-invasive imaging techniques, thus providing more clinically relevant information on tumor sensitivity. If the response rates using standard clinical criteria in Phase II-like studies conducted with the heterotransplants were similar to those observed in human Phase II studies with the same anti-tumor agents, as we have demonstrated with paclitaxel in this study, this observation would help validate the clinical relevance of these models and justify their use for selecting new potential anti-tumor agents for clinical development. Obviously, such relevance would still be limited to drugs whose metabolism in man and mouse are similar, and at doses that result in a similar AUC both in man at the maximum tolerated dose and the dose used in the mouse. This might exclude a few anti-tumor agents from being amenable to this type of screening. The main thrust of this invention is to use these tumors as relevant models of individual patient tumors to predict sensitivity and therefore be useful tools for individualized selection of therapy. We are planning to demonstrate such use in asymptomatic patients with slow growing and in patients with early stage tumors who undergo resection and are treated with chemotherapy upon relapse, thus allowing a correlation between response upon relapse and sensitivity of the heterotransplant derived from the resected tumor. The foregoing discussion discloses and describes merely exemplary embodiments of the present invention. One skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims, that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.
A method of evaluating the chemosensitivity of a tumor to an anti-tumor agent in vivo is provided. The method comprises extracting a portion of a tumor from a human host and inserting the portion of the tumor into an immunodeficient mouse. The tumor portion is permitted to grow to a minimum preselected size to form a test tumor. An amount of an anti-tumor agent is administered to the immunodeficient mouse sufficient to determine whether the anti-tumor agent is effective in treating the test tumor. The anti-tumor activity of the anti-tumor agent on the test tumor is assessed.
2
This is a divisional of copending application Ser. No. 07/899,633, filed on Jun. 16, 1992, now U.S. Pat. No. 5,316,819. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to a bellows, process in production of the bellows. More particularly, the invention relates to a bellows for expandably and/or contractibly insulating movable portions of machineries so as to protect from external disturbance factor, such as dust, light beam, humidity and so forth. Description of the Background Art In the prior art, as shown in FIG. 2, a sheet material 1 which is formed by coating a neoprene rubber on a woven fabric, is pressed into a plurality of essentially channel-shaped pieces 2, 2a, 2b, 2c, . . . having an outer edge 5 and an inner edge 4 by completely cutting along cut edges 4a and 5c, as shown in FIG. 2(b). Then, each two pieces 2, 2a and 2b, 2c, . . . are piled together. The mating inner edges 4 of the piled pieces are sewn along a sewing lines 4c to form an individual bellows segment, as shown in FIG. 2(c). The sewing along the sewing line 4c which extend along the inner edge 4 will be hereafter referred to as "inside sewing". After completing the inside sewing process for forming necessary number of bellows segments, adjacent pieces, such as pieces 2a and 2b in FIG. 2(d) of the adjacent bellows segments are sewn along sewing lines 5b which extend along the outer edge 5 for connecting adjacent bellows segments. The sewing along the sewing line 5b will be hereafter referred to as "outside sewing". Therefore, in the final product of the bellows, the inside sewing and the outside sewing are provided in alternating fashion. It is possible to provide tack bonding along respective sewing lines 4c and 5b upon piling pieces in advance of performing sewing process in order to facilitate sewing process and to prevent the piled pieces from causing displacement during sewing process. In such conventional process, since the pieces are completely separated, piling of respective individual pieces with precisely aligning peripheral edges either for the inside sewing process or for the outside sewing process, is time consuming and labor intensive work. Furthermore, since displacement in the piled pieces during sewing process may results in distortion of the final products, relatively high skill of the experienced labor is required for performing sewing process to make the sewing process as cost intensive process as well. Although tack bonding along the sewing lines may prevent the problem of causing displacement during sewing process, process of tack bonding is also time consuming and labor intensive work. SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide a bellows, and process in production of the bellows, which can provide complete solution for the difficulties or disadvantages in the prior art. Another object of the present invention is to provide a bellows and process for producing thereof which can reduces work load and process time in production and does not require substantial skill in performing sewing process without causing displacement of pieces which results in distortion of the final product. In order to accomplish the above-mentioned and other objects, a bellows comprises a sheet material defining by a plurality of series of pieces of the same configuration of the same size, each piece having outer edges adapted to define the external configuration of the bellows and a recessed portion defined by inner edges and defining a configuration of the inner space of the bellows, an inner connecting portion extending along said inner edges of mating adjacent pieces for interconnection therebetween, a pair of first bridging portions extending over said mating adjacent pieces at positions in the vicinity of both ends of said inner connecting portion, said pair of first bridging portions being formed integrally with the associated portion of both of said mating adjacent pieces for maintaining integrity therebetween, an outer connecting portion extending along said outer edges of the mating adjacent pieces for interconnection therebetween, and a second bridging portion extending over said mating adjacent pieces at a position in the vicinity of said outer connecting portion, said second bridging portion being formed integrally with the associated portion of both of said mating adjacent pieces for maintaining integrity therebetween. In the preferred construction, said pair of first bridging portions may be formed by terminating cut edge at mid-way. In this case, the cut edge may extend transversely with respect to the longitudinal direction of said one piece of sheet material and terminated at positions in the vicinity of both ends of said inner connecting portion. Also, in the preferred construction, the second bridging portion may be formed by a perforation transverse to the longitudinal direction of said one piece of sheet material and defining border between adjacent pieces. According to another aspect of the invention, a sheet material for forming a bellows defining by a plurality of series of pieces of the same configuration of the same size, each piece having outer edges adapted to define the external configuration of the bellows and a recessed portion defined by inner edges and defining a configuration of the inner space of the bellows, a pair of first bridging portions provided at a first border being connected a first piece with second piece adjacent thereto, and a second bridging portion provided at a second border being connected a first piece with a third piece adjacent thereto at opposite side to said second piece. In this case, the first border further may include a cut edge extending transverse to a longitudinal direction of said sheet material and terminated at the intermediate position with leaving said pair of first bridging portions. Also, the second border is defined by a perforation. According to a further aspect of the invention, a process for producing a bellows comprises the steps of providing an elongated continuous sheet having a longitudinal axis, forming a sheet material by defining a plurality of series of pieces of the same configuration of the same size, each piece having outer edges adapted to define the external configuration of the bellows and a recessed portion defined by inner edges and defining a configuration of the inner space of the bellows, a first piece being bordered from adjacent second piece through a first border including at least one bridging portion extending over said first and second pieces and integrally connected to both of said first and second pieces, and said first piece being further bordered from adjacent third piece positioned at opposite side to said second piece through a second border including at least one bridging portion extending over said first and third pieces and integrally connected to both of said first and third pieces, mating respective of adjacent pieces by folding said sheet material at respective of said first and second borders, and rigidly connecting respective of said inner edges and outer edges of said mating adjacent pieces. In the construction of the present invention, since the elemental pieces of the bellows are formed in series with maintaining integrity, those pieces are folded at respective borders to mate with the adjacent pieces during process of production. Upon folding, the respective of the bridging portions may serve as means for identifying the portion to be folded and as means for positioning the piece relative to the adjacent piece for allowing precise positioning of the pieces with avoiding possibility of offsetting or displacement during process for connecting the mating pieces. This substantially reduces labor work and process time required for precisely mating the pieces in comparison with the process in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be understood more fully from the detailed description given herebelow and from the accompanying drawings of the preferred embodiment of the invention, which, however, should not be taken to limit the invention but are for explanation and understanding only. In the drawings: FIG. 1 shows the preferred process in production of a bellows according to the present invention, in which FIG. 1(a) shows a sheet material, from which the preferred construction of bellows is formed, FIG. 1(b) is a plan view of the sheet material after pressing process, FIG. 1(c) is a perspective view showing manner of inside sewing in the preferred process according to the invention, and FIG. 1(d) is a perspective view showing manner of outside sewing in the preferred process according to the invention; and FIG. 2 shows the typical process in production of a bellows in the prior art, in which FIG. 2(a) shows the material of sheet identical to that in FIG. 1(a), FIG. 2(b) is a plan view of the sheet material after pressing process, FIG. 2(c) is a perspective view showing the manner of inside sewing in the prior art, and FIG. 2(d) is a perspective view showing manner of outside sewing in the prior art. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to FIG. 1, the preferred process of production of a bellows according to the present invention will be discussed in an order of process steps. Similarly to the prior art, a sheet material 1 is produced by coating neoprene rubber on a woven fabric, for example, and may be provided in a form of a roll of sheet material, as shown in FIG. 1(a). Although the specific material of the sheet material 1 is mentioned as above, it is possible to use any suitable material for forming an elastically deformable or expandable bellows. The sheet material 1 is subject pressing process to be formed into a pressed sheet as shown in FIG. 1(b). The pressed sheet in the present invention includes series of mutually connected pieces 3, 3a, 3b, 3c, . . . As in the prior art, each piece 3, 3a, 3b, 3c, . . . is formed into essentially channel-shaped configuration. Each piece 3, 3a, 3b, 3c, . . . is defines by a partial cut edge 4a at one longitudinal edge and a perforated edge 5a at the other longitudinal edge. As can be seen from FIG. 1(b), the cut edge 4a is terminated at the lateral mid-way between an outer edge 5 and an inner edge 4 with a leaving connecting strip 4b. With the construction set forth above, the individual pieces 3, 3a, 3b, 3c, . . . are connected to the adjacent pieces through the connecting strip 4b at one longitudinal edge and through the perforated edge 5a at the other longitudinal edge to form a series of sheet. In the preferred construction, the depth of the cut edge 4a may be selected so that it may terminate at a position inside of an inner sewing line 4c so that full expansion stroke of the final bellows can be provided. To perform the inside sewing process, the series of pieces are folded at every connecting strips 4b so that every other pieces 3, 3a and 3b, 3c, . . . mate each other with aligning respective of the inner and outer edges 4 and 5. During this folding process, since the connecting strips 4b serve as folding marks for allowing folding at precisely desired positions and as positioning means for precisely positioning the mating pieces, offsetting or displacement between the mating pieces will never caused. After completion of folding process, the inside sewing is performed for every mating inner edges 4 along the inner sewing line 4c. After completing the inside sewing process, the outside sewing process as shown in FIG. 1d is performed for respective of the pieces 3, 3a, 3b, 3c, . . . . In the outside sewing process, respective pieces 3, 3a, 3b, 3c, . . . are folded at the perforated edges 5a so as to be mated with the adjacent pieces. In this folding process, since the folding positions can be precisely defined by the perforated edges 5a and accurate positioning can be provided by the combination of the sewn inner edges 4 and the perforated edges, precise piling of the pieces can be obtained. Then, outside sewing is performed along outer sewing lines 5b which extends along the outer edges 5 and the perforated edges 5a. By completion of the outside sewing process, the production of the bellows is completed. As can be appreciated herefrom, since the essentially channel-shaped individual pieces, in the present invention, forms a series of at least partially connected sheet, the three points connection, i.e. at the connecting strips 4b and the perforated edge 5a, between adjacent pieces contributes for precise positioning of mating pieces with avoiding relative offset or displacement throughout the production processes including sewing processes. The preferred process thus allows substantial reduction of the labor work and process time with avoidance of distortion in the final products for higher yield. This clearly improves production efficiency. Furthermore, because of the three points connection facilitating positioning of the mating pieces throughout the production process, it does not require substantial skill in performing sewing process and thus contributes lowering of production cost. In addition, since the respective pieces maintain connection through the connection strips and the perforated edges even after completion of the production process, it may assist tight fitting of the adjacent pieces even when loosing of the sewn portion is caused and may avoid entry of the dust, dirt and so forth into the interior space. While the present invention has been disclosed in terms of the preferred embodiment, various modifications, changes or reconstruction of the shown embodiment will be obvious to those skilled in the art without departing from the principle of the invention as defined in the appended claims. Therefore, the present invention should be understood to include all possible and obvious modifications, changes, omissions and reconstructions derived from the shown embodiment. For example, as set out above, the sheet material is not specified to the woven fabric with the neoprene coating. Also, the perforation employed at the border between the adjacent pieces can be replaced with the cut outs with leaving necessary width of the connecting strip or strips in the similar manner to that for the cut edges 4a. The perforation may also be replaced with one or more impression for defining the folding portion. In addition, the way of connecting the pieces should not be limited to sewing but can be any suitable ways, such as bonding, high frequency welding, or so forth. The way to connect the pieces as well as the material to form the bellows may be selected depending upon specific application of the bellows to be produced. Also, the order of connection of the adjacent pieces may not be specified to begin with the connection for the inner edges but may be started from the connection for the outer edges. Furthermore, although the foregoing discussion is made for production of the bellows formed with a plurality of essentially rectangular or square pieces, the present invention is equally applicable for the bellows with any different configurations of pieces, such as semicircular configuration.
A bellows is formed from a plurality of elemental pieces. A plurality of the elemental pieces are integrally formed as a one piece of continuous sheet material defining borders between the pieces. The border includes partial discontinuous for identifying folding portion of the pieces for mating adjacent pieces. Continuity of adjacent pieces is maintained by bridging portions which serves as positioning means for precisely mating the adjacent pieces for connecting peripheral edges for completing the bellows.
8
BACKGROUND OF THE INVENTION The present invention relates to an apparatus for transporting a carriage along a path. The invention particularly relates to such an apparatus used to transport a printhead along a line whereon characters are to be printed in a typewriter or printer. It is known in the typewriter and computer controlled printing machines arts to transport a printing module or printhead along a line of printing, adjacent to a platen. Such printers typically employ dot matrix, daisy wheel or thermal devices to print upon paper held against the platen. In use, the printhead is transported along the line of print such that adjacent characters printed on the paper are properly spaced apart. This transportation of the printhead, in the prior art, is achieved by means of belts, leadscrews, wires and other devices linked to a printhead carriage constrained by tracks, sliders and other means to move along the printing path. The distance moved by the printhead between successive printing operations is small, and in consequence the quality of the drive mechanism for the printhead carriage is required to be high. In the prior art, it is known to use stepping motors to drive the belts or wire, in which instance it is necessary for the stepping motors to be of high quality and accuracy, and to have many steps of angular position in each full rotation. These prior art solutions have the further disadvantage that the quality of the mechanical parts is required to be extremely high since drive from a motor is applied more or less directly to the printhead carriage. The present invention seeks to improve over the prior art by providing a printhead carriage which is driven along the printing path using a principle of differential motion whereby gross movements in a wire, belt or rack causes only a small linear displacement of the carriage, allowing coarse and relatively imprecise mechanical parts to be employed. The present invention further seeks to provide improvement over the prior art by allowing for the motor which moves the printhead to be selectably mounted either on the printhead itself or on the body of the printer, thereby making for a compact construction. SUMMARY OF THE INVENTION The present invention resides in a carriage transport apparatus wherein a carriage is constrained to move in a predetermined path, the apparatus including a first portion of band, movable in a first direction relative to the path and operative in response thereto to impart relative movement between itself and the carriage in a first direction sense along the path; and a second portion of band simultaneously movable with the first portion of band by the same distance in a second direction relative to the path and opposed to the first direction and operative in response thereto, to impart relative movement between itself and the carriage in a second directional sense opposed to the first directional sense along the path, for the carriage to be displaced in the path by the difference between the relative movement in the first directional sense and the relative movement in the second directional sense. In a first preferred embodiment, a differential wheel has a first portion of an endless band looped around a first portion having a first radius of the differential wheel and has a second portion of an endless band wrapped around a portion of itself on a second radius. The band passes around spaced pulleys, one of the pulleys being an idler pulley and the other a driven pulley. The differential wheel itself is attached to a carriage bracket constrained to move along the printing path. A coarse stepping motor drives the driven pulley and the action of the differential wheel assures that gross rotation of the driven pulley produces only small linear displacement of the carriage bracket. In a second preferred embodiment, the stepping motor driving the carriage transport apparatus is mounted on the carriage bracket itself and rotates the differential wheel. The endless band is supported between two idler pulleys and as the differential wheel pays the endless band on and off itself, the carriage bracket moves along its printing path by a relatively small displacement for gross angular displacement of the differential wheel. In a third preferred embodiment, the endless band, which previously was wrapped around a portion of the differential wheel, is replaced by a toothed timing belt engaging only tangentially with toothed portions of the differential wheel and passing around support pulleys in the same manner as for the endless band. In a fourth preferred embodiment, the endless band is replaced by solid racks once again tangentially engaging portions of different radii on the differential wheel. In the fourth embodiment, the racks are constrained to move in opposite directions by equal amount by means of a transfer roller held therebetween. DESCRIPTION OF THE DRAWINGS The preferred embodiments are hereinafter described in greater detail with reference to the appended drawings in which: FIG. 1 shows a projected view of a first preferred embodiment of the present invention. FIG. 2 shows a cross sectional view through the differential wheel of FIG. 1 and depicts in diagrammatic fashion a clutch arrangement interposed between the portions of the wheel. FIG. 3 illustrates the manner in which the endless belt of FIG. 1 passes around the portions of different radii of the differential wheel of FIG. 2. FIG. 4 shows a second preferred embodiment of the invention wherein the motive means has been transferred to the carriage bracket of FIG. 1. FIG. 5 shows a third preferred embodiment of the invention wherein a toothed timing belt is employed. FIG. 6 and FIG. 7 show variations of a fourth preferred embodiment of the invention wherein solid, rigid racks are used to move the differential wheel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 shows a projected view of the first preferred embodiment of the present invention. A printhead carriage 10 in a typewriter or other electro-mechanical printer is constrained to move along a guide rod 12 by a sleeve 14 sliding on the guide rod 12 to allow movement of the printhead carriage 10 along a line of printing as indicated by a first arrow 16. The printhead carriage 10 is shown here as being supported on a guide rod 12 only by way of example. Those skilled in the art will be aware that it is equally possible in the present invention to guide the printhead carriage 10 by tracks, grooves and linear races. The printhead carriage 10 is provided in the form of a bracket whereon a differential wheel 18 is mounted to rotate. FIG. 1 shows the first preferred embodiment in partially exploded form. The differential wheel 18 comprises an axle 20 for mounting through an opening 22 in the printhead carriage 10. The differential wheel 18 may be rotatably fixed to the printhead carriage 10 in any manner known in the art and the method here given is by way of example. An endless belt or band 24 is wrapped in a manner (to be described later) around the differential wheel 18, and is supported at its extremities by an idler pulley 26 which is free to rotate without opposition and by a driven pulley 28 rotated by a motor 30. FIG. 2 shows a cross-sectional view of the differential wheel 18 of FIG. 1 and depicts in diagrammatic fashion a clutch arrangement 15 interposed between portions 32 and 34 which comprise the wheel 18. The wheel 18 comprises a first circular portion 32 of a first diameter and a second circular portion 34 of a second diameter less than the first diameter. Optional guard rings 36 extend beyond the first 32 and the second 34 portion diameters of the differential wheel 18 to prevent the endless belt 24 from slipping off the differential wheel 18. FIG. 3 shows how the endless belt 24 is passed around the differential wheel 18. Here, all elements except the endless belt 24 are omitted for clarity. A first portion 38 of the endless belt or band 24 passes around the first portion 32 of the differential wheel 18 in a first loop 40 and a second portion 42 of the endless belt or band 24 passes in a second loop 44 about the second portion 34 of the differential wheel 18. As the motor 30 rotates the driven pulley 28, so the first 38 and second 42 portions of the endless belt 24 move in opposite directions as indicated by second 46 and third 48 arrows. When the motor 30 is reversed in direction, so the directions of travel of the first portion 38 and the second portion 42 of the endless belt or band 24 also reverse and remain opposite to one another. Referring collectively to FIGS. 1, 2 and 3, as the motor 30 rotates the driven pulley 28, so the belt or band 24 is paid out towards and back from the idler pulley 26 which ensures that the movements of the first and second portions 38,42 of the belt are equal and opposite with regard to the overall apparatus (as exemplified by the guide rod 12). The first loop 40 passing around the first portion 32 of the differential wheel 18 causes rotation of the differential wheel 18 which in turn is accompanied by the first portion 32 of the differential wheel rolling along the first portion 38 of the belt 24 by a first distance. Similarly, movement of the second portion 42 of the belt 24 in the second loop 44 around the second portion 34 of differential wheel 18 also causes rotation of the differential wheel 18 which in turn is accompanied by the second portion 34 of the differential wheel 18 rolling along the second portion 42 of the belt 24 by a second distance in the opposite direction to the movement induced relative to the belt 24 by the first loop 40 and the first portion 32 of the differential wheel 18. Now, the actual movements relative to the belt 24 of the first and second portions 32,34 of the differential wheel are to a large part cancelled by virtue of the movement in opposite directions as indicated by the second and third arrows 46,48 of the belt or band 24. Thus, the residual movement of the differential wheel 18 is caused to be the difference between the distance rolled along the first portion 38 of the belt or band 24 and the distance rolled along the second portion 42 of the belt or band 24. The residual movement is coupled by the axle 20 to the printhead carriage 10 which in turn is constrained to move by the residual motion linearly along the guide rod 12. By bringing the diameters of the first and second portions 32,34 of the differential wheel 18 very close to equality in value, the motor 30 may be made as coarse as is desired for reasons of economy or control. In the limiting case when the diameters of the first and second portions 32,34 are made exactly equal, no movement may be induced in the printhead carriage 10 no matter how many revolutions the driven pulley 28 may make. As the diameters of the first and second portions 32,34 diverge, so the linear velocity of the carriage 10 per unit angular velocity of the driven pulley 28 increases. The motor 30 may thereby be required to impart multiple revolutions to the driven pulley 28 in order to move the carriage 10 along the rod 12 by just one character printing space. This is in marked contrast to the prior art where such a motor or motor/gearbox assembly would be required to execute only a tiny precise fraction of a revolution. Equally, the motor 30 can be replaced by solenoids, ratchet devices and other coarse mechanisms which would otherwise be unacceptable in such an application. All that is required of the motor device 30 is that it is capable of rotating the driven pulley 28 by a controlled amount. Again referring to FIG. 3, while the first 40 and second 44 loops have been shown as consisting solely in a single turn, it is to be appreciated that the loops 40,44 may comprise more than one turn. Further, while the loops 40,44 are shown as having been wound in a particular sense or direction of winding around the first and second portions 32,34 of the differential wheel 18, all that is required in the sense of winding is that, when the belt or band moves as indicated by the second 46 and third 48 arrows, both loops 40,44 tend to urge the differential wheel 18 to rotate in the same rotational direction. FIG. 4 shows a second preferred embodiment of the invention. The motor 30 has been moved from the body or chassis of the printing mechanism (as shown in FIG. 1) onto the printhead carriage 10 itself and the motor 30 is mounted to rotate the differential wheel 18. The endless belt or band 24 is held at its extremities between a pair of support pulleys 50 which are both idler pulleys and which serve to ensure that motion of one portion 38 of the band 24 is countered by equal and opposite motion of the second portion 42 of the band 24. Operation is as before save that it is the differential wheel 18 which imparts movement to the band 24 to move the printhead carriage 10 along the guide rod 12. The same provisions concerning the motor 30 and the diameters of the first 32 and second 34 portions of the differential wheel 18 as apply to the first embodiment shown in FIG. 1, also apply to the second embodiment shown in FIG. 2. FIG. 5 shows a third preferred embodiment of the invention where the endless band or belt 24 is replaced by a toothed endless timing belt or band having a first portion 52 in tangential engagement with a first toothed portion 54 of a differential gearwheel 56 and a second portion 58 in tangential engagement with a second toothed portion 60 of the differential gearhweel 56. Rollers 62 are urged as indicated by fourth 64 and fifth 66 arrows to thrust the first 52 and second 58 portions of the endless timing belt respectively on to their first 54 and second 56 toothed portions of the differential gearwheel 56. The differential gearwheel 56 is mounted upon the printhead carriage 10 in the same manner shown for the first embodiment of FIG. 1 and the second embodiment of FIG. 4. The endless toothed timing belt 52,58 (shown in FIG. 5 only in part) may pass either around an idler pulley 26 and driven pulley 28 arrangement as illustrated in FIG. 1 or may pass around a pair of support pulleys 50 as illustrated in FIG. 4. FIG. 6 and FIG. 7 show variation of a fourth preferred embodiment of the invention where the endless belt 24 or the endless toothed belt 52,58 is replaced by a pair of rigid racks 68,70. While FIG. 6 and FIG. 7 show the racks 68,70 as being smooth it is to be understood that they may equally well be toothed and engage a differential wheel 72 substantially identical to the differential gearwheel 56 shown in FIG. 5. The racks 68,70 move as indicated by sixth and seventh rows 74,76 and a transfer roller 78 is fixed between the first and second rigid racks 68,70 to ensure that movement of the first rack 68 is transferred as equal and opposite movement to the second rack 70. The racks 68,70 roll against the differential wheel 72 in the manner described for the third embodiment of FIG. 5. Either one of the racks 68,70 may be driven or, such as rack 68 in FIG. 7 which is driven by friction gear 35 attached to the shaft of motor 30. Alternately, the differential wheel 72 may be the source of motive power, as seen in FIG. 6 where the shaft of motor 30 is connected directly to the differential wheel 72. The presence of the transfer roller 78 ensures that the two racks 68,70 co-operate to move the printhead carriage 10 in the same manner as does the endless belt 24 and the endless toothed belt 52,58. The present invention also allows for a rapid carriage return stroke to be imparted to the printhead carriage by disengagement of the rack or belts from one part of the differential wheel. Turning first to FIG. 5, when it is desired to execute a rapid carriage return, one of the rollers 62 is moved away from its respective portion of the endless timing belt 52,58 allowing that portion of the timing belt to disengage from its portion 54,60 of the differential gearwheel 56. When the motor 30 is mounted as shown in the second embodiment of FIG. 4, the remaining toothed portion 54,60 of the differential gearwheel 56 engages only one half of the toothed belt 52,58 and the carriage 10 is moved along that portion, when the portion is held immobile, at high speed. Thus the removal of one of the portions 52,58 of the endless toothed timing belt from the differential gearwheel 56 is accompanied by clamping of one of the support pulleys 59 to immobilize the belt 52,58. With regard to FIG. 6, all that is necessary to achieve the rapid carriage return is to lift one or the other of the racks 68,70 away from the differential wheel 72 (for example, rack 70 may be moved in the direction of arrow 75), to clamp the transfer roller 78, and then, with the motor 30 on the printhead carriage 10 as shown in FIG. 4, to allow the differential wheel 72 to transfer rapidly along the rack 68 with which it is still in contact. With regard to FIG. 7, to achieve the rapid carriage return, rack 70 may be moved away from differential wheel 72 in the direction of arrow 75; and motor 30 via its friction gear 35, will allow the differential wheel 72 to transfer rapidly along the rack 68 with which it is still in contact. With regard to FIG. 4, all that is necessary to achieve a rapid carriage return is to ensure that the first 32 and second 34 portions of the differential wheel 18 are selectably independently rotatable. This may be achieved by provision, for example, of a magnetic or other clutch arrangement 15 (FIG. 2) between the first 32 and second 34 portions of the differential wheel 18 whereby one or the other of the portions 32,34 is rendered free to rotate, that is, is not constrained to rotate with the shaft of the motor 30. In order then to execute a rapid carriage return, one of the support pulleys 50 is clamped, the freely rotating portion 32,34 of the differential wheel 18 is freed, and the motor 30 caused to rotate. While in the above embodiment the motor 30 has been shown as imparting direct drive either to the differential wheel 18 or to the driven pulley 28, it is to be appreciated that a gearbox may be employed between any motor and any driven element. The present invention has hereinbefore been described with reference to a printing apparatus. Those skilled in the art will appreciate that many other applications for the present invention exist, in any machinery where a carriage assembly requires to be precisely positioned. While the preferred embodiment hereinbefore described shows the differential wheel 18,56,72 as comprising portions of different diameters, in the present invention it is possible to replace the portions of different diameters by mutually geared portions whose rates of revolution on the axle 20 or motor shaft are thus rendered different.
Disclosed is a precision printhead transport apparatus. The apparatus includes a differential wheel rotatably mounted upon belt or a printhead carriage which is constrained to move along a printing path. A first portion of an endless belt or band is looped around a first portion of the differential wheel having a first radius and a second portion of the band is looped around a second portion of the differential wheel having a second radius. The band further passes around two pulleys positioned on opposite sides of the differential wheel, one of the pulleys being an idler pulley and the other a driven pulley. A course stepping motor drives the driven pulley and the action of the differential wheel assures that gross rotation of the driven pulley produces only small linear displacement of the printhead carriage. Embodiments disclosed include both smooth and toothed bands and the use of a pair of rigid racks in place of the endless band. Also disclosed are modifications providing for a rapid printhead carriage return stroke accomplished by disengagement of the rack or band from one portion of the differential wheel.
1
FIELD OF DISCLOSURE [0001] The inventive concept disclosed herein generally relates to a method and apparatus for transporting data flows over electrical or optical information networks which make use of multipath techniques, and more particularly but not by way of limitation, to a method and apparatus for transporting packets while retaining the order of the packets for traffic aggregates contained within larger traffic aggregates. BACKGROUND [0002] Information networks are well known in the art and function to transmit information such as computer data between various computer systems operably coupled to the information network. [0003] One example of a packet-switched network is defined by the IEEE 802 standards, including the set of standards within IEEE 802 commonly known as Ethernet. These standards have found widespread acceptability and many networks conform to these standards. [0004] Packet switched networks are distinguished from other multiplexing techniques in that each packet header is inspected to determine where to forward the packet to in order to transmit the packet closer to its final destination. [0005] A second example is a purely circuit-switched network which operates by creating, maintaining and transmitting data over a circuit between two network nodes. Circuit switched networks may use Time Division Multiplexing (TDM) in which case such a circuit has a fixed bandwidth which poses many disadvantages. [0006] Packet networks make use of data plane protocols which constitute an agreement among parties regarding the encapsulation or modulation of information. At the lowest physical layer protocols define the modulation or electrical or optical signals. At slightly higher layer protocols layers define bit patterns used to identify the beginning and end of packets. At this layer and at higher layers protocols encode information related to the delivery of information across highly complex networks. [0007] Communication networks whether communicating between computers within a single building, or communicating between two metropolitan areas, e.g., San Francisco and New York are formed by a plurality of interconnected network elements. The network elements and interconnection between elements are commonly referred to using a slight variation on graph theory terminology. Network elements are referred to as “nodes”. Interconnections between network elements are referred to as “links”. In the mathematical discipline of graph theory the term “edge” is used where in information network the term “link” is used. [0008] In information networking the term “edge” is used to indicate part of a network immediately adjacent to one or more “end systems”, where the “end system” transmits and receives packets for their own use but do not forward packets for the benefit of other nodes in the network. In many modern networks all nodes both transmit packets and receive packets that are used for their own purpose. The term end system indicates that the sole purpose of a given node or set of nodes in a network is to use the services of the network rather than provide services. For example, the primary purpose of the core of a network is to forward large volumes of traffic for the benefit of other nodes. The primary purpose of the edge of a network is to deliver traffic to end systems. End systems only source and sink traffic. [0009] Date plane protocols are used to facilitate the delivery of data from one computer or end system in a network to another. Date plane protocols generally place information immediately preceding the data to be delivered. The data to be delivered is known as the payload. The information placed in front of the payload is known as the packet header. The packet header generally carries information regarding where and how to deliver the packet. The payload may be followed by other information defined by the protocol, such as a frame check sequence to insure the integrity of the header and payload. The entire packet definition dictated by a particular protocol is known as that protocol's encapsulation. [0010] A packet may be encapsulated by a computer transmitting the packet into a large network with information about the final delivery of the packet. A series of related packets sent between two end systems is a type of traffic flow known in IETF terminology as a “microflow” and in IEEE 802.1-AX terminology as a “conversation”. [0011] One type of network is referred to as a “packet network”. A key requirement of a packet network is to deliver information from one computer or end system in the network, to another as directed by a specific protocol. Modern networks carry millions, if not billions of individual microflows at any given time, where the microflows are tiny in capacity relative to the capacity of the network and are extremely short lived. [0012] Within the core of a communications network it is useful to forward large traffic aggregates rather than forward individual microflows. The Internet Protocol (IP) for example, supports this directly in its method of address allocation. A full IP address is 32 bits in IP Version 4 (IPv4) and 128 bits in IP Version 6 (IPv6). A set of higher order bits can be used to forward a traffic aggregate. For example, a trading station in the San Francisco financial district may exchange packets with a server operated by a stock exchange in the New York financial district. The full IP addresses identify the end systems. A smaller number of bits in the address may identify the address as falling within the New York metropolitan region. Additional bits used within the New York metropolitan region only might identify the destination as belonging to a particular stock exchange on Wall Street. Once delivered to the exchange, the full address can then be used to reach the specific server. This form of addressing is defined in the IETF as Classless Interdomain Routing (CIDR). [0013] Some protocols make use of further encapsulations when aggregating traffic. Multiprotocol Label Switching (MPLS) is one such protocol. Ethernet Provider Bridging is another such protocol. For example, within the network in the San Francisco Bay area, a node may further encapsulate all traffic destined to the New York metropolitan area with an MPLS header, which in MPLS is called a label stack, or if the packet is already encapsulated as MPLS, add one or more label stack entries. [0014] In many protocols further encapsulations can be added in order to form larger traffic aggregates. Forming larger traffic aggregates reduces the amount of control information exchanged and reduces the number of forwarding entries required deep in the core of a network. Each encapsulation is referred to as a layer of encapsulation. In some circles additional MPLS label stack entries are referred to as sub-layers, but the sub-layer terminology will not be used herein. [0015] The outside encapsulations are transmitted first. In MPLS the outer encapsulation is also referred to as the top label stack entry or top of the label stack. Inner MPLS encapsulations are referred to as lower label stack entries and are referred to as residing below the upper label stack entries. This use of “upper” and “lower” in describing label stack entries conflicts with the use of “upper” and “lower” in describing more general layering. [0016] In many cases more than one link may interconnect a pair of nodes. In other cases, more than one indirect path at a lower layer may be available between a pair of nodes involving one or more intermediate nodes. In many cases it is desirable to spread traffic over one or more direct links, or one or more lower layer paths when forwarding large traffic aggregates across a network. [0017] A number of techniques involve spreading the traffic flows across multiple links or multiple lower layer paths. Collectively these solutions are called multipath techniques. A set of individual links or individual lower layer paths over which a multipath technique operates is called a multipath. Each of the individual links or individual lower layer paths is called a component of the multipath. A term which is roughly synonymous with multipath is composite link, however the two are not quite equivalent. [0018] A common and well documented set of techniques use a hash function applied over information in packet headers as a basis for distributing traffic across the set of links in a multipath. These techniques commonly search for the innermost encapsulation which can practically be identified, such that the largest number of generally small flows or microflows can provide input to the hash, thereby providing a greater probability of an even distribution of traffic. Some multipath techniques support making adjustments to correct slight imbalance in traffic among the component links or lower layer paths. Using information at the innermost encapsulation where the least amount of traffic aggregation has occurred allows a very fine granularity to make adjustments in load balance for those techniques that support this form of adjustment. [0019] MPLS-TP is a restricted subset of MPLS intended to provide capabilities and management that is more similar to transport network operators who are likely to be familiar with the operation of legacy TDM networks. MPLS-TP has placed new requirements on the underlying server layer. Among these requirements are that traffic within an MPLS-TP traffic flow cannot be reordered. This requirement is in conflict with the behavior of existing multipath techniques. [0020] Existing multipath techniques include but are not limited to the following three examples. [0021] 1. ECMP—Equal cost multipath (ECMP) has been applied to IP networks since the 1980s. ECMP is defined for the IETF OSPF protocol and for the ISIS protocol, among others. [0022] 2. Ethernet Link Aggregation—The IEEE has defined 802.1AX 2010. This is a form of multipath to be applied exclusively to Ethernet. [0023] 3. MPLS Link Bundling refers to an MPLS technique which allows multiple links or lower layer paths between a pair of MPLS label switched routers to be announced in a link state routing protocol as a single Label Switched Router forwarding adjacency (link). Any one link or lower layer path in a link bundle is referred to as a component of the link bundle or more briefly as a component link. An LSP may be placed on a single component or may be spread out over multiple components. When traffic is spread out over multiple components, control plane signaling and management protocols report that the “all ones” component is used, indicated by a binary component number containing all ones (a near impossibly large component number). [0024] Within any of these multipath techniques, the traffic across a multipath need not be evenly distributed. For example, an Ethernet Link Aggregation Group (LAG) may have some members (component links) of one capacity (10 Gb/s for example) and some members of another capacity (40 Gb/s or 100 Gb/s for example). In the case of link bundling, the component links may be other MPLS LSP, whose capacity is expressed as a real number in bytes per second. [0025] A method and apparatus which simultaneously meets the following two requirements would be beneficial to the information network, in particular to large information networks. [0026] 1. The method and apparatus should be capable of transporting packets conforming to requirements to avoid packet reordering among traffic aggregates contained within larger traffic aggregates, specifically but not limited to MPLS-TP traffic aggregates within larger MPLS traffic aggregates. [0027] 2. The method and apparatus should be able to take advantage of multipath techniques. [0028] It is to such a method and apparatus that the inventive concept disclosed herein is directed. BRIEF DESCRIPTION OF THE DRAWINGS [0029] As discussed above, the present disclosure describes methods and apparatus for transporting packets through a network which makes use of multipath techniques while retaining the order of the packets for traffic aggregates contained within larger traffic aggregates. [0030] Like reference numerals in the figures represent and refer to the same element or function. Implementations of the disclosure may be better understood when consideration is given to the following detailed description thereof. Such description makes reference to the annexed pictorial illustrations, schematics, graphs, drawings, and appendices. In the drawings: [0031] FIG. 1 is a diagram of an exemplary telecommunication network. [0032] FIG. 2 is a schematic diagram illustrating an exemplary protocol layering supporting traffic aggregates contained within larger traffic aggregates. [0033] FIG. 3 through FIG. 6 illustrate exemplary header encapsulations used by MPLS, IPv4, PW CW, and Ethernet respectively. [0034] FIG. 7 through FIG. 9 illustrate compositions of protocol headers used in accordance with the present disclosure. [0035] FIG. 7 illustrates exemplary MPLS label stack entries followed by an IPv4 header. [0036] FIG. 8 illustrates exemplary MPLS label stack entries of which a label stack entry is supporting an Ethernet PW payload without a pseudowire (PW) code word (CW). [0037] FIG. 9 illustrates exemplary MPLS label stack entries of which a label stack entry is supporting an Ethernet PW payload with a PW CW prior to the Ethernet PW payload. [0038] FIG. 10 illustrates a prior art logic flow within packet processing forwarding decision circuitry used in a network element in the absence of the inventive concept disclosed herein. [0039] FIG. 11 illustrates a logic flow similar to that in FIG. 10 , but having been modified to support the inventive concept disclosed herein. DETAILED DESCRIPTION Definitions [0040] If used throughout the description and the drawings, the following short terms have the following meanings unless otherwise stated: [0041] IEEE is an abbreviation for the Institute of Electrical and Electronic Engineers. [0042] IETF is an abbreviation for the Internet Engineering Task Force. [0043] RFC is an abbreviation for Request For Comment. IETF maintains a numbered series of documents known as the Request For Comment (RFC) series. Documents within the RFC series are assigned one of the following RFC classifications: historic, informational, experimental, best current practices, and standards track. [0044] A packet switched network delineates packets and makes use of information contained in the packets, usually in packet headers, to determine where to forward each packet. [0045] A circuit switched network requires that a connection or circuit be set up before any communication can begin and once set up a connection acts as an electrical circuit would, providing a fixed amount of capacity. [0046] Network capacity can be measured in bits per second. Common units are kilobits per second, abbreviated Kb/s (thousand bits per second), megabits per second, abbreviated Mb/s (million bits per second), gigabits per second, abbreviated Gb/s (billion bits per second), and terabits per second, abbreviated Tb/s (trillion bits per second). If the “b” is capitalized in the abbreviation the “B” stands for bytes where a byte is eight bits. [0047] A connection oriented network is a network which makes use of connection state to forward traffic. Circuit switched networks are connection oriented. Connection oriented networks also include packet switched networks which make use of connection state within a network to forward traffic, but generally allow a variable amount of capacity to be carried by a connection. [0048] A connectionless network is a type of packet switched network which does not rely on connection state within the network to forward traffic. For example, an Internet Protocol network is a connectionless network. [0049] Signal modulation is the method of transmitting electrical signals or optical signals such that bit levels can be determined by a receiver. A very simple modulation is a voltage differential on two wires. The amplitude, frequency, or phase of a carrier wave in an electrical signal may be modulated to indicate bit levels or patterns. The amplitude or phase of light may be modulated to indicate bit levels or patterns. Signal modulation occurs at among the lowest network layers, the physical layer. Where light of different frequency or polarization are multiplexed or switched optically there may be a lower layer that the signal modulation. [0050] A networking protocol is an agreement among parties regarding the interpretation of bit patterns. Data plane protocols, control plane protocols, and management plane protocols serve different purposes within a network. [0051] A data plane protocol makes use of information in packet headers to direct packets toward their destination and to guide other aspects of packet treatment within a network. Packet headers are followed by a packet payload which is uninterpreted data to be delivered to a destination. [0052] Control plane protocols are used by the network elements to coordinate the forwarding of data plane protocols such that packets reach their intended destination. Once enabled on a set of network elements, control protocols exchange information directly among network elements with no further outside intervention. Control plane protocols may or may not use the same data plane that is exchanging information. [0053] Management plane protocols are used by management systems to control or monitor network elements. Management systems may have some level of automation but also provide direct interface to human operators or indirect interfaces through database systems holding information about the network. Information in management system databases is generally at a higher level and often commercial in nature, such as customer information, customer attachment points, and services provided to customers. Management plane protocols may or may not use the same data plane that they are managing. [0054] A routing protocol is a type of control plane protocol which carries information about the reachable destinations and/or network topology. This information may be used directly to create forwarding entries for connectionless data plane protocols or may be used as input to guide the behavior of signaling protocols in connection oriented data plane protocols. [0055] A signaling protocol is a type of control plane protocol used to set up, maintain, and delete connections in connection oriented protocols. [0056] Routing information is the information stored as a result of routing protocol exchange. Routing information often includes a representation of the network topology relevant to the particular routing protocol. [0057] Packet encapsulation refers to the arrangement of bits dictated by a specific protocol. Protocols which define a packet header and packet payload further define the meaning of a set of bits or sets of bytes within the packet header, each set of bits or bytes known as a field in the packet header. [0058] A packet payload is uninterpreted data that is carried within a packet. The payload of one encapsulation may be a complete packet of another type of encapsulation. [0059] A packet header is part of a packet encapsulation which precedes the packet payload. The packet header may include information used to determine the type of packet payload being carried. [0060] A node in a network is said to “forward a packet” when it receives a packet on an interfaces, determines where to send the packet, and transmits the packet. Except in unusual circumstances a packet is transmitted to a different interface than the one on which it was received. In some protocols, packet headers may be modified when forwarding a packet. A node is said to be “forwarding traffic” when it is receiving many packets on one or more interfaces and is forwarding some or all of those packets. [0061] Forwarding state is the set of information stored in packet forwarding hardware such as non-transitive memory or other digital circuit which enables forwarding packets in the data plane based on information in the packet headers. [0062] An outer encapsulation may be added to the packet creating additional network layers of encapsulation. Protocols may also define information following the packet payload, most commonly a single field known as a frame check sequence or cyclic redundancy check (which can be considered to be a specific type of frame check sequence). [0063] An inner encapsulation exists where the packet payload of the outer encapsulation is not end system payload, but rather had already been encapsulated previously. [0064] A network layer refers to either a physical layer or an encapsulation layer or a control plane layer or a management plane layer. For example, from the standpoint of control and management MPLS may be a single layer but from the standpoint of the data plane each MPLS label stack entry can represent a network layer. [0065] A physical layer is one which directly modulates signals across a transmission media, such as electrical wires or optical fibers, or further multiplexes already modulated signals. [0066] A network link layer is an encapsulation layer immediately above the physical layer which provides the lowest layer identification of packet boundaries. [0067] A lower network layer or “inner encapsulation” is an encapsulation layer that is closer to the physical layer or physical layers with respect to some other encapsulation layer. Due to conflict with the MPLS notion of top of stack and bottom of stack, where “up” has the reverse sense, the term inner encapsulation is less ambiguous when referring to data plane encapsulations. [0068] An upper network layer is a further encapsulation layer away from the physical layer or layers relative to some other encapsulation layer or layers. Due to conflict with the MPLS notion of top of stack and bottom of stack, where “up” has the reverse sense, the term outer encapsulation is less ambiguous when referring to data plane encapsulations. [0069] A network topology is the physical or logical arrangement of active network elements and interconnections between network elements. A physical topology is the arrangement of physical network equipment and transmission media. A logical topology is the arrangement of active network elements and interconnections applicable to a specific protocol or set of protocols. A network topology is represented schematically with the type of diagrams used in the mathematics field of graph theory and similar terminology is used. [0070] A node in a network or network topology refers to an active network element in a network topology. This use of the term “node” matches the use of the same term in graph theory. [0071] A link in a network or network topology refers to an interconnection between nodes. The use of the term “link” in networking differs from graph theory terminology, where the term “edge” is used. [0072] An end system is a node whose sole purpose in the network is to make use of the exchange of information provided by the network and not to provide services for other nodes in the network. [0073] An edge node primarily serves to attach end systems to the network. The portion of the network topology that serves this purpose is collectively called the edge network or network edge. [0074] An aggregation node is considered part of the network edge and serves mostly to aggregate edge traffic within a region prior to delivery to the network core. [0075] A core node primarily serves to forward traffic between otherwise disjoint parts of the network edge. The portion of the network topology that serves this purpose is collectively called the core network. [0076] Ethernet refers to a set of standards defined by the IEEE. The Ethernet standards are contained within IEEE 802.1 and IEEE 802.3 standard series. [0077] IEEE 802 refers to a family of IEEE standards dealing with local area networks and metropolitan area networks. [0078] IEEE 802.11s a working group of the IEEE 802 project of the IEEE Standards Association. The primary focus of IEEE 802.11s the IEEE 802 architecture and bridging. [0079] IEEE 802.3 is a working group and a collection of IEEE standards produced by the working group defining the physical layer and data link layer's media access control (MAC) of wired Ethernet. [0080] IP is an abbreviation of Internet Protocol which is a protocol defined by IETF and used for communicating data across a packet-switched internetwork. The Internet Protocol Suite includes IP and others protocols, also commonly referred to as TCP/IP due to the widespread use of Transmission Control Protocol (TCP) with IP. [0081] IPv4 is an abbreviation of Internet Protocol Version 4. [0082] IPv6 is an abbreviation of Internet Protocol Version 6. [0083] CIDR is an abbreviation of Classless Interdomain Routing. CIDR is described in RFC 1466, RFC 1467, RFC 1481, RFC 1518, RFC 1519, RFC 4632 and other IETF RFC Series documents. [0084] Packet traffic or simply “traffic” refers to data in the form of packets that are transmitted through the network. [0085] A microflow is defined by the IETF as a single instance of an application-to-application flow of packets which is identified by source address, source port, destination address, destination port and protocol id. This definition is found in RFC 2475. [0086] Conversation is defined by the IEEE with a similar meaning given to the term microflow as defined in IETF. The IEEE defined a conversation to be a single instance of an application-to-application flow of packets but left it up to the implementation to determine how to identify such a flow. [0087] A traffic aggregate is a flow of traffic containing one or more microflows or smaller traffic aggregates. A traffic aggregate will generally contain very many microflows or smaller traffic aggregates. In many cases, today's networks carry millions of microflows within a single traffic aggregate. [0088] A traffic flow may be either a microflow or a traffic aggregate. [0089] End system traffic is traffic originated by an end system or terminated at an end system. [0090] End system payload is the payload of the innermost packet encapsulation, which is the original encapsulation sent by an end system prior to adding any further layers of outer encapsulation. [0091] Packet reordering refers to transmitting a set of packets in a different order than the order in which the packets were received. Packet reordering within a microflow is highly undesirable. Reasons are documented in RFC 2991. [0092] An ordered aggregate is a traffic aggregate which should be forwarded with little or no packet reordering if possible. IETF defines ordered aggregate in RFC 3260 using terminology in RFC 2475, however that definition would require defining “behavior aggregate”, “ordering constraint”, “Per Hop Behavior (PHB)”, and “PHB Scheduling Class (PSC)”, which are all terms that are not otherwise needed in this context. [0093] A multipath is a set of independent component links or component lower layer paths where traffic flows can be distributed over a set of components and where packet ordering can only be maintained for any traffic flows where all packets are sent on the same component. [0094] A lower layer path is functionally equivalent or near equivalent to the functionality of a link at a higher layer, but where data plane service is delivered transparently over a lower layer and may traverse multiple nodes at the lower layer. [0095] Inverse multiplexing is a technique where traffic can be distributed over a set of links and for which packet ordering can be maintained across the entire set of links. [0096] A composite link may be either a multipath or a set of inverse multiplexed links. [0097] A multipath component is one of the links or lower layer paths that make up a multipath. [0098] A component link is generally accepted as a synonym for multipath component. MPLS Link Bundling uses the term component link regardless as to whether the component is a link or lower layer path. [0099] A multipath technique is the protocol means by which a multipath is identified and managed. Examples are IP ECMP, Ethernet Link Aggregation, and MPLS Link Bundling. [0100] Multipath traffic distribution is the distribution of traffic flows across the component links of a multipath. [0101] A hash algorithm is a mathematical function which takes as input a value from a large number space which is sparsely populated and produces a much smaller set of bits than needed to represent an input value. The goal of a hash function is to spread the set of input values as evenly as possible over the output number space. [0102] A hash operation is a transformation performed according to a hash algorithm. [0103] IP Source and Destination Hash refers to the use of a hash of IP source address and IP destination addresses. The protocol number and UDP or TCP port numbers may also be used, but are generally not used in core networks. [0104] ECMP is an abbreviation of Equal Cost Multi-Path. ECMP is a multipath technique where routing information indicates that a set of paths through the network have equal cost, where cost is simply a name given to a metric used in the network protocol. ECMP will generally try to balance traffic evenly across all paths, or balance traffic proportionally to the capacity of the immediately adjacent links in each path. [0105] Link Aggregation is a multipath technique specific to Ethernet. Link aggregation is defined by IEEE 802.1AX-2008. [0106] LAG is an abbreviation of Link Aggregation Group. A LAG is one instance of the use of Ethernet Link Aggregation. [0107] A LAG member is a component link in the LAG. The use of the term “member” is unique to Ethernet Link Aggregation but is otherwise synonymous with “component” in more general discussion of multipath. [0108] MPLS is an abbreviation of Multi-Protocol Label Switching. MPLS is defined by many documents in the IETF RFC series, including but not limited to RFC 3032 and RFC 3209. [0109] LSP is an abbreviation of Label Switched Path. An LSP is a path through a network using Multi-Protocol Label Switching. An LSP is a form of network connection. Note that Label Switched Paths can be bidirectional or unidirectional. Please refer to RFC series IETF documents for further details. [0110] LSR is an abbreviation of Label Switching Router. An LSR is a node capable of handling MPLS data plane traffic and/or MPLS control plane information. [0111] An MPLS Label currently refers to the first 20 bits of a 32 bit Label Stack Entry (LSE) that is used to direct forwarding of MPLS traffic, although the details of the MPLS Label may change in future variations of the MPLS protocol. [0112] LSE is an abbreviation of Label Stack Entry. A label stack entry is currently a 32 bit entry in the MPLS encapsulation added to the packet header, known as the label stack. A label stack entry currently includes a 20 bit label field, a 3 bit traffic class (TC) field (formerly EXP), a one bit bottom of stack (S) field, and an 8 bit time-to-live (TTL) field although this may change in future variations. The current format is defined in RFC 3032. [0113] A Label Stack is the packet header for the MPLS protocol. A label stack consists of one or more Label Stack Entries (LSE). A first LSE is referred to as the top of the label stack. All LSE in the label stack currently have the S bit (bottom of stack) set to zero, except a last LSE which has the S bit set to one, although this could change in future variations. [0114] ILM is an abbreviation of Ingress Label Map. The ILM is a standard data structure used in the data plane for the MPLS protocol. The ILM is stored on a non-transitive memory or other non-transitive data structure holding a subset of the MPLS forwarding state. The ILM is described in RFC 3031. [0115] MPLS-TP is an abbreviation of Multiprotocol Label Switching-Transport Profile. MPLS-TP is a subset of MPLS intended to provide capabilities and management that is more similar to transport network operators than MPLS. Extensions of MPLS have been defined specifically for MPLS-TP, mostly in the area of operations and management; however MPLS-TP remains a subset or restricted usage of MPLS. [0116] OAM is an abbreviation of Operations and Management. OAM in MPLS and/or MPLS-TP refers to protocols which support measurement of performance, verification of connectivity, diagnostics, and data plane switching to protection capacity when indicated by working path connectivity checks. [0117] LM is an abbreviation of Loss Measurement. LM is a function of OAM. [0118] MPLS Link Bundling refers to a MPLS routing, control plane, and data plane technique which allows multiple links or paths between a pair of MPLS LSRs to be represented in a routing protocol as a single LSR adjacency. Any one link or path in the link bundle is referred to as a component of the link bundle. An LSP may be placed on a single component or may be spread out over multiple components. When traffic is spread out over multiple components, signaling reports that the “all ones” component is used, indicated by a binary component number containing all ones (a near impossibly large component number). [0119] MPLS Label Stack refers to a Label Stack configured in accordance with the MPLS protocol. [0120] PW is an abbreviation of Pseudowire. PW makes use of a label stack entry (LSE) in the packet that is used in providing an edge-to-edge emulated layer-2 service. One such encapsulation is Ethernet, in which case the PW provides an emulated Ethernet service. PW is defined by the IETF Pseudowire Edge-to-Edge Emulation (PWE3) working group (WG). [0121] SS-PW is an abbreviation of single-segment pseudowire. A single segment pseudowire consists of two end nodes (known as endpoints, and/or provider edges) and a single interconnection provided by a lower layer. Typically the lower layer supporting a PW is MPLS. [0122] MS-PW is an abbreviation of multi-segment pseudowire. A multi-segment pseudowire may have one or more intermediate nodes in addition to having two end nodes (known as endpoints and/or provider edges). The interconnection between the end nodes is provided by a lower layer, typically MPLS. [0123] T-PE is an abbreviation of terminating provider edge. A T-PE is an endpoint in either a SS-PW or a MS-PW. [0124] S-PE is an abbreviation of switching provider edge. A S-PE is an intermediate node in a MS-PW. [0125] PW CW or CW is an abbreviation of Pseudowire Control Word. A CW is currently a 32 bit encapsulation that immediately follows the label stack in a PW data plane encoding although the details of the CW may change in future variations. The CW indicates whether the packet payload using the MPLS protocol is a PW payload or PW OAM and also serves to insure that the PW payload is not mistaken for an IP payload if a multipath technique is configured to look for a potential IP payload after the MPLS label stack. [0126] Ethernet Pseudowire is a PW which carries an Ethernet payload. Ethernet PW is by far the most common type of PW. Ethernet PW is defined by RFC 4448. [0127] Network scalability refers to the ability of the network to scale, meaning to grow to a very large size. Some types of network protocols are unable to scale to a very large size and in particular to grow to a support a global network. Many network protocols which are capable of scaling well require that traffic be aggregated to reach their scaling potential. [0128] A telecommunications service provider (“provider”) is a business which operates the network for profit which may deliver services including telephony, circuit based services, virtual private networks, and computer networking services such as Internet service. Some terminology specific to telecommunications service providers has historical origins, accounting for the terminology differing from networking in general. [0129] A provider network is a network that is owned and/or operated by a telecommunications service provider. [0130] A customer site represents the point at which a customer of a telecommunications service provider attaches to the provider network. [0131] A metro node is a historical term used by telecommunications service providers in describing one or more nodes of the provider adjacent to customer sites or providing aggregation near customer sites. The term “metro node” is related to the term metropolitan area network which dates back to when a fiber optical ring around a metropolitan area was considered a network in of itself. [0132] COE is an abbreviation of Connection Oriented Ethernet. Ethernet Provider Bridging and Provider Backbone Bridging are forms of COE, both of which define a data plane but do not define a control plane. COE is commonly used by telecommunications service providers in newer metropolitan area portions of provider networks. [0133] RAM is an abbreviation of random access memory. RAM takes an address as input and returns the content of memory at that address. Currently, there are two general forms of RAM. SRAM (static RAM) is appropriate for small to medium memories on integrated circuits, including those containing custom or semi-custom digital circuits. DRAM (dynamic RAM) is generally used for large external memories. [0134] CAM is an abbreviation of content addressable memory. CAM, unless otherwise specified is assumed to be binary CAM. A CAM matches input against the contents of each entry in parallel and returns either an index or contents associated with the first entry matched. CAM is a common functional module in integrated circuits. [0135] TCAM is an abbreviation of ternary content addressable memory. Unlike binary CAM, TCAM matches against contents after applying a set of mask bits associated with each entry. Like CAM, TCAM returns either an index or contents associated with the first entry matched. TCAM is a common functional module in integrated circuits. [0136] A logic circuit, as used herein, may be any circuit that is sufficiently limited so as to not operate on a set of instructions. Exemplary logic circuits includes combinatorial logic and sequential logic. Combinatorial logic may make use of simple logical “and”, “or”, and “not” operations and may not be clocked. Sequential logic may be clocked and may implement a simple state machine. Further, sequential logic may make use of combinatorial logic. A CAM, TCAM, or memory are also examples of logic circuits. [0137] A processing device or processor may be, for example, as any circuit which operates on a set of instructions to implement an algorithm. A processing device or processor can be composed of digital circuits and may include an instruction pointer and one or more data pointers. The instruction set of a processor resides in non-transitory memory. In one example, the processing device or processor includes a circuit which qualifies as a Turing machine as defined by Alan Turing. [0138] Please refer to RFC series IETF documents for further details regarding IP, MPLS, LSP, LSR, MPLS labels, MPLS label stack entries, MPLS label stack, MPLS-TP, MPLS Link Bundling, MPLS-TP OAM, and PW. DISCUSSION [0139] One embodiment of the inventive concept disclosed is discussed herein in detail. The inventive concept is not limited in its application to the details of construction and the arrangement of the components or steps or methodologies set forth in the following description or illustrated in the drawings. The inventive concept disclosed herein is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting in any way. [0140] FIG. 1 illustrates an exemplary embodiment of a network 10 constructed in accordance with the present disclosure. The network 10 is an example of a telecommunications network with a specific topology and hierarchical design. The network 10 has a first edge network 12 , a second edge network 14 and a core network 16 , however it should be understood that the network 10 may be other types and have other network topologies. For example, the network 10 can be maintained within one or more data centers, and generally can be any type of network for which multipath is useful. [0141] FIG. 1 illustrates a logical topology of the network 10 . It should be understood that the network 10 is not limited to any particular topology. For the purpose of illustrating a usage of the inventive concept the network 10 , the core network 16 will be described as using the MPLS protocols within the core network 16 , using multipath within the core network 16 , using MPLS-TP within the first and second edge networks 12 and 14 , and not using multipath within the first and second edge networks 12 and 14 . The example examined in detail here is one where the core network 16 of the network 10 carries larger traffic aggregates within MPLS LSP which contain smaller MPLS-TP traffic aggregates, which in turn may contain still smaller traffic aggregates and/or may directly contain end system traffic. [0142] For purposes of example, the first edge network 12 includes nodes SF 1 , SF 2 , SF 3 , and SF 4 . The core network 16 includes nodes SC, DEN, CHI, CLE, HTF, LA, NM, STL, DAL, ATL and NJ. The second edge network 14 includes nodes NY 1 , NY 2 , NY 3 and NY 4 . The nodes SF 1 and NY 1 are end systems; the nodes SF 2 , SF 3 , SF 4 , NY 2 , NY 3 , and NY 4 are edge nodes; and the nodes SC, DEN, CHI, CLE, HTF, LA, NM, STL, DAL, ATL and NJ are core nodes. For purposes of this example, the nodes SF 3 , SF 4 , NY 3 and NY 4 may also be considered aggregation nodes which aggregate edge traffic prior to delivery to the core nodes of the core network 16 . [0143] FIG. 2 is a schematic illustration of traffic aggregates contained within larger traffic aggregates. In particular, FIG. 2 illustrates a single exemplary PW carried within an MPLS-TP traffic aggregate carried within a larger MPLS traffic aggregate. A very large number of PW may be carried within the network 10 . [0144] The purpose of FIG. 2 is to illustrate a set of protocols which may be used to deliver a traffic flow. In FIG. 2 , a vertical axis 24 represents relative layering. Not all layers are shown in FIG. 2 , only layers relevant to this discussion. For example, MPLS cannot be used as a link layer and therefore requires a link layer between MPLS and the physical layer. Ethernet in contrast can be used as a link layer or carried within another protocol, such as in an Ethernet PW. Shown in FIG. 2 is a physical layer 26 , a first encapsulation layer 28 , a second encapsulation layer 30 , and a third encapsulation layer 32 . In FIG. 2 , a line with a line beneath it indicates a layer contained within another layer. [0145] Layering may differ in the core network 16 and in each edge network 12 and 14 . For example, the third encapsulation layer 32 includes a PW layer 32 b at the top from node SF 2 to HTF and beyond. The second encapsulation layer 30 includes a region to region MPLS-TP LSP encapsulation layer 30 a from node SF 3 to node HTF and beyond. The first encapsulation layer 28 includes a core MPLS LSP 28 c , which is shown by the wide arrow from SC to HTF. The MPLS-TP LSP 30 a of the second encapsulation layer 30 is carried over this core MPLS LSP 28 c of the first encapsulation layer 28 . The third encapsulation layer 32 is carried within the second encapsulation layer 30 . Ultimately all of these encapsulation layers, i.e., the second and third encapsulation layers 28 , 30 and 32 are carried within the first encapsulation layer 28 and the physical layer 26 , which is drawn schematically along the bottom of FIG. 2 . [0146] It should be noted that the network 10 also includes a link layer which is not shown. In the example shown in FIG. 2 , the number of layers 28 , 30 and 32 can vary and change depending on the location within the network 10 . For example, the customer attachment 32 a may have only an Ethernet which could be drawn above the PW 32 b of the third encapsulation layer 32 . In the edge network 12 , the PW as drawn makes use of COE 28 a . In practice carrying a PW using COE may require using a GRE tunnel over IP over COE or using L2TP over IP over COE. The customer attachment 32 a , the COE in the edge network 28 a , and the optional region to core LSP 28 b are not relevant to the discussion except to provide a more complete example and to illustrate that network layering differs throughout the network 10 . The PW 32 b , inter-region MPLS-TP LSP 30 a , and core MPLS LSP 28 c are directly relevant to the discussion of an example usage of the claim. [0147] For the purpose of example the network 10 in FIG. 1 is assumed to be a subset of a telecommunications service provider network with a customer site in San Francisco and a customer site in New York. One potential path for the PW in FIG. 2 is the path from the node labeled SF 1 to the node labeled NY 1 in FIG. 1 , including nodes SF 1 to SF 2 to SF 3 to SC to DEN to CHI to CLE to HTF to NY 3 to NY 2 to NY 1 . This path is assumed to be bidirectional. [0148] FIG. 2 identifies one end system, i.e., the node SF 1 , and indicates that FIG. 2 is symmetric left to right, with the right side not completely drawn. The end system traffic is this case may be Ethernet. In FIG. 1 the end system traffic may be bidirectional Ethernet traffic from the node labeled SF 1 to the node labeled NY 1 . [0149] FIG. 2 indicates that a multi-segment PW (MS-PW) 32 b is used. The metropolitan area nodes (abbreviated “metro node” in FIG. 2 ) serve as the end points of the PW, are also known as terminating provider edge nodes (T-PE), in the PW in FIG. 2 . The PW terminating provider edge nodes (T-PE) in FIG. 1 would be SF 2 and NY 2 if the same set of protocols were used as are used in the PW 32 b in FIG. 2 . [0150] The PW 32 b in FIG. 2 intermediate nodes are known as signaling provider edge nodes (S-PE). In FIG. 2 , the S-PE function is provided by aggregation nodes. In FIG. 1 , the S-PE would likely be SF 3 and NY 3 . [0151] A lower layer is used to deliver PW traffic from a T-PE to an S-PE and from S-PE to S-PE. In FIG. 2 labeling near 28 a it is pointed out that either Connection Oriented Ethernet (COE) such as Ethernet Provider Bridging (PB) or an MPLS-TP LSP could be used to provide the underlying layer for the T-PE to S-PE traffic flow. This is illustrative of the potential to mix layer types. The T-PE to S-PE traffic flows in FIG. 1 would be from node SF 2 to node SF 3 and node NY 2 to node NY 3 . [0152] A lower layer is used to deliver PW traffic from one S-PE to an adjacent S-PE. In FIG. 2 , the MPLS-TP LSP 30 a , is used from the aggregation node, such as SF 3 in one region to an aggregation in another region (not shown in FIG. 2 , NY 3 in FIG. 1 ). In FIG. 1 this traffic flow from S-PE to S-PE would be carried within an MPLS-TP LSP from node SF 3 to node NY 3 . [0153] The traffic flow carried by MPLS-TP LSP 30 a in FIG. 2 may aggregate many PW and may carry IP traffic directly. The MPLS-TP LSP 30 a in FIG. 2 takes the same path as the S-PE to S-PE portion of the PW 32 b in FIG. 2 . For example, the service provider supporting the network 10 in FIG. 1 is very likely to have more than one customer with locations in San Francisco and New York. The MPLS-TP LSP ( 30 a in FIG. 2 ) from node SF 3 to node NY 3 is an example of a first traffic aggregate within a second larger traffic aggregate (MPLS LSP 28 c in FIG. 2 ) which requires that all traffic for the first traffic aggregate transmitted by one node remain in that same order when received by another node. [0154] For scaling reasons, a provider may chose to further aggregate traffic from a region to an adjacent core node. In FIG. 1 this would be from node SF 3 to node SC or from node NY 3 to node HTF. For example, many aggregated MPLS-TP traffic flows from node SF 3 may use the node labeled “SC” but terminate at many other nodes. In FIG. 2 this is labeled as an optional region to core LSP 28 b . The region to core link may also use multipath, though in FIG. 1 , this is not the case as illustrated for node SF 3 to node SC or node NY 3 to node HTF. [0155] In FIG. 2 , traffic from one core node, across the core network 16 , to a distant core node is aggregated using the first encapsulation layer 28 , which in this example is an MPLS LSP 28 c . In FIG. 1 this MPLS LSP would be from node SC to node HTF by way of the path using the node SC to node DEN to node CHI to node CLE to node HTF. In both FIG. 2 and FIG. 1 , this core to core path makes use of multipath at every section of the path (at each hop). This core to core LSP 28 c may carry a large number of MPLS-TP LSP and may also carry other traffic. [0156] The traffic flow carried by MPLS-TP LSP 30 a in FIG. 2 serves as an example of a traffic aggregate which requires that all packets within the traffic flow be forwarded in the order received whenever practical to do so. [0157] The MPLS LSP 28 c in FIG. 2 in addition to carrying the traffic flow carried by MPLS-TP LSP 30 a in FIG. 2 may aggregate zero or more additional MPLS-TP traffic flows, zero or more MPLS traffic flows, zero or more PW carried directly, and may carry IP traffic. The MPLS traffic flow illustrated in FIG. 2 serves as an example of a traffic aggregate for which strict ordering is not required over the traffic aggregate and for which one or more traffic aggregates is contained within it which requires that traffic in that contained traffic aggregate be forwarded in the order received whenever practical to do so. [0158] In FIGS. 3 , 4 , 5 , and 6 no payload is shown; only the packet headers are shown. FIG. 3 , FIG. 4 , FIG. 5 , and FIG. 6 illustrate the format of the encapsulation of an MPLS Label entry 40 , an IP header 42 (e.g., Version 4), a PW Control Word (CW) 44 , and an Ethernet header 46 . These illustrations are included for clarity and are based on the IETF RFC series document which define these protocols, RFC 3032 (updated by RFC5462), RFC 791 (updated by RFC 1349), RFC 4385, and IEEE 802.3 as modified by RFC 4448 for use as an Ethernet PW payload (Ethernet preamble and start byte omitted). [0159] FIG. 7 , FIG. 8 , and FIG. 9 illustrate common encapsulations of traffic within MPLS networks. The encapsulations illustrated in FIG. 7 , FIG. 8 , and FIG. 9 are composed of combinations of the encapsulations illustrated in FIG. 3 , FIG. 4 , FIG. 5 , and FIG. 6 . These types of encapsulation serve as examples for the purpose of illustration of both existing multipath techniques and illustration of the inventive concept. [0160] Shown in FIG. 7 is a set of packet headers 50 with a label stack 52 followed by the IP header 42 . The label stack 52 has three MPLS label entries 40 a , 40 b and 40 c [0161] FIG. 8 shows a set of packet headers 60 with a label stack 62 followed by the Ethernet header 46 . FIG. 9 shows a set of packet headers 70 with a label stack 72 followed by the PW Control Word (CW) 44 and the Ethernet header 46 . PW encapsulation makes use of an MPLS label stack entry. One of the label entries 40 a , 40 b , or 40 c in FIG. 8 and in FIG. 9 must carry a label number which has been configured for use as a PW or has been set up for use as a PW using a control plane protocol. [0162] Common practice in MPLS networks making use of multipath is to make use of all label entries 40 a , 40 b , and 40 c in the label stack 52 , 62 , 72 and make use of any potential IP header below the MPLS layer in the multipath load distribution. If packets are MPLS encapsulated, a bottom of the label stack 52 , 62 , 72 (which in this example is the label entry 40 c ) is located and the MPLS payload is assumed to be IPv4 if a 4 is found in the first four bits of the MPLS payload and the MPLS payload is assumed to be IPv6 if a 6 is found in the first four bits of the MPLS payload. [0163] In practice, IP and pseudo-wires are the only MPLS payloads found in most (if not all) MPLS networks. A pseudowire code word may be included in the packet, and if used prevents a PW payload from being accidentally interpreted as an IP packet carried as MPLS payload. If a potential IP header is not found, common practice is to use the label stack ( 62 or 72 in FIG. 8 and FIG. 9 ) in the hash, or at least as many label entries 40 near the bottom of the label stack 62 or 72 as practical are used. [0164] Note that in FIG. 8 , a value of 4 or 6 in the first four bits of the Ethernet Destination MAC (media access control) Address would cause the PW payload 46 in FIG. 8 to be mistakenly interpreted as an IP packet by nodes along the LSP path. This risk is noted in RFC 4385 and is the sole topic of RFC 4928. [0165] In the absence of the methods disclosed herein the use of multipath can and generally does degrade the full operations and management capabilities for the MPLS-TP traffic. The use of common multipath techniques can and often does spread aggregated traffic over links with slightly different effective delay, thereby causing potential reordering of traffic within those traffic aggregates. Traffic aggregates such as MPLS-TP require that reordering not occur if possible and this requirement is not met by common multipath techniques. Using the methods disclosed herein, multipath can be used and the reordering of traffic within traffic aggregates can be avoided. [0166] The primary purpose of aggregating traffic is often to improve scalability. More specifically aggregating traffic reduces the amount of routing information, and the amount of forwarding state, for example in the core network 16 of the network 10 . Since routing information changes, the nodes within the core network 16 need only focus on any large shifts in traffic flow made necessary by topology change in the core network 16 , such as a network fault. The nodes in the core network 16 need not be concerned with the much large number of small changes in the way traffic which is carried in the core network 16 is routed closer to the edges of the network 10 . [0167] Providing information on smaller traffic aggregates would defeat the primary purpose of aggregating traffic. This includes providing detailed information on which smaller traffic aggregates have requirements to maintain packet ordering and which do not. [0168] The claim covers a technique which is consistent with the scalability goals that are addressed by further aggregating traffic. Additional information, such as control plane information, can be provided only about the traffic aggregate, preferably with no additional information provided for each of the very large number of individual smaller traffic aggregates contained within the larger traffic aggregate. For example, the control plane information can be set up using RSVP-TE extensions. RSVP-TE is defined in RFC 3209 and in other documents in the RFC series. [0169] The additional information carried within the control plane exchange setting up the larger traffic aggregate is whether the large traffic aggregate itself requires that traffic remain in the order it is received and if not, if any traffic aggregate is contained where the contained traffic aggregate requires that traffic remain in the order it is received, and if so the depth of encapsulation of the first layer at which a traffic aggregate exists which requires that traffic remain in the order it is received. This yields three cases. [0170] If the larger traffic aggregate requires that traffic remain in the order it is received, then traffic can be handled in a conventional manner. Most multipath techniques, such as Ethernet Link Aggregation could not be used. MPLS Link bundling can be used, with the larger traffic aggregate placed on a single MPLS Link Bundle component link. [0171] If the larger traffic aggregate does not require that traffic remain in the order it is received, and the larger traffic aggregate does not contain any traffic aggregates that require that traffic remain in the order it is received, then traffic for the larger traffic aggregate can be handled in a conventional manner utilizing any of a number of existing multipath techniques. In this case, it is desirable to maintain packet order for microflows or conversations (IETF and IEEE terminology respectively) but not for contained traffic aggregates. [0172] The remaining case is where the larger traffic aggregate does not require that traffic remain in the order it is received, but the larger traffic aggregate contains one or more traffic aggregates that require that traffic remain in the order it is received. The information carried for the large traffic aggregate includes the smallest depth of encapsulation of any contained traffic flow or flows which require that traffic remain in the order it is received. [0173] The additional information carried for the large traffic aggregate may also include other information that is useful in constraining the load balance for a specific type of encapsulation. For example, for MPLS, whether it is safe to look past the MPLS label stack for a potential IP header, can be included. It is safe to do so when it is safe for all of the contained traffic aggregates. For example, it is safe to do so if all MPLS-TP LSP are containing only PW payloads and all PW are using PW CW. [0174] For this third case the inventive concept disclosed herein specifies a change to the way packets within the large traffic aggregate are forwarded. Information in the packet headers used as the basis for selecting a component link cannot be retrieved until after a forwarding lookup based on the larger traffic aggregate. A set of instructions is retrieved during the forwarding lookup. The set of instructions can be hash instructions 82 as set forth in FIG. 11 . However, it should be understood that other types of instructions for load balancing, whether hash based or not, can be used. [0175] These hash instructions 82 determine which packet header fields within the encapsulation may be used as a basis for selecting which component of the multipath on which to forward a specific packet. [0176] For example, for MPLS using a hash based algorithm, the hash instructions 82 include a limit on the label stack depth over which the hash may operate, and indicates whether to consider a potential IP header after the label stack 52 , 62 , or 72 , for example. [0177] Returning to FIG. 1 , traffic with the encapsulations illustrated in FIG. 7 , FIG. 8 , and FIG. 9 may be received at the node DEN from the node SC. A specific packet may be associated with the traffic carried within the MPLS LSP from SC to HTF. This is determined by looking at the label stack entry 40 a , which is the top or outermost entry. In current versions of MPLS, the label stack entry 40 a is the first 32 bits in the packet encapsulation transmitted from SC. The lookup based on the label stack entry 40 a makes use of a table (or other data structure) known as the ingress label map (ILM) 80 a in FIG. 10 or 80 b in FIG. 11 . [0178] Conventionally, the ILM 80 a would only indicate that the packet should be directed toward CHI and no constraints on the multipath load distribution method would be contained within the ILM 80 a . Using the inventive concept disclosed herein, additional information 82 is held in the ILM 80 b which guides the multipath load distribution. [0179] FIG. 10 provides a block diagram depicting an exemplary ILM 80 a lookup and load distribution 84 a and 86 a that is typical in the absence of the inventive concept disclosed herein. The load distribution in FIG. 10 is based on a hash algorithm, a very common multipath load distribution technique. [0180] It is desirable to implement many of the functional blocks illustrated in FIG. 10 in dedicated electronic circuitry for reasons of performance and efficiency. Typically this set of functional blocks is implemented as a portion of the functionality on a single integrated circuit, though some functions may be implemented in external circuitry. For example, the ILM may be implemented as an external memory or as an external specialized logic such as a binary content addressable memory (CAM) or ternary content addressable memory (TCAM) when the TCAM is used for other purposes. Processing functionality can be implemented using one or more processors, combinatorial logic, an Application Specific Integrated Circuit (ASIC) and combinations thereof. [0181] FIG. 11 provides a block diagram depicting an exemplary circuit with modifications to implement the inventive concept disclosed herein. A block 82 labeled “Hash Instructions” has been added. The hash instructions 82 determine which portions of the received packet headers are used by the load distribution method, a hash operation in this example. [0182] Existing packet processor designs can be modified to include the inventive concept disclosed herein. To do so requires the following changes. [0183] In the example, the hash instructions 82 comprise a set of information derived from the requirements to retain packet ordering for aggregates at some encapsulation layer. In the example, this information is held in the ILM 80 b , though it could be held in a separate data structure that is also indexed using the MPLS label. The derived information, the hash instructions 82 are available as an output to the ILM lookup in the example and are an input to the hash operation 84 b . The derived information held by a specific implementation would depend on the multipath load distribution technique being used, but are derived from the requirements to maintain traffic ordering of the traffic aggregate and the contained traffic aggregates as outlined previously. [0184] The load distribution is modified, but only in the packet header fields that can be applied to the load distribution algorithm. In the example, a hash operation is used in the load distribution. In FIG. 10 the inputs to the hash operation are received packet headers 90 and a hash seed 92 . In FIG. 11 the inputs to the hash operation are the packet headers 90 , a hash seed 92 , and the hash instructions 82 . In this example, the received packet headers 90 may be the packet headers 50 , 60 , and/or 70 . In FIG. 10 , in the absence of the inventive concept disclosed herein, any hash instructions 82 would be globally configured, and would be applied to all LSP. In FIG. 11 , with the inventive concept disclosed herein, the hash instructions 82 support an ability to limit encapsulation depth. As previously noted, hash instructions 82 are selected per containing LSP (top label stack entry) with the inventive concept disclosed herein, using the ILM 80 b as illustrated in FIG. 11 . [0185] Although only a few embodiments have been described in detail above, those of ordinary skill in the art will readily appreciate that many modifications are possible without materially departing from the teachings of the present disclosure. Accordingly, such modifications are intended to be included within the scope of the present disclosure as defined in the claims.
The method that is disclosed enables specific information network traffic flows to retain packet ordering in a packet network in which multipath techniques are used. In a common network usage a plurality of traffic flows may be aggregated into a larger traffic flow. In such a situation, a finest granularity of individual traffic flow is referred to as a microflow and an aggregation of traffic flows is referred to as a traffic aggregate. The traffic aggregate may take a path from an ordered set of nodes including a first network element referred to as an ingress node through zero or more intermediate network elements referred to as midpoint nodes, to a final network known as the egress node. The ordered set of nodes traversed by such a traffic aggregate is referred to as the path taken by that traffic flow. At any node prior to the egress, the traffic aggregate may be split among multiple links or lower layer paths in reaching the next node in the path. In such a circumstance, the traffic aggregate is split among the available links or lower layer paths. Techniques for splitting traffic are collectively referred to as multipath techniques, or more briefly as multipath. Individual links or lower layer paths within a multipath are referred to as component links. Individual traffic flows may be identified by various existing multipath techniques. A set of existing multipath techniques are able to keep all packets within a given microflow on the same component link. The method disclosed allows specific traffic aggregates within a larger traffic aggregate to be carried on a single component link while allowing other traffic aggregates within the larger traffic aggregate to be spread among multiple component links.
8
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation of U.S. patent application Ser. No. 13/611,696, filed on Sep. 12, 2012, which is related to and claims the benefit of U.S. Provisional Patent Application Ser. No. 61/533,574 filed on Sep. 12, 2011 and U.S. Provisional Patent Application Ser. No. 61/665,701 filed on Jun. 28, 2012, the entire contents of which are herein incorporated by reference. FIELD [0002] The disclosure relates generally to a bimini top, and more particularly to a stowable bimini top. BACKGROUND [0003] Stowing a bimini top for a tower structure that is associable with a watercraft can be difficult and inefficient from a standpoint of both a time and storage space. Accordingly, a need exists in the art for a bimini top that can be easily and efficiently stowed. SUMMARY [0004] Disclosed is a slide piece for a stowable bimini frame associable with a tower structure of a watercraft, the slide piece including a slide piece body portion, at least one frame association structure extending from the body portion, the at least one frame association structure being configured to slidingly associate the bimini frame with the slide piece body portion, and an affixing surface of the slide piece body portion, the affixing surface being positioned and configured for associating the slide piece body portion with the tower structure of the watercraft. [0005] Also disclosed is a stowable bimini frame associable with a tower structure of a watercraft, the bimini frame including a first frame portion, a second frame portion, a hinge associating the first portion and the second portion, the second portion being foldable in a direction of the first portion via rotation about the hinge, a slide piece in sliding association with the first frame portion via at least one frame association structure extending from the slide piece, and an affixing surface of the slide piece, the affixing surface being positioned and configured for associating the slide piece with the tower structure of the watercraft. [0006] Further disclosed is a bimini top system for a watercraft, the system including a tower structure extending the watercraft, a stowable frame including a first frame portion and a second frame portion a hinge associating the first portion and the second portion, the second portion being foldable in a direction of the first portion via rotation about the hinge, and a slide piece affixed to the tower structure and in sliding association with the first frame portion via at least one frame association structure extending from the slide piece, wherein the sliding association allows the stowable frame to be configured between an openable position extended relatively away from the tower structure and a stowable position disposed in relative proximity to the tower structure via a sliding of the stowable frame relative to the slide piece and the tower structure to which the slide piece is affixed. BRIEF DESCRIPTION OF THE FIGURES [0007] FIG. 1 is a perspective view of schematic bimini frame in an open position; [0008] FIG. 2 is a schematic partial and exploded view of a hinge and slide area of the frame shown in FIG. 1 , as well as a portion of a tower structure of a watercraft; [0009] FIGS. 3-9 are various partial and full perspective views of a bimini top shown in positions intermediate to the open position shown in FIG. 1 and a stowed position; [0010] FIG. 10 is a perspective view of a bimini in a stowed position; [0011] FIG. 11 is an enlarged end view of the slide piece shown in FIG. 1 as configured in a first, unlocked configuration; and [0012] FIG. 12 is an enlarged end view of the slide piece shown in FIG. 1 as configured in a second, locked configuration DETAILED DESCRIPTION [0013] FIG. 1 illustrates an exemplary embodiment of a bimini frame 10 that may fold and slide in a manner that allows a bimini top to be stowed against a tower/arch type structures mounted on any desirable style of watercraft (such as but not limited to a sport, ski, wakeboard, fishing, or other watercraft). As is best shown in FIG. 2 , the frame 10 includes a hinge 12 , slide piece 14 , and cam locking device 16 . These elements of the frame 10 allow the frame 10 to fold, slide, and lock in the manner alluded to above and discussed in greater detail below. Along with the frame 10 , these elements may be made of any desirable material, such as but not limited to various metals and hard plastics. The frame 10 and/or tower 20 are also typically equipped with a cover portion 17 (such as but not limited to canvas, plastic, etc.) stretching around and across the bars of the frame 10 and secured via affixing mechanisms such as but not limited to Velcro, snaps, and ties. [0014] As shown in the exemplary embodiment of FIG. 2 , the slide piece 14 includes a slide piece body portion 15 , which may be affixed to a handle 18 of a boat tower structure 20 at affixing surface 19 via any association means such as but not limited to mechanical fasteners 21 . In the exemplary embodiment of FIG. 2 , the body portion 15 is not directly affixed to the handle portion 18 , as spacer 23 is disposed between the affixable surfaces of the handle 18 and the slide piece 14 to create clearance therebetween. Of course, embodiments wherein the surface 19 is directly affixed to the handle 18 and embodiments wherein some or all of the handle 18 , slide piece 14 , and/or spacer 23 elements are of unitary construction with each other are also contemplated. [0015] As shown in FIG. 1 , the frame 10 includes a relatively front portion 22 and a relatively rear portion 30 . The front portion 22 of the frame 10 is associated with the slide piece 14 via frame association structures or slide parts 24 . These slide parts 24 may be affixed to the body 15 of the slide piece 14 via any association means such as but not limited to mechanical fasteners, welding, and unitary construction. In use, slide part portion of the piece 14 may be covered with a protective cover of similar material to the piece 14 . When in the open position shown in FIGS. 1 and 3 , the cams 16 are locked so as to prevent the front portion 22 (and frame 10 in general) from sliding relative to the slide piece 14 and the tower structure 20 to which the slide piece 14 is affixed. The front portion 22 and back portion 30 of the frame may also be locked in this open position at the hinge 12 . [0016] As is best shown in FIG. 4 , which illustrates an upper portion of a bimini top system 8 (including the frame 10 and a portion of the tower structure 20 mounted on a watercraft), the back portion 30 of the frame 10 may be moved towards a folded (and eventually stowed) position by folding the frame 10 at hinge 12 . This is achieved by disengaging rear legs 32 from the tower structure 20 and folding the back portion 30 of the frame 10 (which is fully locked against sliding in a forward position by the cams 16 ) upwards and onto the front portion 22 . As is best shown in FIGS. 5-7 , the front and back portions of the frame 10 may then be clipped together via clips 34 , and the back legs 32 may be stored under Velcro flaps. [0017] Referring now to FIGS. 8-10 , the fully folded frame 10 (which remains locked against sliding via cams 16 in FIG. 8 is positioned for sliding into the stowed position. This stowed position is shown in FIG. 10 , wherein the folded front and back portions of the frame 10 are slid backwards from the folded position of FIG. 9 to the stowed position. This sliding occurs by first unlocking the cams 16 , and then sliding the front portion 22 of the frame 20 backwards through the slide parts 24 . As the slide parts 24 are in a fixed position relative to the tower structure 20 (via the affixing of the slide piece 14 to the tower 20 ), the sliding of the front portion 22 moves the frame 10 backward relative to the tower structure 20 , and into the folded, slid, and stowed position shown in FIG. 10 . The cams 16 are then again locked to prevent the frame 10 from sliding out of the stowed position. [0018] Referring now to FIGS. 11 and 12 , an exemplary embodiment of the slide piece 14 and cam 16 is shown. In FIG. 11 the slide piece 14 and cam 16 are shown in an unlocked configuration. When in this unlocked configuration, a clearance is present between the front portion 22 of the frame and the innermost walls of the slide piece 14 . In an exemplary embodiment, this clearance is at least ⅜of an inch on either lateral side of the frame bar. [0019] In FIG. 12 the slide piece 14 and cam 16 are shown in a locked configuration. When in this locked configuration, the cam 16 is positioned in a manner that biases the frame bar towards and into contact with one of the walls (the wall away from slide piece connection with the handle 18 in the embodiment of FIG. 12 ), causing the bar to traverse and close the clearance that is present on one side of the bar when in the open position of FIG. 11 . The bias caused by the above discussed locking (or any other desirable locking mechanism) is designed to hold the frame 10 in position while traveling at any acceptable speeds of highway or water transportation. [0020] While the front and back portions of the frame 10 are shown to be “U” shaped in the exemplary embodiment of FIG. 1 , it should be appreciated that the frame may include any shape conducive to use with any known tower configuration. In addition, though the sliding of the frame 10 is shown to occur through the slide parts 24 in the exemplary embodiments of FIGS. 2-10 , it should be appreciated that this sliding may occur via any known mechanical mechanism, such as but not limited to telescoping portions and additional hinges. [0021] It should be noted that though portions 20 , 30 of the frame 10 are referred to as “front” and “back” respectively, these qualifiers are merely provided for descriptive purposes. In fact, the portions may be positioned in any desirable orientation relative to a front or back of a watercraft on which the frame is mounted. [0022] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein. [0023] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. [0024] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Disclosed is a slide piece for a stowable bimini frame associable with a tower structure of a watercraft, the slide piece including a slide piece body portion, at least one frame association structure extending from the body portion, the at least one frame association structure being configured to slidingly associate the bimini frame with the slide piece body portion, and an affixing surface of the slide piece body portion, the affixing surface being positioned and configured for associating the slide piece body portion with the tower structure of the watercraft.
5
GOVERNMENT INTEREST The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without payment to us of any royalty thereon. FIELD OF INVENTION In one aspect this invention relates to evaporation tubes. In a further aspect, this invention relates to heat exchange tubes useful in heating and cooling systems. Evaporation tubes and heat exchange mechanisms are well known in the art. One example of a heat exchanger is the well known automotive radiator where air passing over a series of fins is used to cool a recirculating liquid which provides cooling for an internal combustion engine. Another example of heat exchangers commonly used are the well-known air conditioning units wherein a high-pressure refrigerant is fed into an enclosed housing as a superheated vapor and the resulting vapor is condensed by means of a condenser heat exchanger exposed to ambient temperature air, the condensate being fed back through an orifice into a low-pressure evaporator heat exchanger chamber where it vaporizes and removes heat from an enclosed space thus maintaining the enclosed space at a temperature below the ambient environment. In military environments it is proposed to create microclimate cooling units which can be used by individual soldiers or groups of soldiers to cool small climate free from the dangers of the nuclear, biological and chemical compounds occasionally encountered in battle zones. Because such a unit would be carried by or used by a soldier who could be standing or lying in almost any orientation, the heat exchanger or evaporator used in such a unit must be capable of functioning in any orientation. Prior art units used on automobiles and air conditioning systems are designed to be permanently mounted in a fixed orientation and to function in that orientation. Such systems are not designed to be equally effective in any orientation. Other uses for an orientation-insensitive evaporator include cooling applications in space where there is no gravity or in aircraft where the g-forces can operate in a variety of directions. SUMMARY OF THE INVENTION A high-efficiency evaporator tube, according to this invention, which is suitable for functioning in any orientation, is formed having a first housing member with an inlet and an outlet. The outer surface of the housing is exposed to a fluid to be cooled and the inner surface of the housing is exposed to a refrigerant liquid suitable for cooling the housing and thereby the fluid in contact with the outer surface of the housing. A porous, liquid-wicking layer is disposed on and attached to the inner surface of the housing. The porous layer of this invention is adapted to wick the refrigerant liquid through the housing so that refrigerant liquid is dispersed and in contact with the fluid housing without regard to the orientation of the housing. Valve means are disposed between the inlet and the source of refrigerant liquid to control the refrigerant liquid flow into the housing. BRIEF DESCRIPTION OF DRAWING In the accompanying drawing: FIG. 1 is end view of one an embodiment made according to this invention; FIG. 2 is a side view, in section of a second embodiment of this invention with a control mechanism; FIG. 3 shows various evaporator structures which have been experimentally tested; and FIG. 4 shows heat transfer results for the evaporators shown in FIG. 3. DETAILED DESCRIPTION OF THE INVENTION Referring to the accompanying drawing in which like numerals are used to designate like parts, an end view of a evaporation tube according to this invention is shown in section. The basic evaporator includes a housing 10 which is shown as a circular cross section having a circular wall 12 and a plurality of radially extending fins 14 extending outward from the outer surface 16 of the housing. A porous wicking layer 18 is disposed in the interior of the circular housing 12 and has intimate contact with the inner surface 20 of the circular housing 12. The porous wicking layer will provide nucleation sites for bubble formation and provide a larger interior surface area for heat transfer. Both these characteristics increase the heat which can be transferred. The porous wicking layer 18 is shown formed with a plurality of longitudinal arteries 22 which allow the refrigerant liquid to flow freely longitudinally through the porous wicking layer by capillary action to the inner surface of the circular housing 12 when the liquid reaches a point in the evaporator remote from the inlet. As shown in FIG. 1, the cooling fins 14 can be surrounded by a second retention housing 26 defining an enclosed space between the outer surface 16 of the housing and the inner surface of the retention housing. The use of the retention housing is particularly desirable where it is necessary to recycle the fluid being cooled rapidly and efficiently within a small area or where the fluid being cooled is a liquid and it is necessary to hold the liquid in place. FIG. 2 shows an embodiment without a retention housing but having a control mechanism suitable for adjusting the flow of refrigerant liquid through the evaporator. The evaporator housing 12 has an inlet with a plate 28 having a plurality of openings 30 communicating with and corresponding in number and orientation with arteries 22 in the porous wicking layer 18. The openings 30 allow the liquid refrigerant to pass through and into the porous medium and run longitudinally along the evaporator 16. As shown, the longitudinal arteries 22 are closed at the end distal the inlet but they could be open if so desired. If the arteries 22 are closed the liquid would be unable to flow freely through the refrigerant tube and would be forced to exit through the porous structure when it hits the end of the artery. The evaporator in FIGS. 1 and 2 would normally be connected to a compression system in a manner well known in the air conditioning or fluid treating art. Such compression systems deliver a liquid refrigerant into an inlet chamber 34 and the resulting liquid would be transformed by a phase change into a low-pressure vapor which would exit the housing through an outlet 36 formed in the end wall 38 of the evaporator. The low-pressure vapor would be recycled into the compressor for recompression and use. An entire system would comprise an evaporator, condenser, compressor, and various connecting and valving mechanisms to maintain and control refrigerant flow. The basic compressor and valving structures are well known in the art and design of cooling systems. A detailed description of the compressor, condenser, and the associated fluid connections necessary to use the evaporator of this invention is omitted in the interest of brevity. FIG. 2 shows a controlling mechanism useful for regulating the amount of liquid refrigerant which enters the evaporator. Control of the liquid refrigerant is desirable so when the wick is covered with liquid refrigerant, the refrigerant vapors should be at the saturation temperature which corresponds to the pressure in the evaporator tube. When the wick is dry, the vapors would contact the warm wall of the evaporator and become superheated. It is desirable to regulate the superheat in the evaporator since too much superheat would penalize the efficiency of the refrigeration circuit and too little superheat risks flooding the evaporator with liquid refrigerant. If the evaporator becomes flooded, the liquid could enter the compressor causing damage. As shown in FIG. 2 regulation of the amount of superheat can be regulated by means of a thermal expansion valve designated generally 40 which comprises a bulb 42 filled with a liquid 44. As the liquid 44 is exposed to the increasing temperature from gas flow through the evaporator to the outlet 36, the increasing temperature on the liquid will cause an increase in the vapor pressure above the liquid causing the pressure in line 46 to rise as a function of temperature. A reference pressure is provided by reference line 48 which has one end 50 opening into the evaporator 10 and a second end 52 opening into a diaphragm housing 54. The diaphragm housing 54 has a flexible diaphragm 56 disposed across the diaphragm housing dividing the diaphragm housing into two chambers a activation chamber 58 and a reference chamber 60. The pressure in the reference chamber 60 will be maintained at the same interior pressure as the evaporator housing 12. As the superheat of the refrigerant being exhausted increases, the temperature of the bulb 40 will rise. Because the activation chamber 58 is fluidly connected to the temperature bulb 42, the pressure in line 46 rises as a function of temperature causing an increase in pressure in chamber 58 which will move the diaphragm 56 downward as shown in the drawing. The downward pressure will overcome the force of a biasing means 62 shown as a coil spring wrapped about a valve stem 64. As shown, the valve designate generally as 66 has a head 68 located within the inlet chamber 34 and adapted to seat against a shaped valve seat 70 to provide a fluid-tight seal. Both the valve and the valve seat are shown as frusto conical sections although other valve head configurations and seating configurations are known in the art and other valve seating configurations are possible. During operation as the temperature of the refrigerant in the gaseous phase exiting the evaporator raises the pressure of the bulb 42, the diaphragm moves against the biasing means and the valve opens allowing additional liquid refrigerant into the system. As the temperature of the refrigerant exiting the evaporator slowly decreases, the pressure in line 46 will correspondingly decrease and the biasing means will move the diaphragm into the housing allowing the valve to slowly close until a steady-state configuration is achieved. Because the wicking layer 18 is porous, the surface tension inherent in liquids will allow the liquid to flow and wick along the interior of the housing wetting the interior of the housing and allowing the conversion to the vapor state which promotes cooling. As soon as the refrigerant liquid charged at the inlet 24 has turned to a vapor it is free to pass through the porous wick into the center of the housing and exhaust through the outlet 36. Because the wick can carry the refrigerant longitudinally and radially within the housing to the inner surface of 20 of the housing 12, the interior surface of the housing will be maintained in a damp condition at all times allowing the maximum cooling effect without regard to the orientation of the evaporator. If the porous wicking layer 18 were not present in the evaporator tube, the interior of the housing would not be maintained damp with refrigerant throughout its length unless the housing was filled with refrigerant. This is not practical in all devices and it is often desirable to have the refrigerant enter the evaporator as a liquid and exit solely as a gas. This is particularly true in portable applications such as might be used in the micro-atmospheric suits and micro climate structures proposed for battlefields exposed to chemical, biological and nuclear contamination. With respect to producing evaporators of the invention, the evaporator housing, fins, porous wick and related lines and connections would generally be of a metallic nature to provide a substance which would allow easy heat flow from the refrigerant liquid to the fluid being cooled. In producing such a device the metal housing can have the fins 14 attached to its exterior surface by welding, braizing, or where the fins are longitudinally disposed as shown in FIG. 1 by extrusion. The preferred embodiment will have the exterior fins or spines lifted from the parent material of the housing 12 to provide extra heat transfer area and also increased turbulence in the fluid flowing over the exterior surface of the evaporator. Both the increased surface and the increased turbulence augment the heat transfer of the invention. Other augmentation methods which would provide increased surface area and turbulence are known in the art and could be used with the evaporator of this invention. To form the interior wicking surface where the housing and the wick are to be made of a metal material, the housing could be placed in a fixture and a mandrel placed inside the housing having a shape of the final void volume. The housing can then be filled with a powdered metal material and heated to a temperature where the metal powder begins to sinter but prior to the point at which substantial melting occurs. The resulting assembly can then be cooled and the mandrels removed to provide the final void spaces. U.S. Pat. No. 4,196,504 discloses a method of forming a porous structure having arteries inside of a tubular structure; the disclosure of this patent with respect to methods for forming porous structures and types of structures which can be formed are incorporated herein by reference. A number of evaporator geometries which have been experimentally tested are shown in FIG. 3. The evaporators were constructed as 12 inch lengths of 3/8 in diameter high thermal conductivity 102 copper. The outer surface of the housing had spines which were lifted from the parent material into various configurations; the spines were formed so the diameter of the spines was about 1.5 inches. The interior space had a porous wick formed of sintered copper powder which was manufactured by Alcan or Amax. The heat transferred for an evaporator which is 12 inches long is shown in FIG. 4. The various spined and unspined evaporators were placed in a 1 inch ID acrylic jacket 26 fitted with nipples at opposite ends. The tubes 10 were smaller than the spines so the tips were bent to allow the spines to fit aside the jacket. The jacket arrangement allowed a counterflow of water between the jacket and the evaporator housing. A compressor-condenser system was attached to the evaporators and pure dichlorotetrafluroethane used as the refrigerant. Water pumped through the jacket had its inlet and outlet temperature monitored and the flow rate was measured. This data could be used to calculate the heat transfer of the evaporator. A conventional evaporator which has neither spines nor a sintered metal interior is designated " Evaporator 9" to provide a base line evaporator. "Evaporator 8" has only a sintered metal interior. It removes 1.5-2 times more heat than the conventional evaporator. "Evaporator 7" has only spines. It removes twice as much heat as the conventional evaporator. "Evaporators 1-6" have both spines and a sintered metal interior. These evaporators remove 8-10 times more heat than the conventional evaporator at a given waterflow. Thus, it is seen that there is synergism between the spines on the exterior and sintered metal interior; that is, the total effect is greater than the sum of the individual effects. This results because the inside heat transfer coefficient depends on the amount of heat transferred. The exterior spines increase the amount of heat that is transferred and hence increase the interior heat transfer coefficient. In essence, the more heat that is transferred, the more heat that can be transferred. In summary, from the FIG. 4, it can be clearly seen that either fins geometry 7 or an internal wick geometry 8 individually provide slightly better heat transfer than a normal bare wall. In contrast even the least efficient evaporator structure with both fins and a porous wicking layer has a markedly better heat transfer rate. With respect to spine orientation, it appears that spines which are spiral oriented against the flow provide better heat transfer probably by increasing turbulence. For certain specialized applications, it may be desirable to have the evaporator made from material with increased resistance to certain chemical environments but with a penalty of a slightly lower thermal conductivity. Such a system might have a glass tube housing with spherical glass beads held to the interior by means of a chemical binder. One example of particulate material coated with a non-tacky, powdered thermal setting resin is disclosed in U.S. Pat. No. 3,175,935. Such free flowing resin coated beads can be poured into a suitable housing around the desired mandrel to form the desired wicking material and the body then heated to cure the resin in situ within the housing. Heating will cause the contiguous beads to become bounded together and then cured in a thermal set resin matrix forming a solid, consolidated composite porous body suitable for wicking a fluid material to the surface of the evaporation tube. Such beads being spherical in nature are easily handled and can form a highly uniform porous material suitable for use as a wick. Such beads in the appropriate resin can be chosen to be chemically inert to the desired chemicals passed through the evaporator if chemical resistance is an important aspect of the evaporator. Alternatively, glass or plastic beads without a chemical binder could be sintered in a manner analagous to the metal powder. It is believed that the metallic housing and sintered metallic liner will be the most common application in battlefield conditions where the evaporator tube will be exposed to severe shock. We wish it to be understood that we do not desire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art, without departing from the spirit and scope of the appended claims.
A high efficiency evaporator is disclosed. The evaporator is made with a ous wick on the interior of the evaporator housing to facilitate movement of a refrigerant liquid within the housing. This aids in dispersing the refrigerant.
5
CROSS REFERENCE TO RELATED APPLICATIONS This application is a National Stage of International Application No. PCT/CH2011/000023, filed on Feb. 10, 2011, which claims priority from Swiss Patent Application No. 00331/10, filed on Mar. 10, 2010, the contents of all of which are incorporated herein by reference in their entirety. TECHNICAL FIELD The present invention relates to a filling device for filling an applicator with at least one fluid. More particularly the invention relates to a modular filling device which, depending on the requirements, allows an applicator to be filled from various types of containers. In accordance with a further aspect, the present invention relates to a set of at least one applicator holder and several container holders, wherein the container holders are designed to hold different types of container. PRIOR ART In various applications a mixture of two or more flowable components has to be produced and discharged at a predetermined mixing ratio. One example is the production of an adhesive for technical or medical applications, e.g. a fibrin-based medical adhesive. Another example is the production of a bone cement from several components using a monomer. There are also medicinal products which are produced by mixing two or more components but which cannot be stored in the mixed state. In this case it is desirable to initially store the components separately and only mix them immediately before their administration. Similar tasks also arise in the case of other pharmaceutical or chemical systems of two or more components which are not stable in the mixed state. From the prior art it is known to hold the components to be mixed in two reservoirs of an applicator, e.g. in the form of a double syringe, and to discharge them through a suitable mixing device. However, it is often problematical to store flowable substances in plastic applicators over a longer period of time, as on the one hand the substances can chemically react with the plastic, and on the other hand there is a risk that gases, more particularly oxygen in the air, can diffuse through the walls of the applicator and chemically modify the contents. This applies in particular to applications in the field of medicine where chemical purity is of special importance. It is therefore known to store the components to be mixed separately in vials, more particularly glass vials with a septum seal, i.e. in sterilisable glass bottles which are sealed at one end with a self-sealing membrane (known as a septum) that can be punctured in order to remove the components to be mixed from the vials into two separate reservoirs only shortly before application. For this, adapter-like devices are proposed in the prior art which enable the simultaneous filling of two reservoirs from two vials, e.g. the filling devices disclosed in U.S. Pat. No. 6,610,033, U.S. Pat. No. 6,488,650. WO 2009/144085 also discloses a filling device of this type. Here, two vial holders for one vial each are connected with an applicator holder. An applicator can be inserted into the applicator holder along a fastening direction and can be connected to the applicator holder with Luer connections. The vial holders can be pushed or screwed into the container holders from the opposite side. The applicator can be filled from the vials through fluid connections in the applicator holder. This filling device only allows filling from vials, but not from other types of container. However, instead of in vials such components can also be held in other containers, e.g. in glass ampoules, i.e. hermetically sealed glass vessels which have to be broken open to remove their containers, or in tubes with a deformable wall area. It is also conceivable to store one of the components in a syringe, as long as the component in question is not too sensitive to ambient influences, and to only take them up in the actual applicator shortly before they are used. SUMMARY OF THE INVENTION In accordance with a first aspect the present invention provides a filling device allowing at least one reservoir of an applicator to be filled with a fluid from a container, wherein the device can be adapted to different types of container without essential changes to the design. A filling device for filling at least one reservoir of an applicator with a fluid from at least a first container is provided, the filling device comprising: a first container holder with a first holding area, which is designed to hold a first container on the first container holder, wherein the first container holder has a first outlet opening and a fluid channel between the first holding area and the first outlet opening in order to remove a first fluid from the first container through the first outlet opening; and an applicator holder with a fastening area which is designed to detachably fasten an applicator along a fastening direction onto the applicator holder, and wherein the applicator holder has a first inlet opening and a first fluid connection between the first inlet opening and the fastening area in order to take up the first fluid through the first inlet opening into a first reservoir of the applicator; and wherein the first container holder is configured to be connected to the applicator holder along a first connection direction in such a way that the first outlet opening and the first inlet opening are in communication with each other. In order to facilitate the container holders being able to be designed for very different types of container, e.g. for vials, tubes, syringes, ampoules etc., the first connection direction runs transversely (angled at an angle of more than 45°, preferably more than 60°, particularly preferably essentially perpendicular) to the fastening direction for the applicator. Seen from the applicator the container holder is thus laterally connected to the applicator holder. Preferably the applicator can be connected to the applicator holder along the fastening direction by means of a simple pushing movement, e.g. via a plug connection. More particularly the applicator can preferably be pushed onto or into the applicator holder. However, for fastening the applicator can carry out a more complex form of movement, e.g. combined pushing and turning, like in a bayonet fitting for example. The translatory part of the movement then defines the fastening direction. The connection of the applicator to the applicator holder is releasable in order to be able to separate the applicator from the applicator holder after filling and to discharge the fluid taken up in the applicator, e.g. by way of an accessory component that is configured to be attached to the applicator, such as a spray nozzle, a mixer etc. The first container holder is preferably also connectable to the applicator holder by means of a simple pushing movement in the first connection direction. Here too it is preferable that the first container holder is configured to be pushed onto or into the applicator holder. However, in this case as well a more complex movement can be envisaged for fastening, the translatory part of which then defines the first connection direction. The connection between the container holder and applicator holder can be detachable or non-detachable (without destruction). In the connected state the container holder and applicator holder preferably form an essentially rigid unit. There is therefore no flexible tube connection or suchlike between the container holder and the applicator holder which would make handling more difficult. Naturally the term “rigid unit” does not rule out the container holder or the applicator holder themselves having movable, even flexible parts, e.g. for opening the container. The term “rigid unit” should only indicate that the container holder and applicator are in a defined orientation relative to each other. The first container holder is in turn designed in such a way that the first container can be applied to the first container holder along a container guide direction which is transverse to the first connection direction and runs essentially anti-parallel to the fastening direction for the applicator when the applicator holder and the first container holder are connected to each other. After connecting the applicator holder to the container holder the filling device is thus preferably handled in the manner familiar to the user, in that the container is applied, e.g. pushed in, pushed onto, screwed in etc. to the filling device in the opposite direction to the applicator. The container can of course already be pre-mounted on the container holder so that for filling the applicator only the entire unit comprising the container holder and container has to be pushed onto the applicator holder. The container held on the first container holder can be, for example, a syringe with a syringe body with a movable plunger provided therein, a tube with a rigid distal connection area, e.g. in the form of a connecting piece with an external thread and a flexible side wall area, a vial with a closure that can be punctured, more particularly a glass vial with a septum seal, or an ampoule, e.g. a conventional glass ampoule with an ampoule body, tapered neck and ampoule tip that can be broken off. Other types of container are also conceivable, e.g. glass bottles with a screw connection etc. Depending on the container the container holder is designed accordingly. The envisaged purpose of use therefore implicitly also defines the structural design of the container holder within broad limits. Specifically the applicator holder can, in particular, be designed as follows: the applicator holder comprises a basic body with an upper side and an underside. The fastening area is arranged on the underside of the basic body and can in particular be produced in one piece with the basic body. The first fluid connection has a first inlet section extending from the inlet opening in the basic body essentially along the connection direction, and connected thereto a first outlet section leading to the fastening area, wherein the first outlet section runs at an angle to the first inlet section and extends in the direction of the underside. Preferably the first outlet section essentially extends perpendicularly to the first inlet section and, particularly preferably, runs essentially in the fastening direction. The basic body is preferably an essentially flat structure, from the underside of which the fastening area projects. Preferably the basic body is of a length in the first connection direction which is at least three times its thickness in the fastening direction. The width perpendicular to these two directions is preferably at least double the height. A basic body of this type allows a compact design. However, other forms of the basic body are of course also possible. The first container holder can preferably be pushed onto the basic body in the first connection direction in order to connect the first inlet opening with the first outlet opening so that in the mounted position the container holder at least partially surrounds the basic body. It can, however, also be pushed into the basic body for example. In order to assure a secure and simple fluid connection, the first basic body can at the end of the first inlet section have a first inlet connection piece extending in the first connection direction and forming the first inlet opening. This can then be pushed into the first outlet opening of the first container holder in a first connection direction, wherein the outlet opening in this case is designed to complement the inlet connection piece. In order to assure a seal between the first container holder and the applicator holder an O-ring can be pushed onto the inlet connection piece. Other sealing connections are of course also possible, such as tapered connections. In order to improve guiding of the container holder on the applicator holder and/or to establish a fixed orientation of the container holder relative to the applicator holder, the basic body can comprise at least one first guide element, e.g. in the form of an elongated lug or a peg, located at a distance from the first inlet connection piece and extending essentially parallel to the first inlet connection piece. A preferably complementary, hollow connection section of the first container holder can then be pushed onto the guide element. In this way the first container holder can be connected with the applicator holder in a defined orientation and is secured against twisting with regard to the applicator holder. Preferably two such guide elements are arranged on opposite sides of the inlet connection piece and engage accordingly in two hollow connection sections of the container holder. In order to fasten the applicator in the fastening area of the applicator holder, the fastening area can have a holding element, e.g. in the form of a ring, into which a distal end area of the applicator can be pushed and on which a catch structure, e.g. an engaging window, is formed in order to enter into a releasable snap-type connection with a corresponding catch element of the applicator, e.g. an engaging lug. Other types of fastening are of course conceivable, e.g. a normal Luer connection with or without a locking nut. While the invention also relates to a device for filling an applicator with just one reservoir, the filling device is preferably a device for filling an applicator with two or more parallel reservoirs, e.g. a double or multiple syringe, a cartridge with two or more reservoirs, two detachably connected single syringes etc. In this case the filling device can comprise (at least) a second container holder with a second holding area which is designed to hold a second container on the second container holder. The second container holder then in turn has a second outlet opening and a fluid channel between the second holding area and the first outlet opening in order to remove a second fluid from the second container. Accordingly the applicator holder then also has a second inlet opening and a second fluid connection between the second inlet opening and the fastening area in order to take up the second fluid through the second inlet opening into a second reservoir of the applicator. The second container holder can then be connected with the applicator holder along a second connection direction in such a way that the second outlet opening and the second inlet opening are in communication with each other in order to bring about a connection from the second holding area to the fastening area. The second connection direction is also transverse to the fastening direction for the applicator, preferably in a plane vertical to the fastening direction, particularly preferably antiparallel to the first connection direction. In the above specific embodiment with a basic body with an upper and underside and a fastening area arranged on the underside, the second fluid connection has a second inlet section essentially extending in the basic body along the second connection direction from the second inlet opening, and connected thereto a second outlet section leading to the fastening area, and the second outlet section runs at an angle to the second inlet section and extends in the direction of the underside. Preferably the first and the second outlet section run essentially parallel to each other and along the fastening direction. The first and the second inlet section preferably lie in a common plane and particularly preferably are collinear to each other, i.e. they are on the same imaginary straight line and point in opposite directions. In preferred specific embodiments the two container holders can each be pushed onto the applicator holder in order to connect the relevant inlet opening with the relevant outlet opening so that each of the container holders at least partially surrounds the applicator holder. Complementary connection elements can then be formed on the first and second container holder in order to connect the first and second container holder to each other in the mounted state. More particularly this can involve catch elements for a snap-type connection. Therefore, instead of, or in addition, to fixing the container holders on the applicator holder, in this embodiment the two container holders are fixed to each other and are therefore additionally held on the applicator holder. Especially if the second connection direction runs antiparallel to the first connection direction, the first and the second container holder can each have at least one catch element, which in the mounted state engages in the other container holder, more particularly can be moved into a hollow space thereof, bringing about a snap-type connection between the first and second container holder. Preferably the catch element of the second container holder is then arranged on a side of the applicator holder opposite the catch element of the first container holder. In a particularly compact and elegant embodiment, in the mounted state the first and second container completely cover the applicator holder towards a side facing away from the fastening area. In accordance with a further aspect, the present invention provides a modular filling system which allows an applicator to be filled as required from different types of container. Such a filling system comprises an applicator holder of the above-described type and two, three or more container holders designed for holding different types of containers. As indicated above, the container holders can already be pre-fitted with suitable containers. In other words the present invention provides a set, comprising a filling device of the above type and at least one further container holder, wherein the further container holder is designed for holding a different type of container from the first and/or second container holder. The set can also comprise a suitable applicator. BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the invention are described below with the aid of the drawings, which are only for explanation purposes and must not be interpreted as being limiting. In the drawings: FIG. 1 shows a perspective view of the filling system; FIG. 2 shows the filling system in FIG. 1 in a central longitudinal section; FIG. 3 shows a side view of a filling device in accordance with the invention; FIG. 4 shows a perspective view of the filling device of FIG. 3 ; FIG. 5 shows a partial view of an enlarged cross-sectional view of the applicator holder of FIG. 2 with the applicator attached thereto; and FIG. 6 shows a cross-section through the filling device of FIG. 3 in plane VI-VI. DESCRIPTION OF PREFERRED EMBODIMENTS In FIGS. 1 and 2 a first exemplary embodiment of a filling system in accordance with the invention is illustrated. Here the system consists of an applicator 100 , an applicator holder 200 , a first container unit 300 , a second container unit 400 , a third container unit 500 and a fourth container unit 600 . The applicator 100 is designed as a double syringe. It has an applicator body 110 with two cylindrical, parallel, proximally open reservoirs 111 , 112 of the same or (in this case) different diameter and volume. At their distal ends the reservoirs open into two outlets 116 , 117 ( FIG. 5 ). A plunger 121 , 122 is inserted into each proximal open end of the reservoirs. The two plungers are connected to each other at their proximal ends to form one plunger unit. In this area there is an activation surface 123 for the thumb of a user. A holding flange 113 is for holding the applicator by means of the index and middle finger. To this extent the applicator can be used like a commercially available double syringe. The applicator holder 200 has a basic body 210 of an elongated, flat, essentially disk-shaped basic form, on the underside of which there is a fastening area 220 for the applicator 100 . The structure of the basic body 210 is best recognised from FIGS. 5 and 6 . The basic body 210 has two cylindrical inlet connection pieces 211 which are arranged opposite to each other collinearly on a common longitudinal axis of the basic body. Each of the inlet connection pieces has an axial hole, the open end of which forms an inlet opening 216 and which defines a first inlet section 214 of a fluid connection. The two inlet sections 214 therefore also run collinearly to each other. Each of the inlet sections 214 opens into an outlet section 215 , which runs perpendicularly to the inlet section 214 , the two outlet sections 215 running parallel to each other downwards and opening into the fastening area 220 . Parallel to each of the inlet connections 211 , on two sides of each inlet connection there are two guide elements in the form of guide pegs 213 , the free ends of which are angled outwards. The guide pegs project axially well beyond the inlet connection 211 . An O-ring 230 can be pushed onto each of the inlet connections 211 and in the mounted state is in sealing contact with a circumferential shoulder 212 . The fastening area 220 is designed as follows: each of the outlet sections 215 opens into a conically widening insertion area for the outlets 116 , 117 of the applicator 100 . The outlets 116 , 117 complement the insertion areas and can be inserted into these insertion areas. In order to hold the applicator 100 securely on the applicator holder 200 , close to its distal end, adjacent to the outlets 116 , 117 , the applicator has two webs with engaging lugs 115 on two opposite sides ( FIG. 5 ). The fastening area 220 comprises a cylindrical receiving element 221 which radially surrounds the insertion area and the webs with the engaging lugs 115 and on which two opposite snap-in openings are provided. When the applicator is pushed in, the engaging lugs 115 snap into the snap-in openings of the receiving element 221 . This connection between the applicator 100 and the applicator holder 200 essentially functionally corresponds with the connection between a syringe/cartridge and an accessory component described in WO 2007/109915. More particularly, the applicator 100 and the applicator holder 200 have retention means which are designed in accordance with this document. In order to release the applicator 100 from the applicator holder 200 after filling, the receiving element 221 is elastically deformable so that the snap connection between the engaging lugs 115 and the corresponding snap-in openings can be released again by pressing on a wall area of the receiving element 221 offset by approximately 90° to the snap-in openings in relation to the cylinder axis of the receiving element 221 . Through pressing the receiving element 221 is deformed in such a way that the snap-in openings are pushed radially outwards from the engaging lugs 115 and there disengage from the engaging lugs 115 . With regard to further details and further possible embodiments of the connection between the applicator and the applicator holder, reference is made to already cited WO 2007/109915, the contents of which are incorporated herein by way of reference for teaching such a connection. In order to be able to exert this pressure on the receiving element 221 specifically and simply, two press wings 223 which are opposite each other are formed on the basic element 210 . The lateral compression of the two press wings 233 is transmitted, offset to the snap-in openings, to the cylindrical receiving element 221 of the fastening area 220 and thereby results in the release of the snap-type connection between the applicator 100 and applicator holder 200 . A coding wing 114 on the applicator 100 and a corresponding coding wing 222 on the applicator holder 200 show the correct orientation of the applicator 100 when connecting it to the applicator holder 200 . In addition, the connections themselves are different in order to ensure that the applicator 100 can only be connected correctly orientated. The first container unit 300 comprises a container holder 310 with an upwardly directed holding area 320 on which a container in the form of a syringe 330 with a syringe body 331 and syringe plunger 332 is held (in this case by means of a conventional Luer lock connection). The container holder 310 has an outer wall, the form of which very roughly corresponds with a half ellipsoid cut along its short axes, which laterally opens towards the applicator holder. The outer wall defines an inner space, in to which, starting from one end of the half ellipsoid a connection area with an outlet opening 311 formed therein extends towards the applicator holder. On one side of the container holder 310 an engaging arm 312 , inwardly offset with regard to the outer wall, projects toward the applicator holder. At the free end of the engaging arm there is an engaging lug. A fluid channel angled about 90° connects the holding area 320 with the outlet opening 311 . The second container unit 400 also comprises a container holder 410 with holding area 420 directed upwards. Here the holding area is in the form of a sleeve 420 with an internal thread. A container in the form of a tube 430 with an external thread on a rigid cylindrical connection area is screwed into the holding area 420 . With the exception of the holding area 420 the container holder 410 is similar in structure to the container holder 310 and more particularly also comprises an outlet opening 411 , a fluid channel connecting the holding area 420 with the outlet opening 411 , and an engaging arm 412 . The third container unit 500 also comprises a container holder 510 with a holding area 520 directed upwards, which here is designed in the form of a cylindrical chimney with multiple cutouts. A vial 530 with a septum seal is pushed into the chimney. The vial lies loosely on a first flexible engaging arm 521 . By pressing down on the vial the first engaging arm 521 can be elastically pressed outwards via an angled surface formed thereon, and the vial can be brought into a storage position in which, at a distance from a puncturing element in the form of a hollow pin 523 , it is in contact with a second engaging arm 522 which extends further downwards than the first engaging arm 521 . In this storage position the first engaging arm 521 engages in a tapered section of the vial and thereby prevents the vial from being removed from the chimney. Through renewed downwards pressure with increased force on the vial the second engaging arm 522 can be pressed elastically outwards via an angled surface formed on it so that the vial reaches a removal position, in which the pin punctures the septum seal. The vial is then fixed in the removal position by the second flexible engaging arm 522 . In this way it is possible to store a container with a closure that can be punctured on the container holder without the closure being able to be accidentally punctured or the container able to fall out of the holder. In its lower section the container holder 510 is similar in structure to container holder 310 . The fourth container unit 600 again comprises a container holder 610 with an upwardly directed holding area 620 which in this case is designed as an elongated cylindrical chamber 621 with a moveable sealing plunger 622 therein. In the chamber 621 a glass ampoule is 630 is accommodated which through pressing on the plunger 622 can be pushed onto a ramp 623 in order to shear off the tip of the ampoule. Apart from this the container holder 610 is again similar in structure to the container holder 310 . In order to fill both reservoirs 111 , 112 the applicator 100 is attached to the applicator holder with the plunger 121 , 122 fully inserted. For this the applicator is pushed along a fastening direction B ( FIG. 5 ) into the fastening area 220 . The applicator can already be pre-mounted on the applicator holder by the manufacturer. A container unit is pushed onto each of the two opposite sides of the basic body 210 . In the example in FIGS. 3 and 4 these are the first container unit 300 which is pushed on along a first connection direction V 1 , and the second container unit 400 which is pushed on along a second connection direction V 2 . The connection directions V 1 and V 2 are antiparallel to each other, i.e. directed oppositely along the same axis, and perpendicular to the fastening direction B. When the container holders 310 , 410 are pushed on, they surround the basic body 210 from two opposite sides and cover its upper side completely ( FIGS. 3 and 4 ). Towards the bottom too the basic body is largely covered by both container holders in the areas outside the fastening area 220 . In the mounted state the two container holders are in contact with each other. The engaging arm 312 of the first container holder 310 projects into a push-in area 413 ( FIG. 1 ) in the interior of the second container holder 410 , whereas, inversely, the engaging arm 412 of the second container holder 410 projects into the interior of the first container holder 310 . Each of the engaging arms is fixed by its engaging lug in a corresponding recess on the inner side of the outer wall of the other container holder ( FIG. 6 ). In this position each of the inlet connections 211 projects into the corresponding outlet opening 311 , 411 of the relevant container holder and is sealed vis-à-vis the container holder by the corresponding O-ring 230 . In this way a continuous, externally sealed fluid connection is produced between the syringe 330 and the first reservoir 111 and between the tube 430 and the second reservoir 112 . The plunger unit 120 is then retracted in order to remove the fluids from the two containers 330 , 340 separately and simultaneously and to transfer them into the reservoirs 111 , 112 . Thanks to the compact design of the filling device with short channels only a small quantity of each fluid in the filling device is lost (low dead volume). By pressing on the press wings 223 the applicator 100 is now released from the filling device. An accessory component, e.g. a mixer or a sprayer, can then be connected to the applicator and the fluids can be discharged from the applicator through the accessory component. If a fluid is to be taken up into the applicator from a different type of container, instead of the first and/or second container unit 300 , 400 a different container unit, e.g. the third or fourth container unit 500 , 600 or a container unit with yet another type of container is simply fastened to the applicator holder. In this way the greatest possible freedom in selecting the containers to be used for the components is assured. For the sake of completeness some additions to the container holder 510 are set out below. Abstractly expressed the container holder 510 provides an example of an adapter-like device for removing a fluid from a container sealed with a closure that can be punctured, which allows the container to be stored on the device without accidentally opening the container. Such a device can be considered as a separate aspect of the present invention, which is independent of the other aspects described above. In accordance with this aspect a device for removing a fluid from at least one container sealed with a closure that can be punctured, more particularly a vial, is disclosed which comprises: a body in which an inlet opening and an outlet opening are formed which are connected by a fluid channel; a hollow needle-like puncturing element connected to the inlet opening in order to puncture the closure of the container, more particularly a septum seal when the container is in the removal position; and a container holder connected to the body in order to hold the container on the device. In order to also hold the container securely on the device before puncturing of the closure and to prevent accidental puncturing, the container holder has a first catch structure for fixing the container in a storage position in which the container is further from the basic body than in the removal position (and in which the closure is therefore not already punctured) by way of a releasable snap-type connection. Preferably the container is also fixed in the removal position, and for this the container holder then has a second catch structure to fix the container in the removal position by way of a snap-type connection. The catch structures can interact directly or indirectly with the container. Thus, for example, the container can be pushed directly into the container holder wherein the catch structures directly engage on a corresponding retention structure, e.g. a tapered section of the container, or the container can be held on a separate holder, which can be pushed into or onto the container holder, wherein the catch structures of the container holder interact with a corresponding retention structure of the holder. It is also conceivable that the container holder only has one single catch structure, while the container of the holder has two retention structures, wherein in the storage position the first of these retention structures interacts with the (single) catch structure, while in the removal position the second of these retention structures interacts with the catch structure. Each of the catch structures is preferably designed as follows: the container holder has a preferably at least partially cylindrical defining wall, which can have a single cutout or multiple cutouts. The first catch structure and the second catch structure each have a spring arm formed in the defining wall, at the free end of which an engaging lug is provided which extends into the interior of the defining wall. This makes for a simple and cost-effective manufacturing process. The catch structures are preferably offset with regard to the circumferential direction of the defining wall, e.g. next to each other or offset by approximately 180°, i.e. diametrically opposite each other in order to take up the smallest possible space while retaining the greatest possibly stability of the container holder. While the invention has been described above with the aid of an exemplary embodiment, the invention is not at all restricted to the above exemplary embodiment, and a large number of modifications are possible. Thus, instead of an applicator of the type set out here, other types of applicator can of course be used, e.g. an applicator as illustrated in WO 2009/144085 or WO 2007/109915. Conventional double syringes or individual syringes combined into a unit can also be used. Accordingly it is also possible to design the applicator connection in a different manner. More particularly, the distances between the outlets of the applicator can be selected differently as required, more particularly as greater than in the exemplary embodiments illustrated here. While the method of fastening the applicator to the applicator holder shown here is advantageous, another type of fastening between the filling device and the applicator can be selected, e.g. a conventional Luer connection. In other embodiments the applicator can only have one reservoir and accordingly only one single container holder is then present. A large number of further modifications are possible.
A modular filling device for filling at least a first reservoir ( 111 ) of an applicator ( 100 ) with a fluid is proposed. The filling device comprises a container holder ( 310 ) with a holding area ( 320 ) on which a container ( 330 ) is held. The applicator is mounted along a securing direction on an applicator holder ( 200 ). In order to permit the greatest possible flexibility in the choice of the container, the container holder ( 310 ) can be connected to the applicator holder ( 200 ) along a connecting direction that runs transversely with respect to the securing direction for the applicator.
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CROSS REFERENCE TO RELATED APPLICATION This application claims the benefit of the prior filed, provisional application Ser. No. 61/149,344, filed Feb. 3, 2009. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and associated apparatus for lifting, stabilizing and supporting a pre-existing building structure, and more particularly, a method for using a series of brackets to attach a building structure to piers drilled vertically into the ground proximate the building structure, and lifting the brackets substantially concurrently to raise the building structure relative to the piers. 2. Description of the Related Art Methods for lifting pre-existing building structures upon piers driven into the ground around a portion of the structure typically utilize hydraulic rams that drive steel pier pipes into the ground until either sufficient ground resistance is achieved or the lower end of the pier strikes a suitable load-bearing rock stratum. Because hydraulic rams require relatively little horizontal space, a ram assembly may be positioned relatively close to a structure. Piers may thereby be installed in relative close proximity to the structure foundation, which is preferred in most cases. Helical and threaded piers are drilled into the ground using a drill rig assembly, rather than via hydraulic ram, and may offer advantages in certain substrates. Because of the dimensions of a typical drill rig assembly, however, which typically includes a base, stand and drill head, a vertically drilled pier cannot typically be installed as close horizontally to a building structure as a hydraulically driven vertical pier. Typical solutions in the prior art for installing drilled piers closer to a structure include notching the structure footing or drilling the pier into the ground as an angle so that the lower portion of the pier may lie in closer proximity to the footing. Each such solution presents disadvantages in that the first may compromise the structural integrity of the footing, as well as increase installation labor, and the second solution yields a pier unable to bear the same load as a vertically oriented pier. What is needed is a method and apparatus that allows use of drilled piers in close proximity to a building structure so that piers may be drilled a substantial distance into a rock stratum while maintaining a substantially vertical disposition. SUMMARY OF THE INVENTION Embodiments of the present invention comprise means for stabilizing and lifting a building structure using continuous lift methodologies in combination with hollow, threaded bar piers installed proximate to foundations of preexisting structures. In particular, certain embodiments utilize relatively small diameter, threaded, micro piles drilled into the ground using a rotary drill head. Other embodiments utilize larger diameter, unthreaded, pier pipes installed via hydraulic ram. A micro pile typically comprises a hollow, threaded, steel bar that carries concrete slurry, also referred to as grout, through its central cavity to flow from one or more apertures proximate a drill bit. The micro pile and drill bit are driven by a rotary drill head attached to the end of the micro pile distal from the drill bit. The grout is under pressure and as the micro pile is drilled into the ground, grout flowing from the apertures fills the space between the walls of the shaft created by the drill bit and the micro pile, which is of smaller diameter than the drill bit. The micro pile is attached to the structure to be stabilized or lifted by an offset or eccentric pier bracket. The eccentric pier bracket allows for additional space between the micro pile and the structure, thereby providing sufficient room for a drill head and associated support apparatus. Other advantages of the invention will become apparent from the following description taken in connection with the accompanying drawings, wherein is set forth by way of illustration and example several embodiments of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view of micro pile or micro pier drilled into ground proximate a building structure footing with the pier attached to the footing using an eccentric pier bracket. FIG. 2 is a side view of a pipe pier hydraulically driven into ground proximate a building structure footing with the pier attached to the footing using an eccentric pier bracket. FIG. 3 is a side view of a pipe pier hydraulically driven into ground proximate a building structure footing with the pier attached to the footing using an eccentric pier bracket of increased width relative to the brackets shown in FIGS. 1 and 2 . FIG. 4 is a side view of an eccentric pier bracket. FIG. 5 is a side view of an alternative embodiment of an eccentric pier bracket. FIG. 6 is a back view of an eccentric pier bracket. FIG. 7 is a side view of a drilling rig mounted to an eccentric pier bracket. DETAILED DESCRIPTION As required, a detailed embodiment of the present invention is disclosed herein; however, it is to be understood that the disclosed embodiment is merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. Referring now to the drawings. FIGS. 1 through 7 illustrate several embodiments of a pier driving system, and elements thereof, for stabilizing and lifting preexisting structures built upon foundations such as poured concrete or masonry footings. FIG. 1 is a side view of a micro pile pier 100 including a hollow micro pile shaft 105 drilled into ground 110 proximate a building structure footing 115 with the pier 100 attached to the footing 115 using an eccentric pier bracket 120 . As illustrated, soil has been excavated from an area proximate the footing 115 , and the desired location of a pier 100 and bracket 120 , to form a hole 125 for positioning the pier assembly. (In the figures, footings, slabs, walls, grout columns, and soil and rock strata are shown in cross section). In general, holes 125 are excavated along the perimeter, or along the side, of a portion of a structure to be lifted. An eccentric bracket 120 is shown secured to the footing 115 so that the horizontal bearing plate 130 underlies the footing 115 . Fasteners 135 such as screws or bolts adapted for secure fastening to concrete, are driven into the foundation or footing surface adjoining the vertical plate 140 through one or more holes 145 (see FIG. 4 ) provided in the vertical plate 140 in order to attach the bracket 120 securely to the footing 115 . The vertical plate 140 and horizontal bearing plate 130 form a right angle bracket 150 . The horizontal bearing plate 130 is supported by a pair of triangular support plates 155 that are attached to, or integral with, rectangular side plates 160 . The left side plate 160 a and left support plate 155 a of a bracket are shown in several of the figures including FIGS. 1 and 4 . The back view of a bracket 120 provided in FIG. 6 , shows both left 160 a and right 160 b side plates. A guide or lift rod support collar 165 is welded or otherwise attached to the outside surface of each side plate 160 in vertical orientation. An adjustable, threaded lift rod 170 passes through each collar 165 and terminates at the lower end with a threaded nut 175 . A pier cap 180 spans both lift rods 170 and crosses over the space between and over the side plates 160 . A nut 185 at the upper end of each lift rod 170 secures the pier cap 180 . The channel or space between the side panels 160 is sized to accommodate a pier sleeve 190 for holding either a pier pipe 195 or micro pier shaft 105 . After the sleeve 190 is placed within the channel, it is retained by installing the upper 200 a , middle 200 b and lower 200 c face plates. With particular reference to FIGS. 4 through 6 , an eccentric pier bracket 120 differs from brackets in the prior art in that the axis 205 of the pier is moved further from the building structure to allow room for machinery used to drive the pier 100 into the ground. In the embodiments shown herein, this is accomplished by increasing the width of the side plates 160 (side plate width runs left to right as shown in FIGS. 1 through 5 ) so that the pier axis 205 , as well as the threaded lift or guide rods 170 and collars 165 , are moved a further distance from the right angle bracket 150 . FIG. 1 illustrates a micro pile 105 drilled into the ground 110 proximate the footing 115 of an existing structure. Because the micro pile 105 is fitted with a sacrificial drill bit 210 , it may be drilled not only to reach a suitable load bearing rock stratum 215 but may also be drilled into the rock to create and fit within a pocket 220 . As the drill bit 210 moves downward, grout 225 is forced through apertures (not shown) proximate the drill bit 210 to fill the void 230 surrounding the micro pile 105 . When hardened, the grout 225 forms a load-bearing column 235 . Because of the irregular outer surface of the grout column 235 , the pier 100 provides strong frictional and mechanical resistance to vertical movement once the grout 225 sets, even if a pier 100 is installed without reaching rock 215 . Micro piles 105 are drilled into the ground 110 using a drill rig 240 (see FIG. 7 ) typically comprising a base 245 that attaches to the pier bracket 120 , and a vertically disposed stand 250 that projects upward from the base 245 . A rotary drill head 255 is mounted to and slides along the stand 250 . Threaded, hollow micro pile 105 is coupled to the drill rotor 260 . The drill head 255 moves downward along the stand 250 as the pile 105 is drilled into the ground 110 . Typically, the drill head 255 is hydraulically powered. As shown, because the pier bracket 120 is eccentric, sufficient space between the pier axis 205 and the building structure (wall 265 ) is provided to accommodate the drill rig 240 . FIG. 2 is a side view of a pipe pier 100 A hydraulically driven into ground 110 proximate a building structure footing 115 with the pier 100 A attached to the footing using an eccentric bracket 120 . The eccentric bracket 120 allows for installation of the pier 100 A by providing sufficient additional space from the pier axis 205 A to the structure wall 265 (including siding 270 ) to accommodate a hydraulic ram (not shown). FIG. 3 is a side view of a pipe pier 100 B hydraulically driven into ground 110 proximate a building structure footing 115 with the pier 100 B attached to the footing 115 using an eccentric bracket 120 A (see also FIG. 5 ) of increased width (offset) relative to the brackets 120 shown in FIGS. 1 and 2 . By way of example, embodiments of the bracket 120 shown in FIGS. 1 and 2 may provide a 4½ inch pier offset (the distance between the vertical plate 140 and the pier axis 205 ) while the bracket 120 A shown in FIG. 3 may provide a 6½ pier offset. Further embodiments of an eccentric pier bracket may include a vertical plate and a horizontal plate abutting one another at a substantially right angle therebetween to form a right angle bracket. The horizontal plate is supported by one or more support plates positioned below the horizontal plate to receive force applied downward to the horizontal plate. A left side plate and an opposing right side plate are spaced apart and positioned generally parallel to one another. Each side plate is attached to the rearward face of the vertical plate and extends below the vertical plate and the horizontal plate to attach to the support plate. Downward and lateral forces applied to the bracket are thereby substantially transferred to said side plates. The side plates each have a longitudinal axis traversing the center portion of each side plate. These longitudinal axes have generally vertical dispositions when the eccentric bracket is operatively positioned in a pier assembly attached to a building structure. A cylindrical support collar has a longitudinal axis and is vertically disposed between the side plates and rearward of the vertical plate so that the support collar longitudinal axis is rearward of the side plate longitudinal axes. Another embodiment of a pier bracket system for lifting a building structure such as a foundation or footing and the like may include a horizontal plate having a top surface and a bottom surface, a front edge and a rear edge, the horizontal plate being used for insertion at its front edge under a building structure. A vertical plate is mounted at its lower edge to a rearward portion of the top surface of the horizontal plate and extends substantially across and over the rear edge. A left side plate and a right side plate, each vertically oriented, are spaced apart and joined by attachment of the front edge of each side plate to the rear surface of the vertical plate, which spans the front edges of the side plates. A left gusset and a right gusset support the horizontal plate. The left gusset has a horizontal top edge attached along a portion of the bottom surface of the horizontal plate proximate the left margin of the horizontal plate. The left gusset has a rearward facing vertical rear edge attached to a lower portion of the front edge of the left side plate. The right gusset has a horizontal top edge attached along a portion of the bottom surface of the horizontal plate proximate the right margin of the horizontal plate. The right gusset has a rearward facing vertical rear edge attached to a lower portion of the front edge of the right side plate. The side plates are spaced apart horizontally by a distance sufficient to accommodate a pier support sleeve therebetween. The side plates each have a vertically oriented longitudinal axis and the pier support sleeve has a vertically oriented longitudinal axis. The pier support sleeve is positioned between the side plates so that the longitudinal axis of the pier support sleeve is positioned rearward of the longitudinal axes of the side plates. In this manner, the side plates are forwardly eccentric of the pier sleeve and the distance between the vertical bracket and the pier support sleeve is increased sufficiently to allow accommodation of a drill head above the pier support sleeve. It is to be understood that while certain forms of this invention have been illustrated and described, it is not limited thereto except insofar as such limitations are included in the following claims and allowable equivalents thereof.
A method and apparatus for installing remedial piers in which substantially vertical piers are located in close proximity to the wall and footing of an existing structure and are drilled to a substantial depth to penetrate a rock stratum or debris-laden soil. The piers support the structure upon eccentric brackets to transfer the structural load from the footing to the piles. Installation of the piers is followed by a continuous lift of the structure via hydraulic manifold.
4
FIELD OF THE INVENTION This invention relates to image sensors for converting an optical image into electrical signals and, in particular, to a pixel element in such a sensor. BACKGROUND One common type of image sensor, commonly found in digital and video cameras, includes an array of photoelements, where each photoelement generates a signal approximately proportional to the light impinging upon the photoelement area. As shown in FIG. 1, such a photoelement array 10 outputs its signals, typically pursuant to an addressing operation, to an analog-to-digital converter 12 to produce digital signals. Processing circuitry 14 then performs the required processing of the digital data to, for example, display the image on a screen or store the image in a memory. FIG. 2 illustrates one photoelement 20 (or pixel element) in the photoelement array 10 and serves to illustrate a common drawback of photoelements. The circuit of FIG. 1 is described in detail in U.S. Pat. No. 6,037,643, assigned to Hewlett-Packard Company and Agilent Technologies. A similar circuit is described in U.S. Pat. No. 5,769,384, also assigned to Hewlett-Packard Company and Agilent Technologies. Typically photoelements, such as shown in FIG. 2, generate a charge on an integrating capacitor 22 proportional to the light impinging upon the photoelement and the time the shutter is open (i.e., the integration time). The charge is converted to a voltage outside of the photoelement during a reading cycle. The voltage output is then applied to an analog-to-digital converter, as shown in FIG. 1 . In FIG. 2, a bias current is set up by a bias signal PBB controlling a transistor 24 . Transistors 26 and 28 form a bias point amplifier for setting the base bias of a phototransistor 30 at a fixed level with respect to its emitter. Transistors 26 and 28 operate as a negative feedback loop, wherein an increased emitter voltage pulls up the gate of transistor 26 , which causes transistor 28 , connected as a source follower, to lower the emitter voltage. Transistor 28 also provides isolation of the phototransistor 30 emitter from fluctuations at node 32 . In operation, the integrating capacitor 22 is assumed to be initially charged to a reset voltage by coupling the capacitor to the summing node of the transfer amplifier 44 while read transistor 36 is on. A shutter signal is high during the initial charging of capacitor 22 so that the shutter transistor 38 is off and transistor 40 is on. Transistor 40 , when on, provides a path for phototransistor 30 to draw current from the power supply. When the shutter signal goes low, transistor 40 is turned off and transistor 38 is turned on, discharging capacitor 22 through phototransistor 30 at a rate depending on the light impinging on the base of phototransistor 30 . At the end of the shutter period (e.g., 20 microseconds), the shutter signal goes high, decoupling phototransistor 30 from capacitor 22 . Since the rate of discharge of capacitor 22 during the shutter period is approximately proportional to the light incident upon the phototransistor 30 , the charge on capacitor 22 after the shutter is closed now reflects the integral of the light intensity during the time that the shutter was open. A read signal NRD then goes low to couple capacitor 22 to an output line 34 and to the input of a transfer amplifier 44 . Transfer amplifier 44 converts the charge on capacitor 22 to a voltage signal. The transfer amplifier 44 pulls the output line 34 up to Vref (basically a reset level of capacitor 22 ), resulting in the charge that was removed from capacitor 22 by the light-induced current during the shutter open time being transferred to a transfer capacitor 48 . The read signal is now raised to turn off transistor 36 . The output of the transfer amplifier 44 now corresponds to the amount of light that impinged on phototransistor 30 while the shutter was open. This voltage is processed as shown in FIG. 1 for that particular pixel position. The output line 34 may be connected to all pixel elements in a column, where only one row of photoelements is addressed at a time by the NRD line being common to a row of pixels. One problem with such image sensors that convert a charge on an integrating capacitor internal to the pixel area to a voltage outside the pixel area is that the transfer capacitor 48 and integrating capacitor 22 must be fairly large to prevent the capacitors' signals from being significantly distorted by stray capacitances that are coupled to the transfer capacitor 48 , the integrating capacitor 22 , or any of the interconnects between the two when the read transistor 36 is turned on. Further, the additional charge-to-voltage conversion circuitry takes up chip area. Accordingly, the design of the pixel element is relatively inflexible, and its sensitivity (ability to produce large signals in low light conditions) is limited due to the required size of the transfer capacitor 48 . The size of the transfer capacitor 48 has an inverse relationship to both the settling time of the transfer amplifier 44 and the substrate noise coupling into the signal. This means that as the transfer capacitor is made smaller to increase the sensitivity of the photodetector, the settling time and noise get worse. What is needed is a photoelement that does not suffer from the drawbacks of the prior art. SUMMARY A photoelement (or pixel element) for an image sensor is described that does not require a charge-to-voltage conversion, but instead outputs a voltage directly related to the intensity of the light impinging on the photoelement. Hence, a relatively large integrating capacitor is not needed. In one embodiment, only parasitic capacitance is used for the integrating function. Additional capacitance may be added to control the gain of the photoelement. The integrating capacitance is initially charged to a reset voltage. A shutter signal closes a switch that couples the capacitance to a phototransistor or photodiode to discharge the capacitance. The switch is opened after the shutter period so that the remaining charge corresponds to the integral of the light that impinged on the photoelement during the shutter period. An MOS transistor, connected in a source follower configuration, has its gate connected to the integrating capacitance and its source coupled to an MOS read transistor. The read transistor is also connected to an output pin of the photoelement. When the read transistor is turned on, the voltage at the source of the source follower is applied to the output pin. There is no external charge-to-voltage transfer circuitry used. The source follower shields the integrating capacitance from any other parasitic capacitances not intended to be part of the integrating capacitance, thus making the output of the photoelement highly accurate with high gain. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows functional blocks of a conventional image sensor circuit. FIG. 2 is one type of pixel element circuit using a charge-to-voltage converter. FIG. 3 is a circuit in accordance with one embodiment of the invention. DETAILED DESCRIPTION FIG. 3 illustrates a single photoelement 50 in an image sensor array of photoelements. A controller 52 (outside of the photoelement) controls the various signals, such as shutter, read, and reset, to the various photoelements in the array in a conventional manner, and such detail need not be supplied. The photoelements are typically arranged in a two dimensional array, and the elements are addressed by row and column in a typical application. A phototransistor 60 and biasing network comprising transistors 64 , 66 , and 68 may be similar to those shown in FIG. 2. A bias signal is applied to pin 70 , which sets up a bias condition between transistors 64 , 66 and 68 to maintain a stable base-to-collector voltage across phototransistor 60 . Transistor 64 also provides shielding of node 72 from phototransistor 60 . Likewise, a photodiode could be used in place of the phototransistor with the cathode of the diode connected to the source of transistor 64 and its anode connected to ground. Transistor 64 acts as a buffering device so the voltage on the reversed bias capacitance of the diode does not change when the voltage on line 85 changes. If the cathode voltage were allowed to change, the change would result in stealing signal charge away from the generated signal current. In operation, a low reset pulse on pin 72 turns on transistor 74 to couple the power supply voltage VDD to line 76 . The low reset pulse is also applied to an inverter formed by transistors 78 and 80 so as to invert the reset signal. This inverted reset signal is applied to a gate of PMOS transistor 82 , which acts as a charge compensator to absorb the charge spike generated by later switching off transistor 74 . The source and drain of transistor 82 are shorted together. During this initial charging time, a shutter signal applied to pin 83 is low, causing the PMOS shutter transistor 84 to be on. Shutter transistor 84 couples line 85 to line 86 . Thus, VDD charges the parasitic capacitance on lines 76 , 85 and 86 during the reset period. The shutter signal is also inverted by transistors 87 and 88 so as to generate an inverted reset signal on line 90 . This inverted reset signal is coupled the gates of PMOS transistors 92 and 94 , which act as charge compensators to absorb the charge spike generated when shutter transistor 84 is later turned off. Also at this time, a read signal applied to read pin 96 is made high to turn on the NMOS read transistor 98 . The output voltage at pin 99 is then sampled, such as by the analog-to-digital converter (ADC) 12 in FIG. 1 or a capacitor in the sampling circuit of the ADC, to provide a baseline voltage. The read signal is then pulled low to shut off read transistor 98 . To detect the amount of light impinging on the photoelement 50 , a high signal is applied to reset pin 72 to turn off transistor 74 and isolate line 76 from VDD. The low shutter signal remains applied to pin 83 . Phototransistor 60 , which draws a current proportional to the intensity of light impinging upon the base of phototransistor 60 , discharges the initial charge on lines 76 , 85 , and 86 during this time. After a small (e.g., 20 microsecond) shutter period, the shutter signal is then raised to shut off transistor 84 , isolating line 86 from the phototransistor 60 . As mentioned above, transistors 92 and 94 absorb any charge spike when shutter transistor 84 is turned off. Transistors 92 and 94 , acting as charge compensators, are particularly needed when using very small integrating capacitors to avoid large voltage offsets. Also at this time, the reset signal at pin 72 is driven low to connect VDD to line 76 to provide a source for the current through phototransistor 60 and prevent lines 76 and 85 from being pulled low. The remaining charge on line 86 is thus related to the intensity of light that impinged upon phototransistor 60 during the shutter period. Line 86 is coupled to the gate of an NMOS transistor 102 connected as a source follower between VDD and the read transistor 98 . The output pin 99 is coupled to a current source to ground. The charge on line 86 creates a threshold voltage drop across transistor 102 that turns on transistor 102 to a degree so that current flows in transistor 102 . Since transistor 102 is connected as a source follower, the source voltage of transistor 102 is one threshold voltage less than its gate voltage and tracks the gate voltage, so that the source voltage corresponds to the light intensity that impinged upon phototransistor 60 during the shutter period. Transistor 102 also buffers line 86 from any output circuit so any external parasitic capacitances do not distort the charge signal on line 86 . A high read signal applied to pin 96 then turns on NMOS read transistor 98 to output a voltage on pin 99 approximately equal to that at the source of transistor 102 . The voltage at the output pin 99 (connected to a column line) may be applied to an analog-to-digital converter without any conversion of charge into voltage, in contrast to the circuit of FIG. 2 . The difference between the output voltage at reset and the output voltage after integration is used in one embodiment to generate the light information. Using the difference provides offset cancellation and first order cancellation of variations in the source followers that form the output buffer of each pixel. After the voltage at pin 99 is read by conventional circuitry, typically pursuant to row and column addressing operations, the reset signal and shutter signal are pulled low to charge lines 76 , 85 , and 86 for a new detection cycle. A voltage other than VDD may be used to charge the lines 76 , 85 , and 86 . Additional integrating capacitance may be added to line 86 for any reason, such as for gain control. Such capacitance may be provided as parasitic capacitance, FET capacitors, or other types of capacitors. Numerous advantages result from the disclosed photodetector: 1. a small integrating capacitor can be used, resulting in increased light sensitivity of the pixel and a smaller pixel area; 2. the source follower isolates the integrating capacitor from other circuitry, reducing noise and increasing design freedom; 3. there is no need for a charge-to-voltage converter; 4. decoupling the capacitance of the light sensitive device (e.g., phototransistor 60 ) from the integrating capacitance by transistor 64 allows the use of either a phototransistor or photodiode as the light gathering device. It also allows the detector to be made larger to gather more light, but this increase in detector size and detector capacitance does not cause the sensitivity of this circuit to be reduced as it does in prior art sensors. While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of this invention.
A photoelement for an image sensor is described which does not require a charge-to-voltage conversion, but instead outputs a voltage directly related to the intensity of the light impinging on the photoelement. In one embodiment, only parasitic capacitance is used for the integrating function. A transistor connected in a source follower configuration couples the parasitic capacitance to a read transistor. The source follower shields the integrating capacitance from any other parasitic capacitances not intended to be part of the integrating capacitance, thus making the output of the photoelement highly accurate with high gain.
7
STATEMENT OF GOVERNMENT INTEREST The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor. BACKGROUND OF THE INVENTION The present invention relates to structures for human accommodation, more particularly to construction or architecture of such structures, terrestrial or aquatic, having one or more relatively large interior openings. Certain types of marine vessels, such as container ships, have large interior openings (in marine terminology, "hatches") which permit and facilitate access, e.g., to cargo, interior spaces and modular payloads. Conventionally, cargo hatches are large rectangular openings in the deck which allow for easy loading and discharge of cargo; typically, such rectangular openings replace a substantial portion of the deck area, thereby leaving a significantly reduced deck structure. This reduction of the deck structure in conventionally constructed ships can present structural difficulties. In effect to some degree, a conventionally constructed cargo ship with large hatch openings has an "open" top and is thus analogous to a shoe box; subjection to strains of the conventionally constructed ship which has large openings can cause the ship to behave in a similar manner as would a shoe box under similar circumstances. In particular, if the conventionally constructed ship having large hatches is subjected to a twisting load, the structurally reduced deck has reduced rigidity and hence reduced ability to control the deflections from this twist. Such deflections can have adverse effects; for example, large stresses at the hatch corners can lead to structural failure. Conventional approaches to addressing these concerns have involved the utilization of structural reinforcement. One methodology has included increasing the thickness of the plating in the deck structure. Another methodology has included the addition of longitudinal box girders to increase the torsional and longitudinal rigidity of the ship hull. SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide, for a marine vessel, a hatch system which renders an improved structural response of the marine vessel to torsional and other loads. It is another object of this invention to provide such a hatch system which does not entail utilization of auxiliary structure. The present invention features an approximately planar structure which is provided with a plurality of voids. An inventive void is described herein as "geometric" so as to impart the notion that the void approximately defines a closed plane figure wherein the perimeter has particular geometric characteristics in terms of length, straightness, curvature and angularity. For most inventive embodiments the voids are preferably distributed in a regular pattern, i.e., conforming to some principle of order, symmetry, periodicity, repetition, recurrence, uniformity and/or homogeneity; the voids are thus arranged in a cross-diagonal motif which enhances the ability to withstand stresses, strains and deflections when the structure is utilized partitionally, e.g., as a floor, platform or deck, in the context of a plural-level structure such as a building, ship or other comparatively large edifice. The inventive apertural network is especially advantageous when used in connection with marine vessels which, when at sea, are subjected to various forms of potentially damaging or deforming loads. The present invention can be practiced in association with various marine vessel hull forms or types, in particular either with conventional single hull framing or with double hull framing. Container ships are a notable genre of marine vessels which can particularly avail this invention. In marine applications, especially, this invention efficiently and efficaciously utilizes structural material which is included in the construction of one or more decks or one or more portions thereof. The diagonally crisscross hatch pattern of the present invention adds torsional rigidity to the ship structure, thereby controlling, mitigating or reducing the warping deflections and resulting stresses. Conventional measures for controlling high stresses due to hull warping, such as increasing plating thickness or otherwise implementing complex detail or reinforcement, can thus be obviated or avoided by this invention. In testing conducted by the U.S. Navy, a finite element model was analyzed whereby the model was subjected to twisting loading. The resultant stresses of the model were shown to be about three to four times less than would ensue if a typical rectangular-hatch ship were subjected to such loading. Moreover, this invention's configurational standarization of the openings accommodates the modularity which is typical of cargo containment; items of same or similar form or dimension (modules, containerized cargo, payloads, etc.) can be inserted into the openings. In fact, inventive practice can dictate shapes and sizes of the openings in conformity with, or otherwise in anticipation of, the shapes and sizes of the entitities to be passed therethrough. Commercial container ships are among the various genres of marine vessels which can avail the present invention. Container ships are used for transporting cargos which typically are containerized or modularized in rectangular form; hence, container ships conventionally have large rectangular hatches to accommodate such rectangular cargos. The present invention can afford structural benefits to container ships while still accommodating their rectangularly shaped cargos. For some marine applications, the inventive diagonal hatch system includes diagonal hatch patterns on each of a plurality of decks, at least two of which can be vertically adjacent decks; such repetition of the inventive hatch pattern on one or more internal decks, in addition to the top deck, can accommodate entities (e.g., cargo modules) of virtually any desired depth inside the hull. In accordance with many embodiments of this invention, a plural-level structure comprises at least one partition which approximately defines a horizontal plane for separating two vertically consecutive levels of the plural-level structure. The partition is provided with at least four apertures for permitting communication between the two separated levels. The apertures are arranged, in the partition, in a plural number of tiers rows which are approximately parallel with respect to each other. This plural-tier arrangement is characterized by an approximately parallelly iterative positively diagonal apertural alignment mode and an approximately parallelly iterative negatively diagonal apertural alignment mode, whereby successive apertures in each positively diagonal apertural alignment have abutting sides which are approximately parallel to each other and which are approximately perpendicular to the positively diagonal apertural alignment, and whereby successive apertures in each negatively diagonal apertural alignment have abutting sides which are approximately parallel to each other and which are approximately perpendicular to the negatively diagonal apertural alignment. According to some inventive embodiments, a plural-level structure comprises at least two vertically consecutive partitions for separating at least three vertically consecutive levels of the plural-level structure. Each partition is approximately identically provided with at least four geometric (e.g., polygonal) apertures for permitting communication between at least three separated levels. At least two consecutive partitions are configured with respect to one another whereby the corresponding plural-tier arrangements are approximately in vertical spatial alignment. According to some embodiments of the present invention, a plural-level structure comprises at least one wall (in marine terminology, "bulkhead") which engages at least one partition. The wall traverses or substantially traverses the partition while circumventing one or more neighboring apertures. According to some such embodiments, the wall borders upon at least a portion of each of at least two apertures. For embodiments wherein a plurality of inventively apertured partitions are provided in approximate vertical apertural alignment, at least one wall can be provided which engages at least two such partitions, wherein the wall at least substantially traverses each partition while circumventing one or more neighboring apertures in each partition; according to some such embodiments, the wall borders upon at least a portion of each of at least two apertures corresponding to each partition. In fact, some such inventive embodiments provide at least one such wall which at least partially extends (in an approximately vertical direction) into each of at least two levels, thereby intersecting at least one partition. When the plural-level structure is a marine vessel (such as a cargo ship or a military ship), it may be particularly beneficial in inventive practice to orient the tiers approximately longitudinally with respect to the marine vessel, i.e., so that the tiers are not only approximately parallel to each other but are also approximately parallel to the imaginary longitudinal axis of the marine vessel. With the tiers of the hatches being thus oriented, the diagonally crosswise distribution of the hatches can more optimally serve to amplify or embellish resistance of the marine vessel to deflections and stresses of one or more decks due to warping or twisting of the hull. According to most embodiments of the present invention, at least one pair of adjacent positively diagonal alignments define therebetween a positively diagonal traversal of the plural-tier arrangement, and at least one pair of adjacent negatively diagonal alignments define therebetween a negatively diagonal traversal of the plural-tier arrangement. This inventive featural aspect of cross-diagonal structural continuums can contribute to the overall structural fortification afforded by the present invention; this beneficial effect may be heightened by a regularity of the inventive apertural pattern, in that the cross-diagonal structural continuums would likewise be characterized by a type of regularity of distribution. When used in association with a marine vessel, for example, the cross-diagonal structural continuums of an inventively hatched deck can extend at least substantially across the marine vessel (from port to starboard) and, like a truss or rigid framework, thereby afford a structurally supportive quality. At the same time, the inventive cross-diagonal apertural lattice can afford a structurally resiliant quality in response to stresses, strains and deflections. Many inventive embodiments provide a positively diagonal apertural alignment mode and a negatively diagonal apertural alignment mode which are at an approximately equal orientation with respect to the direction of the tiers (and hence at an approximately equal orientation with respect to the direction of the marine vessel's longitudinal axis); for most such embodiments, this orientation is in the approximate range between 30° and 60°. Some such inventive embodiments provide a positively diagonal apertural alignment mode and a negatively diagonal apertural alignment mode which are each oriented at approximately 45° with respect to the direction of the tiers (and hence at approximately 45° with respect to the direction of the marine vessel's longitudinal axis) and are thus oriented approximately orthogonally with respect to each other. A noteworthy class of inventive embodiments includes a two-tier arrangement of approximately congruent symmetrical hexagonal hatches. Each hexagonal hatch has a double-right-angle-interposed side, a positively beveled side and a negatively beveled side. Every beveled side has approximately the same length. Each tier has its own hexagonal apertures approximately equivalently situated so that their double-right-angle-interposed sides face opposite the other tier. The abutting sides for each positively diagonal alignment comprise two negatively beveled sides. The abutting sides for each negatively diagonal alignment comprise two positively beveled sides. Another noteworthy class of inventive embodiments includes a three-tier arrangement of hatches. Two outer tiers are of approximately congruent symmetrical hexagonal apertures. An intermediate tier is of approximately congruent symmetrical octagonal apertures. Each hexagonal aperture has a double-right-angle-interposed side, a positively beveled side and a negatively beveled side. Each outer tier has its own hexagonal apertures approximately equivalently situated so that their double-right-angle-interposed sides face opposite the intermediate tier. Each octogonal aperture has two positively beveled sides and two negatively beveled sides. Every beveled side has approximately the same length. The abutting sides for each positively diagonal alignment comprise at least one pair of negatively beveled sides. The abutting sides for at least one positively diagonal alignment comprise two pairs of the negatively beveled sides. The abutting sides for each negatively diagonal alignment comprise at least one pair of positively beveled sides. The abutting sides for at least one negatively diagonal alignment comprise two pairs of positively beveled sides. Other objects, advantages and features of this invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS In order that the present invention may be clearly understood, it will now be described, by way of example, with reference to the accompanying drawings, wherein like numbers indicate the same or similar components, and wherein: FIG. 1 is a partial plan view of an inventive deck embodiment, wherein the deck is provided with hexagonally and octagonally shaped voids. FIG. 1A is the view of the inventive deck embodiment as shown in FIG. 1, additionally showing some imaginary delineations. FIG. 1B is the view of the inventive deck embodiment as shown in FIG. 1, additionally showing an inventive embodiment of a distribution of bulkheads. FIG. 2 is a partial plan view of another inventive deck embodiment, wherein the deck is provided with hexagonally shaped voids. FIG. 2A is the view of the inventive deck embodiment as shown in FIG. 2, additionally showing some imaginary delineations. FIG. 3 is a partial sectional perspective view of an inventive ship embodiment, shown port side looking forward, wherein the ship comprises an inventive deck embodiment and an inventive bulkhead embodiment such as shown in FIG. 1B. FIG. 4 is a view, similar to the view shown in FIG. 3, of the inventive ship embodiment shown in FIG. 3, here shown port side looking aft. DETAILED DESCRIPTION OF THE INVENTION Referring now to FIG. 1, deck 10a is an approximately planar structure having a plurality of hexagonal hatches 12a hex and octagonal hatches 12 oct . Rectangular array 14a has three horizontal rows and several vertical columns of hexagonal hatches 12a hex and octagonal hatches 12 oct . First row 16a 1 and third row 16a 3 are the outer rows, and second row 16a 2 is the intermediate row. First row 16a, and third row 16a 3 each have a plurality of hexagonal hatches 12a hex . Second row 16a 2 has a plurality of octagonal hatches 12 oct . The columns alternate between having two hexagonal hatches 12a hex and having one octagonal hatch 12 oct . As shown in FIG. 1, columns 18a 1 , 18a 3 , 18a 7 each have one octagonal hatch 12 oct ; columns 18a 2 , 18a 4 and 18a 6 each have two hexagonal hatches 12a hex . Every opening in first row 16a 1 and third row 16a 3 is an approximately congruent hexagonal hatch 12a hex . Every hexagonal hatch 12a hex is a rectanguloid which has a pair of approximately parallel approximately equal columnwise hexagonal sides 20a and 22a, a pair of approximately parallel unequal rowwise hexagonal sides 24a and 26a, and a pair of approximately equal hexagonal oblique sides 28a and 30a adjoining the ends of the shorter rowwise hexagonal side 26a. Every opening in second row 16a 2 is an approximately congruent octagonal hatch 12 oct . Every octagonal hatch 12 oct has a pair of approximately parallel approximately equal columnwise octagonal sides 32 and 34, a pair of approximately parallel approximately equal rowwise octagonal sides 36 and 38, a first pair of approximately parallel approximately equal oblique octagonal sides 40 and 42, and a second pair of approximately parallel approximately equal oblique octagonal sides 44 and 46. Each oblique octagonal side 40, 42, 44, and 46 adjoins an end of a columnwise octagonal side 32 or 34 and an end of a rowwise octagonal side 36 or 38. For every hexagonal hatch 12a hex , the longer rowwise hexagonal side 24a faces outwardly with respect to array 14a. Every hexagonal hatch 12a hex in first row 16a 1 is oriented approximately equally with respect to each other. Every octagonal hatch 12 oct in second row 16a 2 is oriented approximately equally with respect to each other. Every hexagonal hatch 12a hex in third row 16a 3 is oriented approximately equally with respect to each other and approximately invertedly with respect to the hexagonal hatches 12a hex in first row 16a 1 . With reference to FIG. 2, deck 10b is an approximately planar structure having a plurality of approximately congruent hexagonal hatches 12b hex . Rectangular array 14b has two horizontal rows and several vertical columns of hexagonal hatches 12a hex . First row 16b 1 and second row 16b 2 each have a plurality of hexagonal hatches 12b hex . Every column has a hexagonal hatch 12b hex ; as shown in FIG. 2, columns 18b 1 , 18b 2 , 18b 3 , 18b 4 and 18b 5 each have one hexagonal hatch 12b hex . Every hexagonal hatch 12b hex is a rectanguloid which has a pair of approximately parallel approximately equal columnwise hexagonal sides 20b and 22b, a pair of approximately parallel unequal rowwise hexagonal sides 24b and 26b, and a pair of approximately equal hexagonal oblique sides 28b and 30b adjoining the ends of the shorter rowwise hexagonal side 26b. For every hexagonal hatch 12b hex , the longer rowwise hexagonal side 24b faces outwardly with respect to array 14b. Every hexagonal hatch 12b hex in first row 16b 1 is oriented approximately equally with respect to each other. Every hexagonal hatch 12b hex in second row 16b 2 is oriented approximately equally with respect to each other and approximately invertedly with respect to the hexagonal hatches 12b hex in first row 16b 1 . Still referring to FIG. 2 and again referring to FIG. 1, it is seen that array 14a and array 14b bear certain similarities. For instance, hexagonal hatches 12a hex shown in FIG. 1 and hexagonal hatches 12b hex shown in FIG. 2 and are not "similar" in the strict geometric sense, but nevertheless are alike as having what is styled herein a "rectanguloid" shape, akin to an approximate rectangle which has had two adjacent corners beveled or chamfered. Hexagonal hatch 12a hex and hexagonal hatch 12b hex are each a symmetrical hexagonal aperture having a double-right-angle-interposed side, a positively beveled side and a negatively beveled side. For each symmetrical hexagonal aperture: Two sides are situated in the columnwise direction, approximately parallel and having approximately the same length; two sides are situated in the rowwise direction, approximately parallel and having different lengths; and, two sides are each situated in an oblique direction, having approximately the same length and being disposed at approximately equal and opposite angles with respect to the rectangular array's rowwise (horizontal) direction. Referring to FIG. 1A and FIG. 2A, each row of horizontal apertures has its hexagonal apertures approximately equivalently situated so that their double-right-angle-interposed sides face outward (away from the interior of the array), thereby approximately defining linear horizontal upper and lower borders (illustrated by dashed lines) of the respective arrays. The longer rowwise hexagonal sides 24a of first row 16a 1 , define imaginary upper border 48a of array 14a. The longer rowwise hexagonal sides 24a of third row 16a 3 define imaginary lower border 50a of array 14a. The longer rowwise hexagonal sides 24b of first row 16b 1 define imaginary upper border 48b of array 14b. The longer rowwise hexagonal sides 24b of second row 16b 2 define imaginary lower border 50b of array 14b. Typically, at least part of a ship deck's perimeter is approximately coextensive with the ship hull; i.e., to some extent at least, the deck is approximately bounded along its periphery by the hull. Hence, for purposes of envisioning the deck in the context of a ship, the port side (left-hand side of ship as ship faces forward) edge 52a and starboard side (right-hand side of ship as is ship faces forward) edge 54a of deck 10a shown in FIG. 1, and the port side edge 52b and starboard side edge 54b of deck 10b shown in FIG. 2, may be considered as being approximately coincident with the lateral periphery (i.e., port side and starboard side, respectively) of the ship. Imaginary upper border 48a of array 14a is near and approximately parallel to port edge 52a of deck 10a . Imaginary lower border 50a of array 14a is near and approximately parallel to starboard edge 54a of deck 10a. Imaginary upper border 48b of array 14b is near and approximately parallel to port edge 52b of deck 10b. Imaginary lower border 50b of array 14b is near and approximately parallel to starboard edge 54b of deck 10b. Thus considering decks 10a and 10b, it is seen that the ship has an imaginary longitudinal (running fore and aft) axis of symmetry, shown in FIG. 1A and FIG. 2A as dashed line l, which is approximately midway between: port edge 52a and starboard edge 54a of deck 10a shown in FIG. 1A; imaginary upper border 48a and imaginary lower border 50a shown in FIG. 1A; port edge 52b and starboard edge 54b of deck 10b shown in FIG. 2A; imaginary upper border 48b and imaginary lower border 50b shown in FIG. 2A. Longitudinal axis l rowwise bisects array 12a in FIG. 1A, and rowwise bisects array 12b in FIG. 2A. In FIG. 1A, row 16a 1 of octagonal hatches 12 oct is likewise rowwise bisected by longitudinal axis l. In FIG. 2A, longitudinal axis l passes rowwise through the hexagonal hatches 12b hex of both first row 16b 1 and second row 16b 2 . At many locations, an oblique side of an opening faces an oblique side of a diagonally adjacent opening, thereby forming an interfacial portion ("interface") of the approximately planar structure. With regard to the hatches shown in FIG. 1A, each hexagonal hatch 1a hex has at least one oblique side 28a or 30a which is approximately parallel to and forms an "interface" (either a positive interface 60a p or a negative interface 60a n ) with an octagonal oblique side 40, 42, 44 or 46 of an adjacent octagonal hatch 12 oct which is in a next row 16a and a next column 18a. Every interface is oblique in either a selected positive direction (positive interface 60a p ) or a selected negative direction (negative interface 60a n ). With regard to the hatches shown in FIG. 2A, each hexagonal hatch 12b hex has at least one hexagonal oblique side 28b or 30b which is approximately parallel to and forms an "interface" (either a positive interface 60b p or a negative interface 60b n ) with a hexagonal oblique side 28b or 30b of an adjacent hexagonal hatch 12b hex which is in a next row 16b and a next column 18b; such an interface is shown to be formed by a hexagonal oblique side 28b with a hexagonal oblique side 28b, or by a hexagonal oblique side 30b with a hexagonal oblique side 30b. Every interface is oblique in either a selected positive direction (positive interface 60b p or a selected negative direction (negative interface 60b n ). The terms "positive direction" and "negative direction" are intended herein to refer to angles of orientation with respect to longitudinal axis l, wherein longitudinal axis l is designated the "x axis" analogue in an "x-y" Cartesian plane; hence, of the hatches shown in FIG. 1A and in FIG. 1B, in each figure approximately half of the oblique sides are positively directed (i.e., positively "sloped" in terms of deviation from longitudinal axis l) and approximately half of the oblique sides are negatively directed (i.e., negatively "sloped" in terms of deviation from longitudinal axis l). Certain properties become manifest due to inherent symmetrical and geometrical aspects of each of array 14a and array 14b. Every interface is formed by a pair of abutting, approximately parallel oblique sides. The two abutting oblique sides and the interface formed thereby each define approximately the same positive or negative slope. In FIG. 1A, interfaces 60a p (positively sloped) and 60a n (negatively sloped) are aligned with each other, end-to-end approximately colinearly, in approximately the same positive and negative diagonal directions, as indicated by imaginary dashed diagonal lines da p and da n , respectively. Similarly, in FIG. 2A, interfaces 60b p (positively sloped) and 60b n (negatively sloped) are aligned with each other, end-to-end approximately colinearly, in approximately the same positive and negative diagonal directions, as indicated by imaginary dashed diagonal lines db p and db n , respectively. In other words, in FIG. 1A, two positively sloped interfaces 60a p , when considered as connected end-to-end, medially define a positively sloped diagonal line da p ; two negatively sloped interfaces 60a n , when considered as connected end-to-end, medially define a negatively sloped diagonal line da n . In FIG. 2A, each positively sloped interface 60b p medially defines a positively sloped diagonal line db p ; each negatively sloped interfaces 60b n medially defines a negatively sloped diagonal line db n . Moreover, two positively sloped interfaces 60a p , when considered as connected end-to-end, laterally peripherally define a positively sloped continuous rectilinear portion 62a p (for example as indicated in FIG. 1A by a dashed border); two negatively sloped interfaces 60a n , when considered as connected end-to-end, laterally peripherally define a negatively sloped continuous rectilinear portion 62a n (for example as indicated in FIG. 1A by a dashed border). One positively sloped interface 60b p laterally peripherally defines a positively sloped continuous rectilinear portion 62b p (for example as indicated in FIG. 2A by a dashed border); one negatively sloped interface 60b n laterally peripherally defines a negatively sloped continuous rectilinear portion 62b n (for example as indicated in FIG. 2A by a dashed border). The interfaces 60a p and 60a n thereby approximately define in FIG. 1A a "crisscross" of diagonal, linear, continuous portions 62a p and 62a n of structure 10a; continuous portions 62a p and 62a n traverse array 14a. Similarly, the interfaces 60b p and 60b n thereby approximately define in FIG. 2A a "crisscross" of diagonal, linear, continuous portions 62b p and 62b n of structure 10b; continuous portions 62b p and 62b n traverse array 14b. In FIG. 1A, each continuous portion 62a p includes two interfaces 60a p ; each continuous portion 62a n includes two interfaces 60a n In FIG. 2A, each continuous portion 62b p includes one interface 60b p ; each continuous portion 62b n includes one interface 60b n . In FIG. 1A, since upper border 48a and lower border 50a of array 14a are proximately parallel to starboard edge 52a and port edge 54a, respectively, of deck 10a, continuous portions 62a p and 62a n can be considered to traverse or substantially traverse deck 10a. Similarly, in FIG. 2A, since upper border 48b and lower border 50b of array 14b are proximately parallel to starboard edge 52b and port edge 54b, respectively, of deck 10b, continuous portions 62b p and 62b n can be considered to traverse or substantially traverse deck 10b. Hence, in FIG. 1A, every continuous portion 62a p , every diagonal line da p , every interface 60a p , every oblique hexagonal side 28a, every oblique octagonal side 40 and every oblique octagonal side 42 defines approximately the same positive slope; every continuous portion 62a n , every diagonal line da n , every interface 60a n , every oblique hexagonal side 30a, every oblique octagonal side 44 and every oblique octagonal side 46 defines approximately the same negative slope. Thus, all positively sloped diagonal lines da p are approximately parallel to each other; all negatively sloped diagonal lines daa n are approximately parallel to each other. Similarly, in FIG. 2A, every continuous portion 62b p , every diagonal line ddb p , every interface 60b p , and every oblique hexagonal side 28b defines approximately the same positive slope; every continuous portion 62b n , every diagonal line ddb n , every interface 60b n and every oblique hexagonal side 30b defines approximately the same negative slope. Thus, all positively sloped diagonal lines ddb p are approximately parallel to each other; all negatively sloped diagonal lines dd b n are approximately parallel to each other. Furthermore, in FIG. 1A, the absolute value of the positive slope defined by continuous portions 62a p , diagonal lines da p , interfaces 60a p , oblique hexagonal sides 28a, octagonal oblique sides 40 and oblique octagonal sides 42 is approximately equal to the absolute value of the negative slope defined by continuous portions 62a n , diagonal lines da n , interfaces 60a n , oblique hexagonal sides 30a, octagonal oblique sides 44 and oblique octagonal sides 46. Similarly, in FIG. 2A, the absolute value of the positive slope defined by continuous portions 62b, diagonal lines db p , interfaces 60b and oblique hexagonal sides 28b is approximately equal to the absolute value of the negative slope defined by continuous portions 62b n , diagonal lines ddb n , interfaces 60b n and oblique hexagonal sides 30b. In FIG. 1A and FIG. 1B, the slope (degree of deviation from longitudinal axis l) of each of diagonal lines da p , da n , db p and db n is represented to be roughly 45°; hence, diagonal lines da p are approximately perpendicular with respect to diagonal lines da n , and diagonal lines db p are approximately perpendicular with respect to diagonal lines db n . It should be apparent to the ordinarily skilled artisan reading this disclosure that, in accordance with inventive principles, so long as the slope of each of diagonal lines da p in array 14a is approximately equal, the slope of each of diagonal lines da n in array 14a is approximately equal, the slope of each of diagonal lines db p in array 14b is approximately equal, and the slope of each of diagonal lines db n in array 14b is approximately equal: The basic geometric integrity of array 14a can be retained while varying one or both of the slopes of diagonal lines da p and da n ; the basic geometric integrity of array 14b can be retained while varying one or both of the slopes of diagonal lines db p and db n ; in array 14a, the absolute value of the slope of diagonal lines da p need not equal the absolute value of the slope of diagonal lines da n ; in array 14b, the absolute value of the slope of diagonal lines db p need not equal the absolute value of the slope of diagonal lines db n . Notable are certain shared attributes of array 14a and array 14b which are more generally characteristic of the present invention. Reference is still being made to FIG. 1A and FIG. 2A, wherein may be used more generic designations such as follows: approximately planar structure 10 (for deck 10a or deck 10b); geometric opening 12 (for hexagonal hatch 12a hex , octagonal hatch 12 oct or hexagonal hatch 12b hex ); rectangular array 14 (for rectangular array 14a or rectangular array 14b); horizontal row 16 (for horizontal row 16a or horizontal row 16b); vertical column 18 (for vertical column 18a or vertical column 18b); interface 60 (for interface 60a or interface 60b); continuous portion 62 (for continuous portion 62a or continuous portion 62b). In accordance with most embodiments of this invention, approximately planar structure 10 has a plurality of geometric openings 12 in a rectangular array 14 of at least two horizontal rows 16 and at least two vertical columns 18. Each geometric opening 12 has at least one oblique side which is approximately parallel to and forms an interface 60 with an oblique side of an adjacent geometric opening 12 which is in a next row 16 and a next column 18. Every interface 60 is oblique in either of a selected positive direction and a selected negative direction. The interfaces 60 are approximately aligned so as to approximately define a diagonal crisscross of continuous portions 62 of structure 10 which traverse array 14. Each continuous portion 62 includes at least one interface 60. Other properties are seen to be generally true of inventive arrays 14 such as array 14a and array 14b. The rows 16 define rectilinear horizontal sections which are not discrete with respect to each other. Similarly, the columns 18 define rectilinear vertical sections which are not discrete with respect to each other. Rather, there is partial "overlap" between adjacent rows 16 and between adjacent columns 18. This inventive feature entails sufficient propinquity of each pair of adjacent oblique sides which form an interface 60, thereby assuring both (i) a relatively large total open area in structure 10 and (ii) a distinct cross-diagonal pattern of continuous portions 62 in structure 10. Moreover, each intersection of a row 16 with a column 18 defines a common structural area of structure 10. Each intersection of first row 16a 1 or third row 16a 3 with a column 18a defines an approximately rectangular flanking platform 64a f which approximately coincides with a segment of upper border 48a or lower border 50a. Each intersection of second row 16a 2 with a column 18a defines an approximately rectangular medial platform 64a m . Each intersection of first row 16b 1 or second row 16b 2 with a column 18b defines an approximately rectangular flanking platform 64b which approximately coincides with a segment of upper border 48b or lower border 50b. It is also noted that, in array 14a and especially in array 14b, each non-flanking (interior) vertex of a platform 64 is nearly coincident with a non-flanking vertex of the defining columnwise side of an opening 12. Looking at it another way, in array 14a, the opening 12a oct vertices which join oblique sides 40, 42, 44 and 46 with columnwise sides 32 and 34 are nearly in alignment, in a rowwise direction, with the opening 12a hex shorter rowwise sides 26a; in array 14b, the opening 12b hex vertices which join oblique sides 28b and 30b with columnwise sides 20b and 22b are nearly in alignment, in a rowwise direction, with the opening 12b hex shorter rowwise sides 26b. It is emphasized that inventive practice is not limited to array 14a shown in FIG. 1 and array 14b shown in FIG. 2; nor is this invention limited to variations of array 14a and array 14b. In the light of this disclosure, the ordinarily skilled artisan should readily appreciate the application of inventive principles to various patterns of inventive arrays 14 which are markedly distinguishible from arrays 14a and 14b in one or more respects. For example, this invention admits of effectuation not only for hexagonal apertures and octogonal apertures but for a diversity of apertural shapes, e.g., rectilinear, curvilinear, or having indicia of both rectilinearity and curvilinearity. To elaborate, it is seen that there are multifarious inventively "thematic" patterns of apertural arrays. Inventive apertural arrayal motifs can be manifested in terms of rowwise arrangement, columnwise arrangement, diagonal arrangement, type or types of apertural shapes, interrelationships among various apertural shapes, etc. Among the configurational parameters which can be varied by the inventive practitioner are one or more of the following: (i) the number of different types of apertural shapes; (ii) the characteristics of each type of apertural shape; (iii) the relative distribution of the apertural shapes; (iv) the number of rows of apertural shapes; (v) the number of columns of apertural shapes; (vi) the degree of obliqueness of the positively sloped diagonals; (vii) the degree of obliqueness of the negatively sloped diagonals. The openings, according to this invention, can be characterized by rectilinearity, or curvilinearity or both rectilinearity and curvilinearity. For example, an inventive opening can be entirely rectilinear and hence polygonal, i.e., thus defining a closed plane figure bounded by three or more line segments, i.e., wherein three or more line segments are joined end-to-end; hexagons and octagons, for instance, are types of polygons. Or, an inventive opening can be partially rectilinear and partially curvilinear, e.g., substantially define a polygonal figure but have curvature at certain locations around the perimeter of the opening, such as at the vertices or corners where adjacent sides meet. Or, an inventive opening can be entirely curvilinear, e.g., generally define a polygonal figure but have varying degrees of curvature around the entire perimeter of the opening. Reference now being made to FIG. 1B, FIG. 3 and FIG. 4, approximately vertical transverse bulkheads can be inventively provided along continuous, generally crosswise paths which circumvent one or more apertured areas of the deck. For example, transverse bulkheads, such as bulkheads 70 1 , 70 2 , 70 3 and 7 4 shown in FIG. 3 and FIG. 4, can be accommodated by following staggered paths, such as the respectively corresponding paths 71 1 , 71 2 , 71 3 and 71 4 shown in FIG. 1B. FIG. 3 and FIG. 4 reveal cutaway perspectives of approximately half of ship 80, including the layout of an interior deck space. Ship 80 includes ship hull 82 and two decks, viz., top level deck 10a T and bottom level deck 10a B . Top deck 10a T has array 14a T of hexagonal hatches 12a hex-T and octagonal hatches 12 oct-T ; bottom deck 10a B has array 14a B of hexagonal hatches 12a hex-B and octagonal hatches 12 oct-B . Port edge 54a T of top deck 10a T is shown to meet ship hull 82 at the hull's port side 84; similarly, port edge 54a B of bottom deck 10a B is shown to meet ship hull 82 at the hull's port side 84. It can be envisioned that starboard edge 52a T of top deck 10a T meets ship hull 82 at the hull's starboard side (not shown), and that starboard edge 52a B of bottom deck 10a B meets ship hull 82 at the hull's starboard side (not shown). Each of transverse bulkheads 70 1 , 70 2 , 70 3 and 70 4 crosses each of decks 10a T and 10a B so as to partially bound three hatches in each deck. In relation to top deck 10a T , each transverse bulkhead borders upon part of each of two hexagonal hatches 12a hex-T and part of one octagonal hatch 12 oct-T . Similarly, in relation to bottom deck 10a B , each transverse bulkhead borders upon part of each of two hexagonal hatches 12a hex-B and part of one octagonal hatch 12 oct-B . As perhaps best illustrated in FIG. 1B, transverse bulkheads 70 1 , 70 2 , 70 3 and 70 4 cross decks 10a B and 10a B so as to appear "recessed" or "indented" in the fore direction of ship 80. A "mirror-image" inventive embodiment can be readily envisioned wherein transverse bulkheads 70 1 , 70 2 , 70 3 and 70 4 are shown to cross each of decks 10a T and 10a B so as to appear "recessed" or "indented" in the aft direction of ship 80; mentally reversing the port and starboard sides of ship 80 shown in FIG. 3 and FIG. 4, for example, could achieve such a "mirror-image" visualization. The inventive possibilities are endless for arranging and configuring bulkheads in conformity with inventive apertural arrayal. Generally speaking, for inventive marine vessel embodiments wherein bulkheads are implemented, at least one bulkhead at least partially crosses each deck so as not to encroach upon any apertures. The bulkhead will circumvent any aperture which is in the vicinity of the bulkhead. Although the bulkheads are shown in FIG. 1B, FIG. 3 and FIG. 4 to partially bound at least one hatch in each deck, in inventive practice a bulkhead need not be contiguous with one or more apertures or portions thereof. The inventive requirement in this regard is that each bulkhead avoid or skirt the openings so as not to impinge on any opening. As shown in FIG. 3 and FIG. 4, a portion of top deck's array 14a T matches a portion of bottom deck's array 14a B whereby hexagonal hatches 12a hex-T are in approximate vertical alignment with hexagonal hatches 12a hex-B and octagonal hatches 12 oct-T are in approximate vertical alignment with octagonal hatches 12 oct-B . In other words, at least to some extent, array 14a T is approximately "correlative" with array 14a B . A section of array 14a T is shown to be congruous with a section of array 14a B . Depending on the inventive marine vessel embodiment, two or more different (e.g., successive) decks can be entirely or partially correlative in that one, some or all of the apertures of one deck are in approximate vertical alignment with one, some or all of the apertures of one or more other decks. Approximately vertical longitudinal port side bulkhead 86 is shown provided along port side 84, between decks 10a T and 10a B , so as to approximately join upper border 48a T of array 14a T with upper border 48a B of array 14a B . Another longitudinal bulkhead, the starboard side counterpart (not shown), can be envisioned as disposed between decks 10a T and 10a B so as to approximately join lower border 50a T of array 14a T with lower border 50a B of array 14a B . Some inventive marine vessel embodiments feature longitudinal bulkheads, such as depicted in FIG. 3 and FIG. 4, on each of the port and starboard sides. Such longitudinal bulkheads, which approximately coincide with the upper and lower arrayal borders of each of correlative plural decks, afford a "double hull" type of structural reinforcement, which is especially propitious where disposed in the vicinities of populated deck areas. Other embodiments of this invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. Various omissions, modifications and changes to the principles described may be made by one skilled in the art without departing from the true scope and spirit of the invention which is indicated by the following claims.
A ship has at least one deck which is inventively latticed in a regular (e.g., repeating) geometric pattern of hatches. The hatches of each such inventive deck are shaped in standardized geometric forms and disposed in diagonally contiguous interrelationships, thereby enhancing the structural characteristics of the deck and of the ship, especially in terms of attenuation of warping deflections and resultant stresses.
1
BACKGROUND OF THE INVENTION This invention relates to a method of improving the rheological properties of clays, more especially kaolin clays, in water, to a pigment composition for use in aqueous dispersions, for example in paper coating compositions, and to a method of preparing an aqueous suspension containing from about 60% to about 75% by weight of a clay mineral and having improved rheological properties. Many varieties of coated papers are produced today. They are principally coated with a composition, sometimes known as the coating colour, which essentially comprises an adhesive, also known as a binder, and a pigment. A discussion of the constituents of paper coating compositions and of the methods of applying such compositions to paper is given in Chapter XIX, Volume III, of the 2nd Edition of the book by James P. Casey entitled "Pulp and Paper: Chemistry and Technology". The adhesive used can be, for example, starch, casein or a synthetic resin latex; the particular adhesive used will depend, for example, on the printing process to be used, e.g. offset lithography requires the adhesive to be water-insoluble. Generally, the pigment will consist of clay together with an amount, which may be up to 60% by weight, of one or more other constituents, for example, calcium carbonate, calcium sulphate, lithopone, barium sulphate, titanium pigments, talc or satin white. In certain procedures for preparing kaolin clay for use in industry, especially for use in paper coating compositions, and in particular in those procedures which are commonly adopted in the United States of America, the raw kaolin clay is subjected, in aqueous suspension, to various particle size separations. The thus beneficiated fine kaolin product is separated from the water by filtration and the filter cake redispersed in water to form a more concentrated suspension containing from about 50% to about 60% by weight of dry clay. At this stage two alternative methods are available to produce a final suspension which is suitable for transport and storage. In the first method the suspension containing 50-60% by weight of dry clay is spray dried and the spray dried product redispersed in water containing a dispersing agent to provide a suspension containing around 70% by weight of dry clay. In general a final suspension prepared by this method is found to have acceptable rheological properties under conditions of high shear. In the second method, however, the suspension containing 50-60% by weight of dry clay is not spray dried but instead is mixed with sufficient previously spray dried clay to increase the solids content to around 70% by weight. The final suspension prepared by this method generally tends to exhibit a higher viscosity under conditions of high shear than an equivalent suspension prepared by the first method. The present invention provides a way of overcoming the disadvantage of the second method. DESCRIPTION OF THE PRIOR ART It has been discovered that certain raw kaolinitic clays, when subjected to purification and particle size separation to yield a product suitable for use as a pigment in a paper coating composition, give poor results when a paper coating composition containing the clay product is coated onto a base using modern highspeed coating apparatus, for example a trailing blade coater. Such clays tend to give a coating which, instead of being smooth, level and continuous, is marred by streaks, stipples and other defects, and it is known that defects of this type are generally due to the high viscosity of the coating composition under high rates of shear. EP-No. 0110036 A (Georgia Kaolin) discloses a method of processing naturally occurring kaolin clay in which ion exchange resins are employed to remove charged soluble impurities from the clay. This technique suffers from the disadvantage that the ion exchange resin must be separated from the clay after treatment if the clay is to be used as a paper grade pigment. SUMMARY OF THE INVENTION According to a first aspect of the present invention, there is provided a method for improving the rheological properties of a clay mineral which, when dispersed with water, either releases into solution or retains on its surface multivalent cations, which method includes the step of treating the clay mineral in aqueous suspension with a an aluminosiliceaous material having a cation exchange capacity of a least 50 meq/100 g, said aluminosiliceous material being employed in an amount sufficient to react with a significant proportion of the exchangeable cations in the clay mineral. According to a second aspect of the present invention, there is provided an aqueous suspension of a clay mineral which, when dispersed in water, either releases into solution or retains on its surface multivalent cations, and an amount of an aluminosiliceous material having a cation exchange capacity of at least 50 meq/100 g sufficient to react with a significant proportion of the exchangeable cations in the clay mineral. According to a third aspect of the present invention, there is provided a method for preparing a paper coating composition having improved rheological properties which method comprises: treating, in aqueous suspension, a clay mineral which, when dispersed in water, either releases into solution or retains on its surface multivalent cations with an amount of an aluminosiliceous material having a cation exchange capacity of at least 50 meq/100 g sufficient to react with a significant proportion of the exchangeable cations in the clay mineral; and admixing an aqueous suspension of the treated kaolin clay pigment with an adhesive. According to a fourth aspect of the present invention there is provided a method for improving the rheological properties of a clay mineral which, when dispersed in water, either releases into solution or retains on its surface multivalent cations, which method includes the steps of blending a clay mineral having a solids content in the range of about 50% to about 60% by weight of solids with a spray dried clay mineral to increase the solids content to within the range of from about 60% to about 75% by weight of solids, and adding to the blend an aluminosiliceous material having a cation exchange capacity of at least 50 meg/100 g, said aluminosiliceous material being employed in an amount sufficient to react with a significant proportion of the exchangeable cations in the clay mineral. The aluminosiliceous material is preferably used in an amount of at least 0.1% by weight, based on the weight of dry kaolin clay. Preferably, no more than 2.0% by weight of the aluminosiliceous material should be used since greater than 2.0% may affect adversely the properties of the clay mineral. The aluminosiliceous material preferably has a cation exchange capacity of at least 200 meq/100 g, most preferably 500 meq/100 g. The method of the present invention has been found to be particularly suitable where the clay mineral is a kaolin clay. Hereafter, references to kaolin clay should not be construed as limiting the present invention to the treatment of kaolin clays only. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is based on the discovery that one of the causes of poor high shear rheological properties in a paper coating composition containing a kaolin clay as the or one of the pigments is a relatively high content of water-soluble compounds containing multivalent cations, in particular calcium, magnesium, iron and aluminium, closely associated with the kaolin. Paper coating compositions generally contain the minimum quantity of water consistent with a fluidity which is just sufficient to enable the composition to spread over the surface of the paper. In such concentrated suspensions a dispersing agent must be provided for the kaolin. The dispersing agents generally used are alkali metal or ammonium condensed phosphate salts, for example sodium hexametaphosphate or tetrasodium pyrophosphate, or polyelectrolytes such as alkali metal or ammonium salts of poly(acrylic acid) or poly (methacrylic acid). Any multivalent cations which are present in the suspension tend to form complexes with dispersing agents of these types, thus reducing their effectiveness in maintaining the suspended particles of kaolin in a fully dispersed condition. The aluminosiliceous material may be natural or synthetic and may be, for example, a smectite clay, for example bentonite, montmorillonite, hectorite, saponite or fullers earth, or, more preferably, a zeolite, Smectite clays generally have a cation exchange capacity in the range of from 50 to 150 meq/100 g but zeolites may have cation exchange capacities in excess of 200 meq/100 g and up to about 600 meq/100 g. Examples of suitable zeolites are synthetic faujasites (zeolites X and Y) and the natural zeolites clinoptilolite, phillipsite and mordenite and an alkali metal ion exchanged form of chabazite. Especially preferred is zeolite 4A which generally has a cation exchange capacity in the region of 500 meq/100 g. If zeolite A is used as the aluminosiliceous material the amount required is generally smaller and will generally be in the range of 0.1 to 0.5% by weight. The cation exchange capacity of kaolin clays themselves is most commonly in the range from 5 to 15 meq/100 g. A zeolite 4A may be synthesised from a gel comprising sources of oxides of aluminium, silicon and sodium, but may also be prepared by treating metakaolin produced by calcining a kaolinitic clay with a sodium hydroxide solution under the conditions described, for example, in British Patent Specification No. 1603084. It has been found to be advantageous to use a finely divided zeolite having an average particle diameter in the range of from 1 to 4 micron. A zeolite 4A formed from metakaolin according to the process of British Patent Specification No. 1603084 will generally have an average particle diameter within this range but a synthetic zeolite may have to be comminuted to give a finely divided product having the desired average particle diameter. The aluminosiliceous material is preferably mixed with the kaolin clay before, or at the same time as, the dispersing agent is added. One of the advantages of the present invention, particularly when the aluminosiliceous material is a zeolite, is that it is not essential to separate the clay from the aluminosiliceous material after treatment therewith. It is, however, within the scope of the present invention to remove the aluminosiliceous material by means of, for example, a sieve, before the kaolin is contacted with the dispersing agent. Alternatively, the kaolin suspension could be passed through a column which was packed with zeolite granules and which ensured good mixing. The dispersing agent is preferably a polyelectrolyte such as, for example, an alkali metal or ammonium salt of a poly(acrylic acid) or of a derivative of a poly(acrylic acid) and the quantity required is generally in the range of from 0.05 to 1.0% by weight, based on the weight of dry kaolin clay. The invention is illustrated by the following Examples. EXAMPLE 1 A paper coating grade kaolin was prepared by subjecting an aqueous suspension of a raw kaolinitic clay to particle size separations to give a final product having a particle size distribution such that 80% by weight consisted of particles having an equivalent spherical diameter smaller than 2 microns and 0.02% by weight consisted of particles having an equivalent spherical diameter larger than 10 microns. The final product was found by chemical analysis to contain 70 ppm (parts by weight per million parts by weight of dry kaolin) of water-soluble calcium and 18 ppm of water-soluble magnesium. Suspension A An aqueous suspension was prepared containing 68.6% by weight of the dry kaolin product, sufficient sodium hydroxide to raise the pH of the suspension to 7.5 and 0.3% by weight, based on the weight of dry kaolin, of a sodium polyacrylate dispersing agent having a number average molecular weight of 1680. Suspension B A second suspension of the dry kaolin was prepared as described above except that 0.2% by weight, based on the weight of dry kaolin, of a zeolite 4A having an average particle diameter of 2 microns and a cation exchange capacity of 550 meq/100 g was mixed with the kaolin before the dispersing agent was added. Each of the two suspensions prepared as described above was used to form a paper coating composition suitable for a coated offset printing paper according to the following formulation: ______________________________________Parts by weight of dry solidsin each ingredient Ingredient______________________________________100 suspension A or B.11 styrene-butadiene rubber latex adhesive (approx. 50% by weight of solids latex)0.6 sodium carboxy- methylcellulose______________________________________ The paper coating of dry solids compositions were made up with water to about 62% by weight and sodium hydroxide to pH 8.5. The high shear viscosity of each paper coating composition was measured at a shear rate of 12840s -1 by means of a Ferranti-Shirley viscometer. The results obtained are set forth in Table 1 below: TABLE 1______________________________________ % by weight of dry Viscosity at 12840s.sup.-1 of solids pH shear rate (mPa.s)______________________________________With zeolite 4A 61.9 8.4 1032Without Zeolite 4A 62.2 8.5 too high to measure______________________________________ Each of the two paper coating compositions was coated on to an offset printing base paper having a substance weight of 86 gm -2 and a caliper of 100 microns using a "HELI-COATER" (Registered Trade Mark) laboratory paper coater of the type described in British Patent Specification No. 1032536 rotating at a speed of 400 rpm. Samples of paper coated with each of the two compositions were dried and inspected visually. The paper coated with the composition which did not contain the zeolite 4A was seen to have a surface which was severely marred by pitting and streaking while the paper coated with the composition containing the zeolite 4A had a surface which was substantially completely free from pitting and streaking. EXAMPLE 2 Two offset paper coating compositions, C and D, were prepared according to the method described in Example 1. Composition C contained as the pigment the paper coating grade kaolin of Example 1 untreated with zeolite 4A. Composition D contained as the pigment the same paper coating grade kaolin as used in Example 1, but which had been treated by contacting an aqueous suspension of the kaolin with zeolite 4A granules which were removed after treatment of the kaolin by means of a sieve. This treatment procedure was then repeated using a second batch of fresh zeolite 4A granules, following which the dispersing agent was added. Each paper coating composition was tested for high shear viscosity by means of the Ferranti-Shirley viscometer at a shear rate of 12840s -1 . The results obtained are set forth in Table 2 below: TABLE 2______________________________________ Viscosity at 12840s.sup.-1 shearComposition rate (mPa.s)______________________________________C too high to measureD 1050______________________________________ EXAMPLE 3 Further suspensions of the same paper coating grade kaolin as used in Example 1 were prepared by the method described in Example 1, but containing differing amounts of a bentonite clay having a cation exchange capacity of 97 meq/100 g, instead of zeolite 4A. Each suspension was used to form an offset paper coating composition as described in Example 1 and the high shear viscosity of each composition was measured at a shear rate of 12840s -1 by means of the Ferranti-Shirley viscometer. Samples of coated paper were then prepared with each composition using the same base paper and experimental method as used in Example 1. After drying each sample was inspected visually. The results obtained are set forth in Table 3 below: TABLE 3______________________________________ % by weightbentonite Viscosity atbased on % by weight 12840s.sup.-1weight of of dry shear Appearancedry kaoline solids pH rate (mPa.s) of coating______________________________________0 62.2 8.5 too high to severely measure streaked and stippled0.1 62.4 8.5 6328 streaked and stippled0.25 62.1 8.5 5255 some streaking and stippling0.5 62.1 8.6 4691 some very fine stippling______________________________________ EXAMPLE 4 Kaolin slurries which contained 70% by weight of beneficiated kaolins, Kaolin A and Kaolin B were prepared in each case by blending an aqueous suspension containing 55% by weight of the beneficiated kaolin with sufficient of a particulate material which was formed by spray drying a suspension of the same beneficiated kaolin to increase the solids content to 70% by weight. Kaolin A was a paper coating grade kaolin having a particle size distribution such that 94% by weight consisted of particles having an equivalent spherical diameter smaller than 2 microns and 84% by weight consisted of particles having an equivalent spherical diameter smaller than 1 micron. Kaolin B was a paper coating grade kaolin having a particle size distribution such that 93% by weight consisted of particles having an equivalent spherical diameter smaller than 2 microns and 75% by weight consisted of particles having an equivalent spherical diameter smaller than 1 micron. Samples taken from each of the two slurries were treated with varying quantities of zeolite 4A having a cation exchange capacity of 500 meq/100 g by adding the zeolite in the form of a dry powder to the sample of suspension and stirring the mixture for 3 minutes. Samples of each mixture were withdrawn and the viscosity of the sample was measured by means of : (a) a Brookfield Viscometer at a spindle speed of 100 rpm and (b) a Hercules Viscometer and the results obtained are set forth in Table 4 below: TABLE 4______________________________________% by weight Kaolin A Kaolin Bof zeolite Hercules Hercules4A(based on Viscosity Viscosityweight Brookfield (rpm for Brookfield (rpm forof dry Viscosity full scale Viscosity full scaleKaolin) (m Pa.s) deflection) (m Pa.s) deflection)______________________________________0 430 950 230 19400.25 430 1120 240 22000.5 410 1380 260 24401.0 500 1560 300 2440______________________________________ It is to be noted that a full scale deflection on the Hercules Viscometer represents a measured torque of 18×10 5 dyne cm. For a given rate of shear (measured in rpm) a higher scale reading represents a higher viscosity and the viscosity generally increases with the rate of shear. It can therefore by seen that the high shear viscosity of both slurries decreases with increasing dose of zeolite 4A, although the low shear viscosity, as measured with the Brookfield Viscometer, tends to increase with zeolite dose.
There is disclosed a method for improving the rheological properties of a clay mineral which, when dispersed with water, either releases into solution or retains on its surface multivalent cations, which method includes the step of treating the clay mineral in aqueous suspension with an aluminosiliceous material having a cation exchange capacity of at least 50 meq/100 g, said aluminosiliceous material being employed in an amount sufficient to react with a significant proportion of the exchangeable cations in the clay mineral. Also disclosed is an aqueous suspension of a clay mineral, a method for preparing a paper coating composition and a method for improving the rheological properties of a clay mineral.
3
This is a continuation of application Ser. No. 618,868 filed Oct. 2, 1975 and now abandoned. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates in general to the field of bubble memory devices, and in particular to bubble memory devices of the lattice type. 2. Description of the Prior Art In magnetic bubble lattice devices wherein information is stored in the domain wall structure of the bubble, the two information states representing "1" and "0" are represented by the presence or absence of a pair of Bloch lines. For purposes of this discussion, Bloch lines may be defined as a transition zone through which the magnetization at the center of the domain wall reverses direction. For reliable information storage, both states must be equally stable. In conventional prior art bubble lattice devices such as disclosed in U.S. 3,996,577 magnetic garnet films are grown on oriented substrates and are ion implanted (i.e., the film surface has been bombarded and implanted with ions). In such films, only one stable information state can be obtained. In order to obtain the second information state, an appropriate external in-plane field must be applied. The presence of the in-plane field has the effect of stabilizing this second information state without destroying the first state. If the in-plane field were not present, one information state would be overwhelmingly more stable than the other state. The requirement of an external in-plane field is an undesirable characteristic of the known prior bubble lattice devices since it requires additional fabrication steps or hardware. This results from the facts that additional conductors must be deposited on the substrate or a set of external field coils must be included. The conductor or external coils are an added cost because of the additional circuitry required to be connected thereto in order to energize it at the proper time. SUMMARY OF THE INVENTION Broadly, the invention employs a process for stabilizing S=0 and S=1 type bubbles in magnetic lattice devices wherein S is defined as the number of times the magnetic spin at the center of a domain wall turns through 2π radians. Process means are disclosed for providing bubbles of this type in a zero in-plane field. BRIEF DESCRIPTION OF THE DRAWING FIGS. 1(a) and (b) depicts the domain wall arrangement of the S=1 and S=0 lattice type bubbles. FIG. 2 is a block diagram of the process steps which are utilized with this invention. FIG. 3 is a boule (cylinder) of a 3G garnet substrate material. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to FIGS. 1(a) and (b) in greater detail there is shown the domain walls of two different types of bubbles found in bubble lattice devices. At the center of each domain wall are depicted the magnetic spins associated with each different type of bubble. S is called the revolution number and identifies the number of times the magnetic spin at the center of the domain wall turns through 2π radians as the complete wall is traversed. FIG. 1a depicts an S=1 bubble 5 since the magnetic spin undergoes a net change of direction of 2π radians. The dot inside the domain wall indicates that the magnetization is pointed outwardly from inside the bubble. The S=1 type bubble is considered the simplest bubble configuration and because the magnetic spin is slowly re-oriented, around the center of the domain wall, the energy to form this domain wall structure is a minimum. The S=0 bubble type 6 shown in FIG. 1(b) indicates that there is no net rotation as the spin is followed completely around the center of the wall. This spin configuration has a higher energy than that of the S=1 bubble accounting for the difference is stability. The two binary states of "1" and "0" are represented by the absence or presence of a pair of Bloch lines. One state is represented by the presence of an identical pair of Bloch lines shown in FIG. 1(b), whereas the second state is represented by the absence of such a pair of Bloch lines as seen in FIG. 1(a). Referring now to FIG. 2, there is shown the process steps that are utilized in arriving at the bubble memory which is the subject of this invention. The first process step consists in synthesizing the non-magnetic substrate, which in the present embodiment is comprised of a gadolinium gallium garnet, Gd 3 Ga 5 O 12 (hereinafter 3G) by forming a cylindrical boule 7 of such material as seen in FIG. 3. The boule 7 is formed in a conventional manner by slowly rotating a 3G seed having a cubic crystallographic structure in a melt of Gd 3 Ga 5 O 12 over a long period of time. Eventually, a boule will be formed from which substrates can be obtained by slicing at the desired angle. The boule 7 is grown so that its longitudinal axis is along the [111] direction. The [111] direction defines the diagonal of the cube which has one unit of distance respectively in the x, y, z direction. Therefore, the diagonal of the cubic garnet crystals which comprise the boule cylinder 7 are along the longitudinal axis. The next step in the process of this invention comprises intentionally tipping the [111] direction. This is readily achieved for slicing the boule at an angle, as shown in FIG. 3 into substrates of useable thickness. In the preferred embodiment of this invention the [111] direction has been tipped by approximately 4 degrees from the normal. This is accomplished by slicing the boule 7 at the 4 degree angle with respect to the [111] growth direction. The typical substrate size is from 1-2 inches in diameter, and from 10-20 mils thick. Referring again to FIG. 2 it is seen that the process step comprises depositing the magnetic bubble film on the tilted substrate. A magnetic garnet bubble film is deposited by a known process on the nonmagnetic garnet substrate. In the preferred embodiment of this invention the bubble material used is Y 2 .38 La 0 .09 Eu 0 .53 Fe 3 .9 Ga 1 .1 O 12 (Yttrium, Lanthanium, Europium, Iron, Gallium Garnet). The magnetic bubble material is deposited on the non-magnetic substrate by the well-known liquid phase epitaxy process (i.e., the magnetic film assumes the same crystallographic structure as the substrate, i.e., cubic). Liquid phase epitaxy is accomplished, for example, by dissolving oxides of the various metal and rare earth ions that are desired in the garnet film. Enough oxides are dissolved so that the solution becomes supersaturated (a solution containing more solid than the quantity that can be dissolved normally at a given temperature) and then the solution is supercooled (cooling the liquid below its freezing point without causing solid matter to separate). At this point, the nonmagnetic 3G substrate is lowered into the melt. It is rotated around the vertical axis at about 100 RPM and epitaxial growth occurs provided the proper concentration of the various oxides exist in the supercooled melt. It has been found that films grown on tilted substrates have their EASY axis tipped several times as much as the substrate tilts. It has been found that a 4 degree substrate tilt produces a 22 degree tilt of the bubble film's EASY axis. Therefore, there is a component of the EASY axis in the plane of the substrate. FIG. 2 indicates that after the tilted magnetic bubble film has been deposited on the substrate, it is implanted with ions. Ion implantation is the technique of shooting electrically charged atoms formed when neutral atoms gain or lose an electron into the surface of the bubble film. The ions are shot into the bubble surface a distance of 1,000 A. The implanted ions cause the bubble film to develop strains in its upper layer. Since the films are magnetostrictive (i.e., a change in magnetic properties produced by mechanical stress), the implanted ions cause a compressive stress in the upper layer of the film. This causes the surface magnetization to be oriented in the plane of the film instead of pointing normal to the film. In summary, by ion implanting the tilted bubble films as above described, two stable bubble types (i.e., S=0 and S=1) are present in a zero in-plane field arrangement. The S=1 bubble is a type that is normally found in ion-implanted conventional films. The S=0 bubble is a type which is stabilized by the combination of the in-plane magnetization of the implanted layer and the in-plane component of the growth induced anisotropy (arising due to a preferential ordering of the rare earth ions Y, L a , Eu) which arises from the EASY axis tilt.
The disclosure teaches how binary information may be stabilized in magnetic bubble lattice devices. In bubble lattice devices, information storage is determined by the state of the domain wall structure of the bubble. Fabrication means are disclosed for stabilizing two different types of bubbles found in such films.
7
BACKGROUND OF THE INVENTION This invention concerns a device for simplified adjustment and set-up of a sewing machine with known drive and control systems in conjunction with machine parts and adjustment devices assigned to these control systems. The adjustment possibilities of modern sewing machines with regard to the sewing operation and material to be sewn are so extensive that for a minimum number of typical sewing operations and materials, the operator must be provided with data on machine adjustment, the use of certain accessories, a particular thread type and similar operations. Such data is commonly provided in a table on the inside of a hinged cover of the sewing machine (U.S. Pat. No. 4,079,683) or in the form of a folded table under the cover (U.S. Pat. No. 3,871,310). However, such tables are disadvantageous for various reasons. Only a very limited number of combinations of sewing operation prerequisites for adjustment and set-up instructions can be compiled in such a table. The larger the table and consequently the combination of predefinable conditions and readable information, the more unsurveyable, thus increasing the possibilities for errors to occur. It is not especially practical if additional operations in the machine must be performed for machine set-up, e.g. the opening of a cover. Errors, mistakes and omissions can easily occur when individual adjustment units are set-up according to numerical table data. SUMMARY OF THE INVENTION The objective of this invention is to prevent the above-mentioned disadvantages of existing concepts by creating a device which handles a substantially broader scope of data and simultaneously precludes reading and/or adjustment errors and the need for additional machine alterations by ensuring automatic sewing machine adjustments. This objective is attained by an input device for different variable data such as material type, sewing operation to be performed, etc. and memories which are addressed and programmed by the input unit. These memories handle storage of optimum adjustment values or ranges which are necessary for performing different sewing operations on different materials and which are required for the sewing machine as well as operation-related accessories such as the foot, needle, thread, etc. The device is also distinguished by adjustment mechanisms as well as optical displays assigned to set-up devices located to some extent on the sewing machine. These adjustments can be memory-controlled for adjusting machine parts within the above-mentioned adjustment values or ranges and their displays are also memory-controlled for indication of the necessary accessories. Individual data or conditions for the sewing operation can be consecutively entered after which machine parts are automaticlly adjusted; instructions are unmistakeably displayed preferably on the adjustment and setup devices themselves, thus precluding the possibility of errors and thereby ensuring optimum machine adjustment and set-up even by personnel with limited experience in sewing machine operation. A more detailed description of the invention will now be given on the basis of the example in the illustration. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 shows a perspective view of the sewing machine; FIG. 2 shows a top view of the keyboard in larger scale; FIGS. 3-8 show adjustment mechanims used for machine part adjustment; FIG. 9 shows a section of the keyboard model variant; FIG. 10 shows a schematic of a monitoring system. DESCRIPTION OF THE PREFERRED EMBODIMENT The sewing machine shown in FIG. 1 has conventional adjustment and set-up elements, i.e. needle bar 21 which permits attachment of needle 22; pressor foot bar 23 which accepts the replaceable foot; adjustment thumbwhell 24 for thread tensioning; selection lever 25 for standard and fancy stitching; rotary adjustment knobs 26 and 27 for stitch width and needle deflection; adjustment knob 29 for stitch length selection; selector knob 29a for switchover to reverse stitching and switchover knob 30 for sewing or darning/freehand stitching. Buttonhole symbol 28 is anticipated in place of a control knob for buttonhole sewing and illuminates when selecting a buttonhole program. The buttonhole is automatically sewn in the conventional manner according to the size of the button inserted in the buttonhole foot. A keyboard with sections 1-5 is located on the protruding panel 31 of the housing. As shown in FIG. 2, section 1 pushbuttons permit data entry of material type, i.e. wovens, knits and foil or leather. Section 2 pushbuttons permit the entry of additional data on material type, i.e. cotton, wool or mixture, synthetics or silk. Section 3 pushbuttons permit data entry of material thickness, i.e. lightweight, medium and thick material. Section 4 pushbuttons permit data entry of the density of wovens or knits. Section 5 pushbuttons permit data entry of the many diverse sewing operations indicated in part by symbols and in part by words. The LED or liquid crystal displays comprise a display 34 on the machine housing above the foot. This 2-digit display is designated by a foot symbol and indicates the foot number provided on the foot by suitable means. Display 35 located above the needle bar is the needle display which is also designated by a symbol. A 2-field display indicates needle thickness and type. Display 36 located on the housing section 31 indicates the thread to be used and is also identified by a symbol. A 3-field display provides additional data on the strength and quality of the thread to be used. Needle and thread types are digitally displayed in code for which the key text is located on the unit itself, on the accessory container or in the operating instructions. Display 37 is activated when the bobbin thread guide designated by a stylized symbol must be used for sewing operations, e.g. buttonhole sewing. Displays 38 and 38a designed as scales for the respective adjustment knobs 26 and 27 have a number of display fields which can be individually activated to display the stitch width and needle deflection. Display 28 illuminates when the buttonhole program is selected. Display 40 which has a scale of individually operative fields, indicates stitch length, whereby the scale position of adjustment element 29 must correspond with the position on the scale of display 40. Display 41 indicates the position in which adjustment element 30 must be set for material feed to be operative or inoperative; one position is for darning and freehand stitching and the other is for sewing. Display 42 indicates the thread tension and the value to be adjusted between 0-8 is indicated by an illuminated field of the scale. Thread tensioning can be adjusted by thumbwheel 24 immediately adjacent to the display. Display 43 indicates the number or symbol of the stitch pattern to be set. All adjustment elements 24, 25, 26, 27, 29, 29a and 30 have an electromechanical adjustment mechanism. The electronics system located in housing section 31 has a memory for storage of instructions assigned to different combinations of data to be entered for sewing machine adjustment. These instructions contained in the memories can control adjustment mechanisms used for adjusting the assigned elements into the proper positions as well as the control of above-mentioned displays of these adjustment mechanisms or elements. FIGS. 3-8 show the electromechanical adjustment mechanisms assigned to the adjustment elements which are designed as stepper motors, electromagnets or other motors and are described in the following examples: FIG. 3 shows the thread tensioning adjustment mechanism. Wheel 24 shown in FIG. 1 is rotary-mounted on spindle 50 and is designed as a one-piece unit with gear wheel 51 which engages in gear wheel 52 on the shaft of stepper motor 53. Wheel 24 is coupled to nut 54 located on the threaded section of spindle 50. Nut 54 acts on the thread tension disk by means of spring 55 and sleeve 56. Permanent magnet 58 installed in wheel 24 acts together with a positioning sensor 59 which displays the zero position of wheel 24 if permanent magnet 58 is opposite to positioning sensor 59. By manual rotation of wheel 24 or automatic rotation by means of stepper motor 53, nut 54 is rotated on spindle 50 and is axially shifted so that thread tensioner 57 is more or less tensioned. During each automatic adjustment procedure, stepper motor 53 first proceeds into the zero position in the initialization phase and then makes the required number of steps from this position. FIG. 4 shows switchover knob 30 for preselecting sewing or darning/freehand stitching. Pinion 60 with which toothed segment 61 engages in one of the levers 63 mounted on pin 62 is located on the shaft of switchover knob 30. The limit positions of lever 63 are defined by stop pins 64. Two electromagnets 65 and 66 can influence lever 63, and the limit positions of the lever are determined by toggle lever compression spring 67 which, in turn, acts on it. Switchover can be performed either manually or by keyboard preselection according to FIG. 2. In the latter case, one or the other magnet 65 or 66--according to the preselection--is activated and lever 63 is switched over if it is not already in the correct position. When lever 63 is tilted, switchover knob 30 is rotated by 180° into the other operating position by toothed segment 61 and pinion 60. FIGS. 5 and 6 show the adjustment mechanism for adjusting selector lever 25 or for preselection of certain standard and fancy stitches. Lever 25 with sensor 70 which acts together with one cam disk of cam disk set 71 can be shifted on rocker frame 73 fastened to spindle 72. Spindle 72 is also connected to zigzag slide 74 which transfers the zigzag motion with varying amplitude according to the rocker arm position via rocker arm 75 (see FIG. 6) and rod 76. One chain link or hole of perforated belt 77 engages at lever 25. The chain travels over sprocket wheels 78 one of which can be driven by stepper motor 79. Permanent magnet 80 located on lever 25 is only situated in front of positioning sensor 81 if sensor 70 of the lever 25 is on the first cam disk 71. Tension spring 82 acts on rocker frame 73 which usually maintains contact between sensor 70 and a cam disk. However, the rocker frame can be tilted clockwise by means of electromagnet 83 laterally lifting sensor 70 into a position removed from the cam disk set to permit rocker frame adjustment. Electromagnet 83 is activated for automatic readjustment after which stepper motor 70 shifts lever 25 and sensor 70 into the zero position by means of perforated belt 77. Elements 80 and 81 report this status to the electronics system. Then, step-by-step adjustment is performed to the preselected position, whereby sensor 70 is brought into the zone of desired cam disk 71. FIG. 7 shows the adjustment mechanism for adjustment knobs 26 and 27 for the stitch or zigzag width or the needle deflection. Adjustment knob 26 is located on hollow shaft 90 together with toothed segment 91 which can be driven by stepper motor 93 via pinion 92. The spring-loaded brake which can be activated by electromagnet 93 acts on toothed segment 92. Toothed segment 92 adjusts stitch width in the well-known manner by means of the linage which is not illustrated. Adjustment knob 27 is located on spindle 94 to which toothed segment 95 is also attached. Pinion 96 of stepper motor 97 engages in toothed segment 95. Toothed segment 95 is provided with engagement toothing 98 into which a spring-loaded engagement pin 99 engages. This pin can be actuated by electromagnet 100. Toothed segment 95 adjusts the needle deflection in a well-known manner by means of a linkage which is not depicted. Both toothed segments 91 and 95 are each provided with a magnet 101 which acts on a positioning sensor 102. To adjust stitch width and needle deflection, electromagnets 93 and 100 are activated to release the respective toothed segment after which the assigned stepper motors 93 or 97 first bring the segment into the zero position. This status is reported by positioning sensor 102 and the stepper motor then brings the assigned toothed segment into the preselected position so that adjustment is obtained. FIG. 8 shows the adjustment mechanism required for stitch length preselection. Adjustment knob 29 is positioned on hollow shaft 110 while knob 29a is located on rod 111 which passes through shaft 110. The inner end of rod 111 acts together with bracket 112 of stitch position slide 113. Return spring 114 acts on knob 29a. Hollow shaft 110 has a control groove limited by two opposing, inclined surfaces 115 and 116. Normally, sensor 117 of stitch position slide 113 makes contact with surface 115 due to tension spring 118 which controls normal advance sewing if guide groove 113a of stitch position slide 113 is inclined for rocker arm 120a of stitch position fork 120 according to FIG. 8. The inclination of groove 113a and thereby the stitch length can be selected in a well-known manner by rotating hollow shaft 110 or its surface 115, thus adjusting the inclination of stitch position slide 113. By actuating knob 29a or activation of electromagnet 121, stitch position slide 113 can be temporarily pivoted into the opposite, inclined position in which case sensor 117 makes contact with surface 116 and reverse sewing with shorter or longer stitches results. Hollow shaft 110 is provided with gear wheel 119 which is engaged in pinion 112 or stepper motor 123. Spring-loaded brake 124 acts on a flange of hollow shaft 110 and can be actuated by an electromagnet 125. Furthermore, a zero position indicator with magnet 126 and positioning sensor 127 is anticipated. For automatic stitch length adjustment, brake 124 is released by activation of magnet 125 after which stepper motor 124 first brings the hollow shaft into the zero position and then into the preselected position. By activation of magnet 121 switchover to reverse sewing can be accomplished by activating magnet 121. A positioning annunicator can be anticipated in all cases which responds when the desired position is obtained and reports this status to the electronics system. Such an annunciator 130 is illustrated as an example in FIGS. 5 and 6. This device reads code indications from perforated belt 77 and transmits coded position signals to the electronics system. Position annunciators can be anticipated for other adjustment mechanisms whereby code indications are provided on gear wheels, flanges and similar units or on special code disks. The machine can be activated in the automatic buttonhole sewing mode according to FIG. 2 by pushbutton actuation, e.g. according to one of the U.S. Pat. Nos. 4,182,087, 3,841,146 or 4,056,070, whereby a display can illuminate above presser foot bar 23, thereby indicating that a respective foot must be mounted for buttonhole sewing. However, instead of only one pushbutton, three pushbuttons for buttonhole sewing can be anticipated in a slightly modified keyboard according to FIG. 9, whereby pushbutton 140 controls adjustment for each of the buttonhole bar tack stitches; and pushbuttons 141 and 142 control left and right bead stitching. In this case, the operator must only actuate the respective pushbutton and the adjustment for the individual sewing operation to be carried out is automatically performed by means of the above-mentioned mechanisms. It would also be possible to control the adjustment for individual operations by repeated actuation of a single pushbutton assigned to buttonhole sewing according to FIG. 2. To perform sewing machine adjustment, the operator enters all data by means of pushbuttons 1-5, i.e. material type, material thickness and sewing operaton to be performed. When this procedure is completed, i.e. after the corresponding pushbuttons of sections 1-5 have been actuated, the display for sewing machine adjustment and set-up automatically appears. The individual displays have already been discussed. If necessary, the operator interchanges accessories and thread and checks adjustments according to displays 28-33. Adjustment can be adapted to special conditions if required. It is obviously apparent that the described device permits highly diverse selection of conditions and displays of instructions under the preclusion of errors. Should special conditions not permit mounting on the sewing machine, the keyboard and electronics system could be accommodated in a separate unit connected to the sewing machine by a fixed or movable power cord. Displays 36 and 37 can be situated at other positions on the sewing machine and more precisely near those positions where thread or bobbin thread guide are located. A different input system, e.g. one which employs sensors, a telephone dial or similar devices can be used in place of the described keyboard. Variable data can be recorded on a digit conversion table and input in this case occurs in digital sequence, i.e. with the above-mentioned dial. The digit conversion table can be provided on a section of the sewing machine or on the above-mentioned device. An annunciator system with an optical signal transmitter could be anticipated which checks and indicates whether or not the sewing machine is properly adjusted to perform the sewing operation to be carried out, i.e. whether all adjustments have been carried out according to instructions contained in the memories. It may be advantageous to contemplate sequential data entry and/or to provide for sequential sewing machine adjustments as well as display of required accessories. Sequential data entry would be possible with a substantially simplified and clearly surveyable keyboard, and sequential adjustment permits operation with relatively minimal power output and simplified electronics system so that the design of the device can be relatively compact. Automatic sewing machine adjustment shall only occur if the needle bar is in the upper limit position or at any rate in the vicinity of this position. Such an interlock can only occur if the upper end of the needle bar is sensed in its limit position by a light barrier which disables electronics system outputs when the needle bar is not in the light barrier. A respective schematic of this concept is shown in FIG. 10. In the upper limit position, the upper end of needle bar 150 enters between light source 151 and casing 152 provided with a light entry slot. Photodiode 153 controls signal lamp 155 by means of amplifier 154. The circuit can operate in such a manner that the signal lamp is illuminated as long as the needle bar is not in the upper limit position.
The device for simplification of adjustment and set-up of a sewing machine comprises a keyboard allowing introduction of information relating to the sewing operation to be performed to the material to be sewn and the like. The information introduced are applied to addresses of memory means, and data relating to the adjustment and set-up of the sewing machine are transmitted to adjusting means and displays illustrating set-up and adjustment. The sewing machine is automatically adjusted and may be set-up by the operator in accordance with the setting-up data indicated on displays provided on the sewing machine. In this way, adjustment and setting-up of the sewing machine is rendered easy and reliable.
3
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for the production of polyurethanes using substituted triamino(imino)phosphoranes as catalysts. These catalysts may be used as a substitute for, or in combination with, urethane catalysts known per se, for example for the production of rigid or flexible polyurethane foams and many other polyurethane products. In the context of the invention, polyurethane products are understood to be any reaction products of polyisocyanates of compounds containing at least two isocyanate-reactive hydrogen atoms, i.e., the term polyurethane as used in the present context is understood to encompass, for example, pure polyurethanes, polyurethane polyureas or pure polyureas. 2. Description of the Prior Art The rate of reaction between isocyanate groups and compounds containing NCO-reactive hydrogen atoms is influenced not only by the temperature of the starting products and their structure, but more importantly by suitable catalysts. In practice, bases (for example tertiary amines such as triethyl amine) are predominantly used as nucleophilic catalysts while organometallic compounds (for example Sn carboxylates such as Sn(III) octoate) are predominantly used as electrophilic catalysts. The combined use of Lewis acids and Lewis bases, which is normally characterized by synergistic effects, is known. However, it is also known that, in many applications, amines are solely used as catalysts. Of the large number of known amine catalysts (cf. Kunststoff-Handbuch, Vol. VII, Polyurethane, Hansen-Verlag, Munchen, 1983, pages 92-98), relatively few have previously been adopted for wide scale use in practice. Those which have include 1,4-diazabicyclo[2.2.2]-octane (DABCO), bis-(2-dimethylaminoethyl)-ether, triethyl amine, dimethyl cyclohexyl amine, dimethyl ethanolamine, dimethyl benzyl amine, methyl morpholine and ethyl morpholine to name the most important. Catalysts distinguished by high activity, economic production and broad spectrum application are of course used above all. Another aspect gaining in importance is the toxicological evaluation of the catalysts in regard to processing safety and odor emission. Many of the amine catalysts used today, including DABCO and triethyl amine, are unsatisfactory due to their high volatility and their relatively strong amine odor which is transmitted to the end product produced therefrom. In view of the many potential applications of polyurethane plastics, it is equally desirable to provide catalysts "custom-made" to suit particular requirements. One possibility is to chemically modify a given type of catalyst to adapt its activity to the particular application envisaged. Another class of compounds suitable as basic polyurethane catalysts are the bicyclic amidines described in DE-OS 1,745,418 which are comparable in activity with the strongest of the previously known amine bases and which also have a considerably weaker odor. However, a serious disadvantage of these compounds which has previously restricted their application lies in their poor hydrolysis stability which, in view of the frequent use of water as a blowing agent or chain extender in polyurethane systems, largely precludes their use because the corresponding formulations are not stable in storage. It has now surprisingly been found that certain triamino(imino)phosphoranes may be used with advantage as catalysts for the production of polyurethanes and also polyepoxide resins. The compounds to be used in accordance with the invention show high stability to hydrolysis and, thus, are not sensitive to atmospheric moisture or water. In addition, they show even higher catalytic activity when compared to the bicyclic amidine bases mentioned above. Another welcome effect of the catalysts proposed in accordance with the invention is that, in contrast for example to DABCO which may not be chemically altered under economically reasonable conditions, the activity of the products can be "tailored" by the choice of suitable substituents at the nitrogen. Further advantages of the compounds are their weak odor and their low volatility which leads to a distinct reduction in odor emission during the production of polyurethane products. Further advantages include ease of handling (because the triamino(imino)phosphoranes used are liquid), good hardening behavior and also the very simple production of some of the compounds. SUMMARY OF THE INVENTION The present invention is directed to a process for the production of polyurethanes using substituted triamino(imino)-phosphoranes corresponding to formulas I, II or III ##STR2## wherein R represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl groups or alkylaryl groups, R' represents linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, cycloalkylene groups containing 4 to 6 carbon atoms, R" represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl groups or alkylaryl groups, R"' represents linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl groups or alkylaryl groups and n and m may be the same or different and represent 0, 1 or 2, as catalysts. The present invention also relates to compounds corresponding to general formula (II) wherein R represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups, R' represents linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms or cycloalkylene groups containing 4 to 6 carbon atoms, R" represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl groups or alkylaryl groups, R"' represents linear or branched alkyl groups containing 2 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups, aryl or alkylaryl groups and n is 0, 1 or 2; compounds corresponding to general formula (II) wherein R represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups, R' represents a methyl group or branched alkyl groups containing 3 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms or cycloalkylene groups containing 4 to 6 carbon atoms, R" represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups, R"' represents linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups and n is 0, 1 or 2; and compounds corresponding to general formula (III) wherein R represents hydrogen, linear or branched alkyl groups containing 2 to 8 carbon atoms, cycloalkyl or alkyl cycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups, R' represents linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms or cycloalkylene groups containing 4 to 6 carbon atoms, R" represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups, R"' represents hydrogen, linear or branched alkyl groups containing 1 to 8 carbon atoms, cycloalkyl or alkylcycloalkyl groups containing 5 to 9 carbon atoms, aryl or alkylaryl groups and n and m may be the same or different and represent 0, 1 or 2. DETAILED DESCRIPTION OF THE INVENTION Preferred catalysts are: N,N',N"-hexamethyl-triamino(methylimino)phosphorane ##STR3## N,N',N"-hexaethyl-triamino(methylimino)phosphorane ##STR4## N,N',N"-hexamethyl-triamino(t-butylimino)phosphorane, 2-t-butylimino-2-diethylamino-1-methylperhydro-1,3,2-diazaphosphorine ##STR5## 2-t-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, 7-ethyl-5,11-dimethyl-1,5,7,11-tetraza-6-phosphaspiro-[5.5]undec-1(6)-ene ##STR6## The triaminoiminophosphoranes corresponding to general formulae (I) to (III) are prepared by known reaction mechanisms. Compounds corresponding to general formula (I) may be prepared, for example, by reaction of phosphorous acid triamides (prepared from phosphorus trichloride and secondary amines) with N-substituted chloroamines or alkylazides with elimination of hydrogen chloride and nitrogen in accordance with the following equation: ##STR7## wherein Y represents HCl, N 2 [see K. Issleib, M, Lischewski, Synth. Inorg. Met. Org. Chem. 3 (1973) 255; P. Hassmann, 3. Goueau, Z. anorg. allg. Chem. 408 (1974) 293] or by treatment of triaminohalophosphonium halides prepared by halogenation of the phosphorous acid triamides mentioned above with primary amines or ammonia in accordance with the following equation: ##STR8## wherein x represents halogen (see G.N. Koidan et Ja., Zh. Obsh. knim. 52 (1982) 2001). Compounds corresponding to general formula (II) may be prepared in a multistep synthesis (see R. Schwesinger, Chimia 39 (1985) 269) from N-substituted iminophosphorus trichlorides by treatment with a secondary amine and subsequent reaction with an N-monosubstituted-α,ω-diaminoalkane in accordance with the following equation: ##STR9## wherein R" represents hydrogen. The compounds thus obtained (R"=H) may optionally be converted by treatment with suitable alkylating agents into compounds corresponding to formula II wherein R" represents H. Compounds corresponding to general formula III may be obtained by a multistep synthesis also described by Schwesinger from phosphorus pentachloride and N-monosubstituted-α,ω-diaminoalkanes in accordance with the following equation ##STR10## The resulting compounds corresponding to formula III (R"=H) may optionally be converted by treatment with suitable alkylating agents into compounds corresponding to formula III in which R"=H. To improve the yield of the monoalkylation, one of the two reactive nitrogen atoms may have to blocked by a suitable protective group. After alkylation of the second reactive nitrogen atom, the protective group is removed again by standard methods. The described processes for the production of the triaminoiminophosphoranes corresponding to general formulas I to III enable a variety of previously unknown compounds to be synthesized. It is possible to adapt the properties of the triaminoiminophosphoranes to the application envisaged through the choice of various amines and by modification of the substituent R". The new catalysts according to the invention are colorless compounds, the preferred types being liquid. They are soluble in organic solvents and are soluble or dispersible in water. The quantity of these compounds used as catalysts is generally about 0.01 to 5% by weight, based on the compound containing the active hydrogen atoms. Although it is possible to use more than the quantity mentioned above, this does not afford any advantages. The compounds containing active hydrogen atoms or isocyanate-reactive groups which are used as component b) in the process according to the invention are known and have previously been used for the production of polyurethanes. Note, for example, Kunststoff-Handbuch, Vol. VII, Polyurethane, Hansen-Verlag, Munchen, 1983, pages 42-62 or in Houben-Weyl, Makromolekulare Stoffe, Vol. E20, pages 1595-1604. The compounds containing NCO groups used in accordance with the invention as component a) are also known and have previously been used for the production of polyurethanes. Note, for example, Kunststoff-Handbuch, Vol. VII, Polyurethane, Hansen-Verlag, Munchen 1983, or in Houben-Weyl, Makromolekulare Stoffe, Vol. E20. In the process according to the invention, the substituted triamino(imino)phosphoranes are used in the same way as known catalysts. For example, the catalyst may be used as such in its liquid form or by dissolution in a polyol or suitable solvent. It may be used at any temperature--or other conditions --either individually or in combination with known catalysts for the production of polyurethanes, including for example organic or inorganic tin compounds or other organometallic compounds; tertiary amines; alkanolamines; cyclic amines; polyamines; alkali metal compounds; and other co-catalysts. The process according to the invention is suitable for conventional production methods, including the one-shot process or prepolymer process for the production of polyurethane foams, polyurethane elastomers, polyurethane coatings, etc., and for cross-linking reactions which are often desirable after the initial polyaddition reaction. All other conditions are the same as in conventional urethane polyaddition processes. In each of these cases, it is possible to use other known such as chain-extending agents, blowing agents, foam stabilizers, emulsifiers, dyes, pigments and fillers. The above-mentioned catalysts according to the invention accelerate the polyaddition to a considerable extent, so that the quantity of catalyst required is very small. Since the compounds according to the invention have only a weak odor and because they are not volatile liquids or solids, the polyurethane products obtained are free from unwanted odors. The following examples are intended to illustrate the invention without limiting it in any way. In all of the examples, parts and ratios are by weight. EXAMPLES Example 1 This example demonstrates the catalytic activity of the triamino(imino)phosphoranes according to the invention in a PUR cold-cure flexible molded foam system using N,N',N"-hexamethyl triamino(methylimino)phosphorane (prepared by the method described in the specification) which has the following physical characteristics: Bp. (0.3 mm): 60 to 62° C. ______________________________________CHNP analysis: calculated found______________________________________C 43.7 44.1H 10.9 11.0N 29.1 29.0P 16.1 16.0______________________________________ Component A: 37.10 parts of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a ratio of 80:20 and 4,4'-diisocyanatodiphenyl methane having polymeric components and an NCO content of 44.5±0.5% by weight; a commercial product of Bayer AG. Component B: 100.00 parts of a polyether polyol, OH value 28 ±2 mg KOH/g, prepared by reaction of trimethylol propane (TMP) with propylene oxide (PO) and subsequent reaction with ethylene oxide (EO), PO/EO ratio 82:18 3.00 parts water 0.05 parts of a 70% solution of bis-(2-dimethylaminoethyl)-ether in dipropylene glycol (DPG) 0.25 parts of a 33% solution of diazabicyclo-[2.2.2]-octane (DABCO) in DPG 0.20 parts foam stabilizer B 4617, a product of Goldschmidt AG x parts of the triamino(imino)phosphorane described above. Component A was combined with component B and the two components were thoroughly mixed for 10 seconds with a high-speed stirrer. The reaction mixture was then foamed at room temperature in an open mold. The results obtained with various additions of the triamino(imino)phosphorane are shown in Table I below. TABLE I______________________________________x (parts) 0 0.2 0.4 0.6Cream time (secs) 9 7 5 4Gel time (secs) 135 60 48 40Rise time (secs) 180 130 100 90______________________________________ The strong catalytic activity of the catalyst is clearly apparent. Example 2 This example demonstrates the activity of the new catalysts by comparison with diazabicyclo-[2,2,2]-octane (DABCO) in a PUR cold-cure flexible molded foam. Processing is carried out as in Example 1. Foam 1 containing the catalyst of Example 1 according to the invention: Component A: 33.40 parts of the isocyanate of Example 1 Component B: 100.00 parts of the polyol of Example 1 3.20 parts water 0.12 parts of a 70% solution of bis-(2-dimethylaminoethyl)-ether in dipropylene glycol (DPG) 0.10 parts of the foam stabilizer of Example 1 0.30 parts of the catalyst of Example 1 Foam 2 containing DABCO for comparison: The formulation was the same as used for foam 1, except that the catalyst according to the invention was replaced by 0.5 part of a 33% solution of DABCO in dipropylene glycol. Both foam 1 and comparison foam 2 had open cells and were highly elastic. The cells were of normal size. The cream, gel and rise times are shown in Table 2. TABLE 2______________________________________ Foam I Comparison Foam 2______________________________________Cream time 5 secs 5 secsGel time 50 secs 50 secsRise time 85 secs 85 secs______________________________________ This example shows that the catalysts according to the invention are at least as active as DABCO. Example 3 This example demonstrates the catalytic effect of the compounds according to the invention in an aliphatic flexible foam: Component A: 41 parts isophorone diisocyanate pre-reacted with a polyether polyol (OH value 670 g KOH/g), prepared by the propoxylation of glycerol to form a semiprepolymer having an NCO content of 29% by weight. Component B: 80.00 parts of a polyether polyol (OH value 268 g KOH/g), prepared by the reaction of trimethylol propane with propylene oxide (PO) and subsequent reaction with ethylene oxide (EO), PO/EO ratio 78:22 ______________________________________7.00 parts ethylene glycol0.50 parts dibutyl tin dilaurate5.00 parts trichlorofluoromethane0.50 parts of the catalyst of Example 1.______________________________________ Processing was carried out as in Example 1. The cream time of the system was 10 seconds and the rise time 2 minutes. Example 4 This example demonstrates the catalytic activity of another representative of the triamino(imino)phosphoranes, i.e., 2-t-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, in a flexible foam system. This catalyst was prepared by the method described in the specification. GC purity:>98% Bp (0.03 Torr): 72° C. Component A: 18 parts of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a ratio of 80:20 Component B: 50.00 parts of a polyether polyol (OH value 35 mg KOH/g) prepared by the reaction of trimethylol propane with propylene oxide (PO) and subsequent reaction with ethylene oxide (EO), PO/EO ratio 86.55:13.45 1.50 parts water 0.50 parts of a polyether polysiloxane as stabilizer, Stabilisator OS 50, a product of Bayer AG 0.30 parts of the triamino(imino)phosphorane described above. Component B was stored at room temperature and, after various periods of storage, was processed as in Example 1 with the addition of 0.05 parts tin(II) octoate. ______________________________________ Cream time Rise time______________________________________Comparison 6 secs 105 secs(0 days)Storage time: 1 day 6 secs 101 secs 8 days 6 secs 103 secs20 days 7 secs 104 secs______________________________________ It can be seen that storage of the water-containing component B for three weeks had no effect on the catalytic activity of the catalyst according to the invention. Example 5 This example demonstrates the hydrolysis stability of the catalysts according to the invention by comparison with 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU). The following aqueous solutions were prepared: Solution 1: 0.3 parts catalyst of example 1 in 1.5 parts water Solution 2: 0.3 parts catalyst of example 4 in 1.5 parts water Solution 3: 0.3 parts DBU in 1.5 parts water Component A: 18 parts of the isocyanate of Example 4 Component B; ______________________________________50.00 parts of the polyol described in Example 50.50 parts of the stabilizer of Example 50.05 parts tin(II) octoate1.80 parts of solution 1, 2 or 3.______________________________________ After the aqueous solutions had been stored for various periods, the following results were obtained: ______________________________________ Cream time Rise time______________________________________Comparison without storageSolution 1 5 secs 70 secsSolution 2 6 secs 105 secsSolution 3 10 secs 90 secsAfter 4 daysSolution 1 6 secs 105 secsSolution 2 6 secs 108 secsSolution 3 12 secs 195 secsAfter 18 daysSolution 1 6 secs 105 secsSolution 2 6 secs 105 secsSolution 3 23 secs 210 secs______________________________________ In contrast to the catalysts according to the invention, DBU underwent a marked reduction in its catalytic activity in aqueous solution. Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
The present invention is directed to a process for the production of polyurethanes using catalysts based on triamino(imino)phosphoranes corresponding to formulas I, II or III ##STR1## wherein R, R', R" and R"' represent hydrocarbon substituents and n and m may be the same or different and represent 0, 1 or 2. The present invention also relates to certain of the triamino(imino)phosphoranes used as catalysts.
2
FIELD OF THE INVENTION [0001] This invention relates to the treatment of wells penetrating subterranean formations and more particularly to the isolation of an interval within a well for the introduction of a treating fluid into an adjacent formation. BACKGROUND OF THE INVENTION [0002] Various treatment procedures are known in the art for the treatment of a well penetrating a subterranean formation. One common treatment procedure involves the hydraulic fracturing of a subterranean formation in order to increase the flow capacity thereof. Thus, in the oil industry, it is a conventional practice to hydraulically fracture a well in order to produce fractures or fissures in the surrounding formations and thus facilitate the flow of oil and/or gas into the well from the formation or the injection of fluids from the well into the formation. Such hydraulic fracturing can be accomplished by disposing a suitable fracturing fluid within the well opposite the formation to be fractured. The well is open to the formation by virtue of openings in a conduit, such as a casing string, or by virtue of an open completion in which a casing string is set to the top of the desired open interval and the formation face then exposed directly to the well below the shoe of the casing string. In any case, sufficient pressure is applied to the fracturing fluid and to the formation to cause the fluid to enter into the formation under a pressure sufficient to break down the formation with the formation of one or more fractures. Oftentimes the formation is ruptured to form vertical fractures. Particularly, in relatively deep formations, the fractures are naturally oriented in a predominantly vertical direction. One or more fractures may be produced in the course of a fracturing operation, or the same well may be fractured several times at different intervals in the same or different formation. [0003] Another widely used treating technique involves acidizing, which is generally applied to calcareous formations such as limestone. In acidizing, an acidizing fluid such as hydrochloric acid is introduced into the well and into the interval of the formation to be treated which is exposed in the well. Acidizing may be carried out as so-called “matrix acidizing” procedures or as “acid fracturing” procedures. In acid fracturing, the acidizing fluid is injected into the well under a sufficient pressure to fracture the formation in the manner described previously. An increase in permeability in the formation adjacent the well is produced by the fractures formed in the formation as well as by the chemical reaction of the acid with the formation material. In matrix acidizing, the acidizing fluid is introduced through the well into the formation at a pressure below the breakdown pressure of the formation. In this case, the primary action is an increase in permeability primarily by the chemical reaction of the acid within the formation with there being little or no effect of a mechanical disruption of the formation, such as occurs in hydraulic fracturing. [0004] Various other treatment techniques are available for increasing the permeability of a formation adjacent a well or otherwise imparting a desired characteristic to the formation. For example, solvents can sometimes be involved as a treating fluid in order to remove unwanted material from the formation in the vicinity of the well bore. SUMMARY OF THE INVENTION [0005] In accordance with the present invention, there is provided a method for the treatment of a subterranean formation penetrated by a well. In carrying out the invention, first and second flow paths are established within the well, extending from the wellhead into the vicinity of the subterranean formation. A plugging fluid comprising a suspension of a particulate plugging agent in a carrier liquid is circulated into the first of the flow paths and into the well in contact with the wall of the well within the subterranean formation. The carrier liquid is separated from the particulate plugging agent by circulating the carrier liquid into a second flow path. Circulation of the liquid is accomplished through a set of openings leading to the second flow path, which are dimensioned to allow the passage of the carrier liquid while retaining the particulate plugging agent in contact with the set of openings. The circulation of the plugging fluid continues until the particulate plugging agent accumulates to form a bridge packing within the well. The bridge packing acts similarly as a mechanical packer to form a barrier within the well. Subsequent to establishing the bridge packing, a treating fluid is introduced into the well through the first flow path and in contact with the surface of the formation in the well adjacent to the accumulated plugging agent forming the bridge packing. [0006] In a further aspect of the invention, a treatment procedure is carried out in a section of a well penetrating a subterranean formation and having a return tubing string provided with spaced screened sections at a location in the well adjacent the subterranean formation. A working tubing string opens into the interior of the well intermediate the spaced screen sections. In carrying out the invention, a plugging agent comprising a suspension of particulate plugging agent in a carrier liquid is circulated through the working string into the intermediate interval between the screen sections. The carrier liquid is flowed through openings in the spaced screen section, which are sized to allow the passage of the carrier liquid while retaining the particulate plugging agent in the well in contact with the screen sections. The flow of the plugging agent within the well is continued until the particulate plugging agent in the fluid accumulates in the well adjacent the screen sections to form spaced bridge packings within the well and surrounding the return string. Thereafter, a treating fluid is introduced into the well and into the interval of the well intermediate the spaced bridge packings and introduced into the formation. In a specific application of the invention, the treating fluid is a fracturing fluid introduced into the treating interval under pressure sufficient to hydraulically fracture the formation. In another embodiment of the invention, the treating fluid is an acidizing fluid effective to acidize the formation in either a matrix acidizing or acid fracturing operation. Preferably, subsequent to the introduction of the treating fluid into the well, a clean-up fluid is circulated down the well into the return tubing string to displace the accumulated particulate plugging agent away from the screened sections and disrupt and remove the bridge packings. In carrying out the hydraulic fracturing operations, the fracturing fluid is normally in the nature of a cross-linked gel having a high viscosity. The clean-up fluid can incorporate a breaker to break down the viscosifying agent in the fracturing fluid. For example, where the viscosifier in an aqueous-based fracturing agent takes the form of hydroxethylcellulose, the clean-up fluid can incorporate an acid such as hydrochloric acid, which functions to break the fracturing fluid gel to a liquid of much lower viscosity. Subsequently, the tubing strings can be moved longitudinally through the well to a second location within the well bore spaced from the originally treated location and the operation then repeated to treat a different section of the well bore. The tubing strings employed in carrying out the invention may be parallel tubing strings or they may be concentrically oriented tubing strings in which the working string disposed within the return string provides a return pathway formed by the annulus of the working string and the return string. [0007] In a further application of the invention, a treating process is carried out in a well section that extends in a horizontal orientation within the subterranean formation. The fracturing operation is carried out to hydraulically fracture the formation and form a vertically oriented fracture within the formation extending from the horizontally oriented well bore. Thereafter, the return and working strings are moved longitudinally through the horizontally extending well section to a second location, and the operation is repeated to form a second set of bridge packings followed by hydraulic fracturing to form a second vertically oriented fracture within the well section spaced at some distance from the initially formed vertically oriented fracture. These operations can be repeated as many times as desired in order to produce multiple fractures. BRIEF DESCRIPTION OF THE DRAWINGS [0008] [0008]FIG. 1 is a schematic illustration of a well with parts broken away, showing the formation of spaced bridge packings using concentrically oriented tubing strings. [0009] [0009]FIG. 2 is a schematic illustration of a well with parts broken away showing the invention as carried out employing parallel tubing strings. [0010] [0010]FIG. 3 is a schematic illustration of a section of a well showing a preferred form of screen section in a parallel string configuration. [0011] [0011]FIG. 4 is a schematic illustration of a well with parts broken away showing the application of the invention in a deviated well having a horizontal well section within a subterranean formation. [0012] [0012]FIGS. 5 and 6 are schematic illustrations with parts broken away of a horizontal well section showing sequential operations within the well section. [0013] [0013]FIG. 7 is a schematic illustration of a well with parts broken away showing the application of the invention in forming a single bridge packing with a concentric tubing string assembly. [0014] [0014]FIG. 8 is a schematic illustration of a well with parts broken away showing the application of the invention in forming a single bridge packing with parallel tubing string configuration. [0015] [0015]FIG. 9 is a side elevation with parts broken away showing a downhole well assembly suitable for use in carrying out the present invention. [0016] [0016]FIG. 10 is a side elevation with parts broken away showing another form of a downhole well assembly suitable for use in carrying out the present invention. [0017] [0017]FIG. 11 is a side elevation of a tubing section employed in a preferred screen section for use in the present invention. DETAILED DESCRIPTION OF THE INVENTION [0018] The present invention provides for the formation of one or more downhole bridge packings which can be placed at precise locations in a well by fluid circulation techniques in order to permit well-defined access to a formation by a suitable treating agent. The bridge packings can be assembled within the well without the use of special downhole mechanical packings and can be readily removed after the treatment procedure by a reverse circulation technique. The bridge packings are formed by the circulation downhole of a particulate plugging agent which is suspended in a suitable carrier liquid. The plugging fluid is circulated through a downhole screen at a desired location which permits the suspending liquid to readily flow through the screen openings but retards passage of the particulate plugging agent so that it accumulates in the well at the desired downhole location. The plugging agent may take the form of gravel or a gravel/sand mixture as described in greater detail below. Other suitable mixtures of porous permeable materials may be employed. The gravel-plugging agent is suspended within a liquid that may be either oil- or water-based for circulation down the well to the desired downhole location. The carrier liquid typically is treated with a thickening agent in order to provide a viscosity, normally within the range of 10-1,000 centipoises, preferably within the range of 30-200 centipoises, which is effective to retain the plugging agent in suspension as the plugging fluid is circulated through the well. However liquids of low viscosity, for example, water having a viscosity of about 1 cp can be used with low density plugging agents. [0019] The invention may be carried out employing tubing sections suspended down hole from a mechanical packer, which may be equipped with a crossover tool, or it may be carried out employing tubing strings which extend from the wellhead to the downhole location of the well being treated. The invention will be described initially with respect to the latter arrangement, which normally will be employed only in relatively shallow wells, in order to illustrate in a simple manner the flow of fluids in the course of carrying out the invention. [0020] Turning now to the drawings and referring first to FIG. 1, there is illustrated a well 10 , which extends from the earth's surface 12 into a subterranean formation 14 . Formation 14 may be of any suitable geologic structure and normally will be productive of oil and/or gas. The well 10 is provided with a casing string 15 which extends from the surface of the earth to the top of formation 14 . Typically, casing string 15 will be cemented within the well to provide a cement sheath (not shown) between the outer surface of the casing and the wall of the well. It is to be recognized that the well structure of FIG. 1 is highly schematic. While only a single casing string is shown, as a practical matter a plurality of casing strings can be and usually will be employed in completing the well. Also, while FIG. 1 depicts a so-called “open hole” completion, the well may be set with casing and cemented through the formation 14 and the casing then perforated to provide a production interval open to the well. [0021] The well is completed with concentrically run tubing strings comprising an outer tubing 17 and an inner tubing string 18 . The tubing strings 17 and 18 are hung in the well from the surface by suitable wellhead support structure (not shown). A flow line equipped with a valve 20 extends from the tubing 18 to allow for the introduction and withdrawal of fluids. A similar flow line with valve 21 extends from tubing string 17 and allows for the introduction and withdrawal of fluids through the annulus 22 , defined by the tubing strings 17 and 18 . The casing string is provided with a flow line and valve 23 providing access to the tubing-casing annulus. The tubing strings 17 and 18 are both closed at the bottom by closure plugs 17 a and 18 a . The tubing string 17 is provided with spaced screen sections 24 and 25 . The screen sections may be of any suitable type as long as they provide for openings sufficient to permit the egress and ingress of the liquid carrier while blocking passage of all or at least a substantial portion of the particulate plugging agent. In a typical downhole configuration involving a 4-inch diameter tubing set within a well bore having a nominal diameter of about 8-9 inches, the screen sections may be formulated by grid screens having sieve openings within the range of about 0.006-0.01 inch, corresponding generally to a standard sieves of 60-100 mesh. Other configurations can be used. For example, the screen sections can be provided by perforated sections of tubing or tubing which has been slotted vertically or vertically and horizontally, providing openings sufficient to block the passage of plugging agent. Also, sintered metal screens can be employed. The screen sections may be of any suitable dimension. In a well configuration as described above, the screen sections 24 and 25 may each be about 2-30 feet in length with an interval between the screen sections (from the top of the lower section to the bottom of the upper section) of about 5-30 feet. The downhole well assembly is provided with one or more flow ports such as provided by a spider assembly 28 comprised of a plurality of tubes extending from the interior of tubing string 18 to the exterior of tubing string 17 to permit the flow of fluid between the interior of tubing string 18 and the exterior of tubing string 17 . [0022] In carrying out the invention, the slurry of particulate plugging agent in the carrier liquid is circulated through line 20 and down the well through tubing 18 . The slurry flows through the downhole spider assembly 28 into the annular space 30 between the wall of the well and the outer surface of tubing 17 . Within the well annulus 30 , the slurry flows through the screens 24 and 25 into the annulus 22 defined by tubing strings 17 and 18 . If desired, a packer (not shown) may be set in the well annulus above screen 24 in order to direct the flow of fluid into the annulus 22 rather than up the well annulus 30 . However, this often will be unnecessary. The plugging fluid flowing down the well (having a suspension of gravel or the like in the carrier liquid) will have a higher bulk density than the carrier liquid itself. Thus, as the carrier liquid flows through the screens 24 and 25 causing the granular plugging agent to accumulate in the vicinity of the screens, the pressure gradient across the screens will be less than the pressure gradient up the well. Thus, flow will be predominantly through the screen and into the tubing annulus 22 . [0023] At the conclusion of the preliminary circulation step, effective bridge packings 32 and 34 are formed adjacent the screens 24 and 25 . The packings are retained in place by the hydrostatic pressure in the well annulus 30 , and the packings are sufficiently impermeable to prevent any significant migration of fluid from one side of a packing to the other. [0024] At the conclusion of the formation of the bridging plugs, a suitable treating fluid is injected via line 20 into tubing 18 and through the spider assembly 28 into the space between the bridge packings 32 and 34 . By way of example, a fracturing fluid may be injected down tubing 18 and under pressure sufficient to form a fracture 36 in the formation 14 . Alternatively, the treating procedure may take the form of an acidizing procedure or an acid fracturing procedure. [0025] Standard procedures can be employed in carrying out the treating operation. Where a fracturing operation is involved, initial spearhead fluid will be injected in accordance with accepted practice under a sufficient pressure to exceed the breakdown pressure of the formation and fracture the formation. Normally the spearhead fluid will be a viscous fluid, typically having a viscosity within the range of 10-1,000 centipoises which is free of propping agent or has a very low propping agent concentration. In order to insure that the bridge packings remain in place during the initial fracturing procedure, the spearhead fluid can incorporate a bridging agent such as sand employed in relatively low concentration, typically within the range of 1-50 pounds per barrel. [0026] After fracturing is initiated in the formation, a fracturing fluid carrying a propping agent, is pumped down tubing 18 to propagate the fracture in the formation and leave it packed with propping agent. Typically a “sand out” condition will occur, as indicated by an increase in pressure, and the fracturing operation is then concluded. [0027] At the conclusion of the treating procedure, the bridge packings may be removed. In order to remove the bridge packings 32 and 34 , a reverse circulating fluid, which may be the same or different from the fluid employed as the carrier liquid initially, is injected through valve 21 into the tubing annulus 22 . This creates a reverse pressure differential through the screen sections 24 and 25 causes the bridge packings to begin to disintegrate. Ultimately, the bridge packings are removed by the particulate plugging agent becoming suspended in carrier liquid and carried away from the vicinity of the formation. Normally, the particulate plugging agent will be reverse circulated up tubing string 18 to the surface and removed from the well. The suspension of particulate plugging in the carrier liquid can be circulated up the annulus 30 . The reverse circulation fluid may be different from the fluid employed as the initial carrier liquid. The reverse circulation fluid may take the form initially of a lower viscosity fluid to facilitate the initial removal of the particulate plugging agent. Where the carrier liquid incorporates a cross linked gel, the reverse circulation flow may contain a breaking agent to help remove the cross-linked gel from the bridge packing. Suitable gelling agents include guar gum or hydroxyethylcellulose. They may be used in any suitable amounts. Typically, they are used in minimum amounts of about 20-25 to perhaps 30 lbs. per thousand gallons. The gel may be broken through the use of oxydizers or enzymes to effect suitable decomposition reactions. Typically, oxydizers are used. Suitable oxidizers include sodium hypochlorite and ammonium persulfate. [0028] Turning now to FIG. 2, there is illustrated an alternative well structure for use in carrying out the present invention in which parallel tubing strings are employed. In FIG. 2 like elements are designated by the same reference numerals as shown in FIG. 1 and the foregoing description is applicable to FIG. 2 with the exception of the modification involving the use of parallel tubing strings. In FIG. 2, string 38 (analogous in function to tubing string 18 ) and tubing string 40 (analogous in function to tubing string 17 ) are run in a parallel configuration. The tubing strings are dimensioned to take into account the parallel configuration. By way of example, in a well having a nominal diameter of 8-9 inches, each of strings 38 and 40 may be 2-3-inch tubing strings. Tubing string 40 is provided with screen sections 41 and 42 , which may be configured with respect to the size of the openings, similarly as described above with respect to FIG. 1. Tubing string 40 is closed at its lower end with a suitable plug indicated by reference numeral 40 a . Tubing string 38 is provided with a closure or seal 44 at its bottom end and is provided with a perforated section 45 to allow for the flow of fluid from tubing 38 into the well bore. Alternatively, instead of providing tubing string 38 with a perforated section, the tubing string may be open at its bottom end to provide for flow of fluids from the interior of the tubing string into the well. In this case the lower end of the tubing sting should be located approximately midway between the locations of the screen sections 41 and 42 . The operation of the invention employing the parallel tubing configuration shown in FIG. 2 is similar to the operation employing the concentric tubing strings as shown in FIG. 1. A plugging fluid comprising a suspension of particulate plugging agent is circulated down the well via tubing 38 . The openings in the perforated section 45 of tubing 38 are sufficient to permit the passage of the particulate plugging agent in suspension in the carrier liquid without the plugging agent screening out of suspension and accumulating in the interior of the tubing string 38 . [0029] The plugging fluid is circulated down tubing 38 into the well and through the screen sections 41 and 42 in order to form bridge packings 47 and 48 . As the carrier liquid passes through the screen sections and into tubing string 40 , the bridge packings 47 and 48 are formed similarly as described above. At the conclusion of formation of the bridge packings, the treating fluid is then injected down tubing string 38 and into the interval of the well between bridge packings 47 and 48 to carry out the desired treating operation. At the conclusion of the treating operation, the bridge packings 47 and 48 may be removed by circulation of the viscous carrier liquid down the well in tubing string 40 . Alternatively, a different fluid may be used as described previously. [0030] In carrying out the invention with the parallel tubing configuration of FIG. 2, the lower bridge packing 47 will occupy a substantially greater cross-sectional area of the well bore than in the case of employing concentric tubing strings. In a preferred embodiment of the invention, in order to facilitate removal of the lower screen section in conjunction with dispersion of the bridge packing, the lower screen section can be formed in a tapered configuration. This embodiment of the invention is shown in FIG. 3, in which the tubing 40 is shown to terminate in a tapered screen section 49 . By way of example, where the tubing string 40 is a 3-inch tubing, the screen section may taper downwardly to provide a lower dimension indicated by reference numeral 50 of about half of the dimension of the tubing string. [0031] A preferred application of the present invention is in carrying out multiple treatments in a single wellbore. This is facilitated by the fact that the bridge packings can be readily removed by a reverse circulation technique, the tubing assembly then moved to a new location in the well, and a new set of bridge packings put in place. This mode of operation is particularly advantageous in the operation of wells in which the producing section is slanted substantially from the vertical in some cases to a nominally horizontal orientation. Such horizontal well bores are typically employed in relatively thick gas or oil formations where the slant well follows generally the dip of the formation and especially where the formation permeability is relatively low. Such slant wells or horizontal wells can be formed by any suitable technique. One technique involves the drilling of a vertical well followed by the use of whipstocks to progressively deviate from the vertical in a direction to arrive at the horizontal orientation. Such horizontal wells may also be formed using coiled tubing equipment of the type disclosed, for example, in U.S. Pat. No. 5,215,151 to Smith et al. Turning now to FIG. 4, there is illustrated a well 52 which has been deviated from the vertical into a horizontal configuration to generally follow the dip of subterranean formation 54 . The well is equipped with a concentric tubing arrangement having inner and outer tubing strings 56 and 57 corresponding generally to the tubing strings 17 and 18 of FIG. 1. The outer tubing string 57 is equipped with upper and lower screen sections 58 and 59 , which are disposed above and below a spider assembly 60 providing for the flow of fluid between the interior of tubing string 56 and the exterior of tubing string 57 . In operation of the system of FIG. 4, the suspension of a particulate plugging agent is circulated down tubing string 56 and through spider assembly 60 into the annulus 62 between the wall of the well 52 and the outer tubing string 57 . The carrier liquid flows through the screen elements 58 and 59 and into the tubing annulus 64 , resulting in the formulation of bridge packings similarly as described above. A tubing fracturing operation is then initiated in order to form one or more vertical fractures as indicated by reference character 65 . [0032] In the stimulation of formations penetrated by horizontal or deviated wells as shown in FIG. 4, it is sometimes desirable to form a series of spaced vertical fractures. This sequence of operation is shown by FIGS. 5 and 6. FIG. 5 illustrates the location of the tubing strings 56 and 57 at a second location moved uphole from the initial location where fracture 65 was formed. The circulation procedure is repeated to again provide spaced bridge packings 67 and 68 followed by a fracturing operation in order to form a second fracture system 70 spaced horizontally from the first fracture system 65 . Thereafter, circulation is reversed as indicated in FIG. 6 with a carrier liquid (without particulate plugging agents) circulated down the annulus 64 to disrupt the bridge packings with return of fluid up the inner tubing string 56 and, if desired, also within the well-tubing annulus 62 . If desired, the process can be repeated by again moving the tubing assembly uphole and forming new bridge packings at yet another location followed by fracturing to produce a third vertical fracture system spaced from the systems 65 and 70 . [0033] Usually in carrying out the invention in deviated wells as depicted in FIGS. 4 through 6, it will be preferred to employ a concentric tubing arrangement rather than a parallel tubing arrangement configuration of the type depicted in FIG. 2. When using the concentric tubing arrangement, suitable centralizers can be employed along the length of the concentric tubing strings in order to maintain the generally annular spacing shown. [0034] A further embodiment of the invention, as carried out employing only a single bridge packing, is shown in FIG. 7. In the system of FIG. 7, a concentric tubing arrangement similar to that shown in FIG. 1 is employed with the exception that the interior tubing string 72 extends through the bottom of the exterior tubing string 74 . The exterior tubing string is provided with a suitable closure element 79 in order to seal the annulus 76 between the inner and outer tubing strings at the bottom. In this embodiment of the invention, normally carried out near the bottom of a well, the dispersion of plugging agent in the carrier liquid is circulated down tubing string 72 and into the well bore. The carrier liquid is returned from the well bore through string screen 77 into the tubing annulus 76 to form a bridge packing 78 similarly as described previously. Once the packing is formed, a suitable treating operation can be carried out by the injection of a treating fluid such as a fracturing fluid or an acidizing fluid down the interior tubing string 72 into the well section below the bridge packing 78 . At the conclusion of the treating operation, flow can be reversed by circulating the carrier liquid down the tubing annulus 76 to displace the accumulation of particulate plugging agent away from the screen section 77 . [0035] [0035]FIG. 8 illustrates a parallel tubing string configuration employed to provide a single bridge packing. Here, tubing string 80 is open at the bottom, and tubing string 82 is provided with a closure 83 and a screen section 84 spaced upwardly from the lower end of the tubing string. A carrier liquid containing a particulate plugging agent in suspension is circulated down tubing string 80 through the screen section and up tubing string 82 in order to form a bridge packing 86 . The treating operation can be carried out through tubing string 80 , and at the conclusion of the treating operation, reverse circulation down tubing 82 is instituted to disrupt the bridge packing 86 , similarly as described above. [0036] The invention as thus far described involves the use of separate tubing strings run in parallel or concentrical configuration from the wellhead to the vicinity of the formation undergoing treatment. While applications of this nature are useful, particularly in relatively shallow wells, the tubing arrangements involved become relatively cumbersome when the invention is carried out in wells of substantial depth, particularly where the depth of the well to the formation undergoing treatment exceeds about 1,000-2,000 ft. In such cases it will usually be desirable to run a well tool providing separate flow paths as described above on a single tubing string equipped with a packer. If desired, the packer may be equipped with a flow control tool of conventional configuration to permit different flow paths from the surface of the well to the downhole location through a single tubing string and/or through the tubing-casing annulus. [0037] Turning to FIG. 9, there is illustrated a well 10 having a single tubing string 90 extending from the surface of the well (not shown). Supported on the tubing string 90 is a mechanical packer 91 which supports sections of tubings 92 and 93 . Tubing section 93 is equipped with upper and lower screen sections 94 and 95 and is analogous in operation to the tubing string 40 described above with reference to FIG. 2. Tubing string 92 is provided with a perforated section 96 and is analogous in operation to the tubing string 38 described above with reference to FIG. 2. The tubing sections 92 and 93 are secured to one another in a fixed space location by the packer 91 and by means of spacing elements 97 extending between the tubing sections. Spacing elements 97 do not, of course, provide fluid passages between the tubing sections. Tubing 92 can be placed in fluid communication with the tubing string 90 through a passageway 99 in the packer, and the interior of tubing string 93 placed in fluid communication with the tubing-casing annulus 98 by means of passageway indicated by broken lines 100 . In operation of the well tool shown in FIG. 9, a suspension of the particulate plugging agent in a suitable carrier liquid is circulated down the well via tubing 90 and exits into the well bore via perforations 96 . The carrier liquid is circulated through screen sections 94 and 95 , which are configured as described previously, to permit the passage of the carrier liquid but retain the particulate plugging agent on the screen sections to form bridge packings (not shown) similarly as described above. Return flow in the configuration shown is through the tubing-casing annulus 98 . The lower screen section 95 is tapered as described previously in order to facilitate removal of the well tool. At the conclusion of the treating operation carried out through tubings 90 and 92 , carrier liquid may be circulated down the tubing casing annulus 98 into tubing section 93 . At the same time, the packer 97 may be released, and upward strain imposed by the working tubing 90 with the tapered screen section 95 facilitating removal from the lower bridge packing as described previously. [0038] [0038]FIG. 10 is a side elevation with parts broken away of a downhole tool incorporating concentric tubing sections, which function similarly as described above with reference to FIG. 1. In FIG. 10, like elements as are shown in FIG. 9 are designated by the same reference numerals as used in FIG. 9. In the tool of FIG. 10, an outer concentric tubing 101 is provided with upper and lower screen sections 102 and 103 . Also suspended from the packer 91 is a concentric inner tubing section 105 , which is provided with an upper spider section 106 and a lower spider section (not shown) terminating in perforations in the outer tubing section 101 indicated by reference numeral 108 . The spider sections provide flow passages from the interior of tubing section 105 to the exterior of the tubing string 101 . The annulus 109 between the inner and outer tubing strings is placed in fluid communication with the tubing-casing annulus 98 through a passageway 110 in the packer 91 as indicated by broken lines. The interior of the tubing string 105 is placed in fluid communication with the working tubing string 90 as indicated by the broken line passageway 112 . The operation of the well tool shown in FIG. 10 is similar as that described above with reference to FIG. 1. The carrier liquid containing the particulate plugging agent is introduced into the well through tubing 90 into tubing section 105 and thence outwardly through the spider passageways to the exterior of outer tubing section 101 . Return flow is directed into annulus 109 and then upwardly through the tubing-casing annulus 98 to form bridge packings (not shown) adjacent screen sections 102 and 103 . [0039] As disclosed previously, the screen sections employed in the present invention may be of any suitable type but normally will take the form of a 0.006-0.01 inch mesh screen. FIG. 11 shows a suitable screen section configuration in which the screen section of the tubing 114 is provided with perforations 116 . A wire mesh screen (not shown) is wrapped around the perforated section of pipe 114 . The pipe functions to support the screen element. In addition, by appropriately sizing the perforations 116 when the reverse circulation carrier liquid is pumped down the well flow and flow through the constricted perforations 111 , it exits at a relatively high velocity, thus facilitating disruption of the particulate bridging agent around the screen section. [0040] As described previously, the present invention may be carried out employing treating fluids other than those commonly used in acidizing, fracturing, or acid fracturing operations. A treating fluid may take the form of a solvent, other than an acidizing fluid, in order to remove material immediately adjacent the well bore to facilitate fluid flow between the well bore and the formation. Alternatively, a treating agent in the nature of a plugging agent can be introduced into the well in order to seal a section of the formation intermediate the bridge packings formed adjacent the screen sections. For example, a suspension of a thermoset polymer may be introduced into the well, followed by the introduction of a setting agent to crosslink the polymer and form a seal within a limited portion of the well bore. Suitable materials useful in the embodiment of this nature include crosslinked hydroxyethylcellulose. [0041] The screen sections employed in the various embodiments of the invention may, as noted previously, be relatively short, e.g., on the order of about one or two feet. However, as a practical matter, screen sections will usually be provided ranging in lengths from about 5 to 20 feet. The interval between screen sections may range from a low as 2 feet up to perhaps 60 feet in length, depending upon the formation interval to be treated. However, a typical spacing between the screen sections will be about 10-30 feet from the top of the lower screen section to the bottom of the upper screen section. [0042] From the foregoing description, it will be recognized that the viscosity of the carrier liquid and the particle size range and density of the particulate plugging agent are interrelated. In addition, the size of the screen openings is related to the characteristic of the particulate plugging agent since all or most of the plugging agent should be retained on the screen to form the bridge packing. The particulate plugging agent preferably will take the form of a sand/gravel mixture having a specific gravity of about 1.5-3.5 with a particle size distribution which promotes packing of the relatively fine sand particles within the interstices formed by the somewhat coarser gravel particles. For example, a suitable particulate plugging agent may comprise about 40-60 wt. % gravel having a particle size distribution of about 20-40 mesh and a relatively fine 40-60 mesh size sand portion comprising about 40-60 wt. % of the mixture. For such a particulate plugging agent, the viscosity of the carrier liquid should be within the range of about 20-200 centipoises. The screen section may take the form of a 0.006-0.01 inch mesh screen. Where the screen is wrapped around underlying perforated pipe as shown in FIG. 11, the perforations may have a diameter of about ⅛-⅜ inches with about 2-50 perforations per foot of pipe. [0043] Having described specific embodiments of the present invention, it will be understood that modifications thereof may be suggested to those skilled in the art, and it is intended to cover all such modifications as fall within the scope of the appended claims.
A method for the treatment of a subterranean formation penetrated by a well in which, first and second flow paths are established from the wellhead into the vicinity of the formation. A plugging fluid comprising a suspension of a particulate plugging agent in a carrier liquid is circulated into the first flow path and into contact with the wall of the well within the subterranean formation. The carrier liquid is separated from the particulate plugging agent by circulating the carrier liquid through a set of openings leading to the second flow path, which are dimensioned to allow the passage of the carrier liquid while retaining the particulate plugging agent in contact with the set of openings. The circulation of the plugging fluid continues until the particulate plugging agent accumulates to form a bridge packing within the well. Subsequent to establishing the bridge packing, a treating fluid is introduced into the well through the first flow path and in contact with the surface of the formation in the well adjacent to the bridge packing. The treating fluid may be a fracturing fluid under or an acidizing fluid. A clean-up fluid is circulated into the second flow path to remove the bridge packing.
4
INCORPORATION BY REFERENCE This application claims the benefit of U.S. Provisional No. 62/407,215 filed Oct. 27, 2010. All documents cited therein or during their prosecution (“appln cited documents”) and all documents cited or referenced in the appln cited documents, and all documents cited or referenced herein (“herein cited documents”), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention. More specifically, all referenced documents are incorporated by reference to the same extent as if each individual document was specifically and individually indicated to be incorporated by reference FIELD OF THE INVENTION The present invention relates to the field of plant breeding and more particular to the development of inbred spinach line SP6111. BACKGROUND OF THE INVENTION Spinach ( Spinacia oleracea ) is a flowering vegetable plant in the family of Amaranthaceae. It is native to southwestern and central Asia, but nowadays is being cultivated worldwide, mostly in temperate regions. The consumable parts of spinach are the leaves. These are produced during the first stage of the life cycle of a spinach plant, during which the plant forms a leaf rosette. The second stage is the flowering stage or bolting stage. Bolting is the growth of an elongated stalk with flowers grown from within the main stem of a plant. During the bolting stage it is not possible anymore to harvest any marketable product of the plant. The leaves of a spinach plant are usually sold loose, bunched, in prepackaged bags, canned, or frozen. There are three basic types of spinach, namely savoy, semi-savoy and smooth. Savoy has dark green, crinkly and curly leaves. Flat or smooth leaf spinach has broad smooth leaves. Semi-savoy is a hybrid variety with slightly crinkled leaves. SUMMARY OF THE INVENTION The present invention provides a new inbred line of spinach plants, called SP6111. Seeds of inbred spinach line SP6111 have been deposited with the National Collections of Industrial, Marine and Food Bacteria (NCIMB) in Bucksburn, Aberdeen AB21 9YA, Scotland, UK and have been assigned NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, representative seed of which having been deposited under NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, and 11, representative seed of which having been deposited under NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, and downy mildew isolate US2209, representative seed of which having been deposited under NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant exhibiting a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, representative seed of which having been deposited under NCIMB Accession No. 41758. (The growth rate of the spinach plant of the invention, e.g. SP6111, representative seed of which having been deposited under NCIMB Accession No. 41758, is comparable to dixie market (see e.g. US2009/0300787). The bolting of the spinach plant of the invention, e.g. SP6111, representative seed of which having been deposited under NCIMB Accession No. 41758, is comparable to Bloomsdale (e.g. US20100031381). And the color of the spinach plant of the invention, e.g. SP6111, representative seed of which having been deposited under NCIMB Accession No. 41758, is akin to Bloomsdale, see also table 2.) In one embodiment, the invention provides a spinach plant exhibiting a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, representative seed of which having been deposited under NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant exhibiting a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, and downy mildew isolate US2209, representative seed of which having been deposited under NCIMB Accession No. 41758. In one embodiment, the invention provides a spinach plant designated SP6111, representative seed of which having been deposited under NCIMB Accession No. 41758. In an embodiment of the present invention, there also is provided parts of a spinach plant of the invention, including parts of a spinach plant having resistance against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, or parts of a spinach plant having resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, or parts of a spinach plant having resistance to both downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, and downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, or parts of a spinach plant having any of the aforementioned resistance(s) and a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, or parts of a spinach plant having any of the aforementioned resistance(s) and one or more morphological or physiological characteristics tabulated herein, including parts of inbred spinach line SP6111, wherein the plant parts are suitable for sexual reproduction, which include, without limitation, microspores, pollen, ovaries, ovules, embryo sacs or egg cells and/or wherein the plant parts are suitable for vegetative reproduction, which include, without limitation, cuttings, roots, stems, cells or protoplasts and/or wherein the plant parts are tissue culture of regenerable cells in which the cells or protoplasts of the tissue culture are derived from a tissue such as, for example and without limitation, leaves, pollen, embryos, cotyledon, hypocotyls, meristematic cells, roots, root tips, anthers, flowers, seeds or stems. The plants of the invention from which such parts can come from include those wherein representative seed of which has been deposited under NCIMB Accession No. NCIMB 41758. With regard to morphological or physiological characteristics, it is understood that these are compared when plants are grown in the same environmental conditions. In another embodiment there is a plant grown from seeds, representative seed of which having been deposited under NCIMB Accession No. 41758. In a further embodiment there is a plant regenerated from the above-described plant parts or regenerated from the above-described tissue culture. Advantageously such a plant has morphological and/or physiological characteristics of inbred spinach line SP6111 and/or of plant grown from seed, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758—including without limitation such plants having all of the morphological and physiological characteristics of inbred spinach line SP6111 and/or of plant grown from seed, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758. Accordingly, in still a further embodiment, there is provided a spinach plant having all of the morphological and physiological characteristics of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758. Such a plant can be grown from the seeds, regenerated from the above-described plant parts, or regenerated from the above-described tissue culture. A spinach plant having any of the aforementioned resistance(s), a spinach plant having any of the aforementioned resistance(s) and one or more morphological or physiological characteristics recited or tabulated herein, and a spinach plant advantageously having all of the aforementioned resistances and the characteristics recited and tabulated herein, are preferred. Parts of such plants—such as those plant parts above-mentioned—are encompassed by the invention. In one embodiment, there is provided progeny of inbred spinach line SP6111 produced by sexual or vegetative reproduction, grown from seeds, regenerated from the above-described plant parts, or regenerated from the above-described tissue culture of the inbred spinach line or a progeny plant thereof, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758. In another embodiment, there is provided progeny of inbred spinach line SP6111 produced by sexual or vegetative reproduction, grown from seeds, regenerated from the above-described plant parts, or regenerated from the above-described tissue culture of the inbred spinach line or a progeny plant thereof, in which the regenerated plant is resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758. Progeny of the inbred spinach line SP6111 can be modified in one or more other characteristics, in which the modification is a result of, for example and without limitation, mutagenesis or transformation with a transgene. In still another embodiment, there is provided progeny of inbred spinach line SP6111 produced by sexual or vegetative reproduction, grown from seeds, regenerated from the above-described plant parts, or regenerated from the above-described tissue culture of the inbred spinach line or a progeny plant thereof, in which the regenerated plant is resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209. Like most vegetables varieties, spinach varieties are usually hybrids. The breeding of a hybrid spinach variety basically involves four steps: The first step comprises selecting and crossing of plants in order to obtain plants with desired traits, such as e.g. disease or pest resistances, better yield, better tolerance to climatic conditions, etc. The second step comprises selfing those plants with superior traits for several generations in order to produce inbred lines. Although these lines are different from each other, each line will become highly uniform after several generations of inbreeding. The third step comprises crossing the inbred lines to produce hybrid plants. Finally, the inbred lines that give rise to the best hybrid are identified. From there, commercial production of hybrid seed can start. In one embodiment, the invention comprises a method of producing a hybrid spinach seed comprising crossing a first parent spinach plant with a second parent spinach plant and harvesting the resultant hybrid spinach seed, wherein said first parent spinach plant or said second parent spinach plant is a spinach plant of the invention, e.g., a spinach plant having resistance against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, or a spinach plant having resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, or a spinach plant having resistance to both downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209, and downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, or a spinach plant having any of the aforementioned resistance(s) and a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, or a spinach plant having any of the aforementioned resistance(s) and one or more morphological or physiological characteristics tabulated herein, including a spinach plant of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB 41758. In another embodiment, the invention comprises producing a spinach plant being resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209 comprising: crossing a mother spinach plant with a father spinach plant to produce a hybrid seed; growing said hybrid seed to produce a hybrid plant; selfing said hybrid seed to produce F2 progeny seed; selecting said F2-plants for being resistant against downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) isolate US2209. In still a further embodiment, the invention comprises a method of producing a spinach cultivar containing a combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, and downy mildew isolate US2209 comprising: crossing a mother spinach plant with a father spinach plant to produce a hybrid seed; growing said hybrid seed to produce a hybrid plant; selfing said hybrid seed to produce F2 progeny seed; selecting said F2-plants for having medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, 11, and downy mildew isolate US2209. The invention even further relates to a method of producing spinach comprising: (a) cultivating to the vegetative plant stage a plant of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758, and (b) harvesting spinach from the plant. The invention further comprehends canning, freezing or packaging the spinach plants or leaves. It is noted that in this disclosure and particularly in the claims, terms such as “comprises”, “comprised”, and “comprising” and the like (e.g., “includes”, “included”, “including”, “contains”, ‘contained”, “containing”, “has”, “had”, “having”, etc.) can have the meaning ascribed to them in US patent law, i.e., they are open ended terms. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps. Similarly, any plant that “comprises,” “has” or “includes” one or more traits is not limited to possessing only those one or more traits and covers other unlisted traits. Similarly, the terms “consists essentially of” and “consisting essentially of” have the meaning ascribed to them in US patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention. See also MPEP §2111.03. In addition, the term “about” is used to indicate that a value includes the standard deviation of error for the device or method being employed to determine the value. These and other embodiments are disclosed or are obvious from and encompassed by the following Detailed Description. DEPOSIT The Deposit with NCIMB Ltd, Ferguson Building, Craibstone Estate, Bucksburn, Aberdeen AB21 9YA, UK, under deposit accession number NCIMB 41758 was made pursuant to the terms of the Budapest Treaty. Upon issuance of a patent, all restrictions upon the deposit will be removed, and the deposit is intended to meet the requirements of 37 CFR §1.801-1.809. The deposit will be maintained in the depository for a period of 30 years, or 5 years after the last request, or for the effective life of the patent, whichever is longer, and will be replaced if necessary during that period. BRIEF DESCRIPTION OF THE DRAWINGS The following Detailed Description, including the Examples, given by way of example, but not intended to limit the invention solely to the specific embodiments described, may be best understood in conjunction with the accompanying drawings, incorporated herein by reference, in which: FIG. 1 shows leaf shapes; and FIG. 2 shows leaf tip shapes. FIGS. 1 and 2 are provided to assist the reader in appreciating the appearance round leaf tip, and arrow shaped leafs of the inventive spinach. DETAILED DESCRIPTION OF THE INVENTION The invention provides methods and compositions relating to plants, seeds and derivatives of a new inbred line of spinach plants herein referred to as inbred spinach line SP6111. Inbred spinach line SP6111 is a uniform and stable line, distinct from other such lines. Crossing inbred spinach line SP6111 with another distinct inbred spinach line will yield uniform F1 hybrid progeny plants. The F1 may be self-pollinated to produce a segregating F2 generation. Individual plants may then be selected which represent the desired phenotype in each generation (F3, F4, F5, etc.) until the traits are homozygous or fixed within a breeding population. Inbred spinach line SP6111 was developed by half sib family selection out of GB25398. After 6 selection and selfing cycles. A final round of mass selection was performed, selecting for uniformity. TABLE 1 Breeding history of SP6111 (M = mass selection). Year 1 Pedigree selection from GB25398 Year 1 F2 Generation gown, no selection Year 2 F3 generation grown Year 3 F4 generation grown Year 4 F5 generation grown Year 5 F6 generation grown Year 6 F7 generation grown Year 7 F8 generation grown Year 8 F8.M1 In one embodiment, a plant of the invention has all the morphological and physiological characteristics of inbred spinach line SP6111. These physiological and morphological characteristics of spinach of the invention, e.g., line SP6111, are summarized in table 2. Embodiments of the invention advantageously have one or more, and most advantageously all, of these characteristics. TABLE 2 Physiological and morphological characteristics of SP6111 and comparison variety Squirrel. Line/Cultivar SP 6111 Squirrel For patent or comparison patent Comparison Characteristics Species Spinacia oleracea L. Spinacia oleracea L. Ploidy Diploid Diploid Maturity Growth Rate Fast (Dixie Market) Medium (Long Standing Bloomsdale) Days from planting to prime 20 23 market stage Plant (prime market stage) Habit Semi-erect Flat (Viroflay) (long Standing Bloomsdale) Size Small (America) Large (Giant Nobel) Spread (cm) 33 50 Height (cm) 10 12 Seedling Cotyledon Width (mm)  8  6 Length (mm) 65 45 Tip Rounded Color Medium Green Medium Green Color Chart Name RHS CC — Color Chart Value 144 A — Leaf (First Foliage Leaves) Shape Ovate Ovate Base Lobed Lobed Tip Round Round-pointed Margin Flat Slightly Curled Upper Surface Color Dark Green Dark Green (Long Standing (Long Standing Bloomsdale) Bloomsdale) Color Chart Name RHS CC RHS CC Color Chart Value 137B 137 A Lower surface Color Lighter Lighter (compared with upper) Color Chart Name RHS CC RHS CC Color Chart Value 137 C 137 C Leaf (Prime Market Stage) Surface Smooth (Viroflay) Semi-savoy Shape Arrow-shaped Arrow-shaped Base Lobed Lobed Tip Round Round Margin Flat Slightly Curled Upper Surface Color Dark Green Dark Green (Long Standing (Long Standing Bloomsdale) Bloomsdale) Color Chart Name RHS CC RHS CC Color Chart Value 137 B 137 B Lower surface Color Lighter Lighter (compared with upper) Color Chart Name RHS CC RHS CC Color Chart Value 146 B 146 B Luster Glossy Dull Blade Size Medium Large (Virginia Savoy) (Giant Nobel) Blade Lobing Lobed Lobed Petiole Color Medium Green Medium Green Color Chart Name RHS CC RHS CC Color Chart Value 144 A 144 C Petiole Red Pigmentation Absent Absent Petiole Length to the Blade  5  5 (cm) Petiole Length Medium Medium Petiole Diameter (mm)  5  5 Petiole Diameter Medium Medium Seed Stalk Development Start of bolting (10% of the Medium Medium plants) (Long Standing (Long Standing Bloomsdale) Bloomsdale) Height of Stalk (cm) 60 60 Leaves on Stalk of Female Many Many plant Leaves on Stalk of Male — — plant Plants that are Female 91-100% 91-100% Plants that are Male — — Plants that are Monoecious — — Seed Surface Smooth Smooth Disease reaction Pf1 Resistant Resistant Pf2 Susceptible Resistant P2 Resistant Resistant Pf4 Susceptible Resistant Pf5 Resistant Resistant Pf6 Susceptible Resistant Pf7 Susceptible Resistant Pf8 Resistant Resistant Pf9 Resistant Resistant Pf10 Susceptible Resistant Pf11 Resistant Resistant Downy mildew isolate Resistant Susceptible US2209 Fusarium Susceptible Not tested White Rust Not tested Not tested Curly Top Virus Not tested Not tested CMV Susceptible Susceptible Colletotrichum Susceptible Susceptible Winter Hardiness Not tested Not tested In an embodiment, the invention relates to spinach plants that has all the morphological and physiological characteristics of the invention and have acquired said characteristics by introduction of the genetic information that is responsible for the characteristics from a suitable source, either by conventional breeding, or genetic modification, in particular by cisgenesis or transgenesis. Cisgenesis is genetic modification of plants with a natural gene, coding for an (agricultural) trait, from the crop plant itself or from a sexually compatible donor plant. Transgenesis is genetic modification of a plant with a gene from a non-crossable species or a synthetic gene. Just as useful traits that can be introduced by backcrossing, useful traits can be introduced directly into the plant of the invention, being a plant of inbred spinach line SP6111, by genetic transformation techniques; and, such plants of inbred spinach line SP6111 that have additional genetic information introduced into the genome or that express additional traits by having the DNA coding there for introduced into the genome via transformation techniques, are within the ambit of the invention, as well as uses of such plants, and the making of such plants. Genetic transformation may therefore be used to insert a selected transgene into the plant of the invention, being a plant of inbred spinach line SP6111 or may, alternatively, be used for the preparation of transgenes which can be introduced by backcrossing. Methods for the transformation of plants, including spinach, are well known to those of skill in the art. Vectors used for the transformation of spinach cells are not limited so long as the vector can express an inserted DNA in the cells. For example, vectors comprising promoters for constitutive gene expression in spinach cells (e.g., cauliflower mosaic virus 35S promoter) and promoters inducible by exogenous stimuli can be used. Examples of suitable vectors include pBI binary vector. The “spinach cell” into which the vector is to be introduced includes various forms of spinach cells, such as cultured cell suspensions, protoplasts, leaf sections, and callus. A vector can be introduced into spinach cells by known methods, such as the polyethylene glycol method, polycation method, electroporation, Agrobacterium -mediated transfer, particle bombardment and direct DNA uptake by protoplasts. To effect transformation by electroporation, one may employ either friable tissues, such as a suspension culture of cells or embryogenic callus or alternatively one may transform immature embryos or other organized tissue directly. In this technique, one would partially degrade the cell walls of the chosen cells by exposing them to pectin-degrading enzymes (pectolyases) or mechanically wound tissues in a controlled manner. A particularly efficient method for delivering transforming DNA segments to plant cells is microprojectile bombardment. In this method, particles are coated with nucleic acids and delivered into cells by a propelling force. Exemplary particles include those comprised of tungsten, platinum, and preferably, gold. For the bombardment, cells in suspension are concentrated on filters or solid culture medium. Alternatively, immature embryos or other target cells may be arranged on solid culture medium. The cells to be bombarded are positioned at an appropriate distance below the macroprojectile stopping plate. An illustrative embodiment of a method for delivering DNA into plant cells by acceleration is the Biolistics Particle Delivery System, which can be used to propel particles coated with DNA or cells through a screen, such as a stainless steel or Nytex screen, onto a surface covered with target spinach cells. The screen disperses the particles so that they are not delivered to the recipient cells in large aggregates. It is believed that a screen intervening between the projectile apparatus and the cells to be bombarded reduces the size of projectiles aggregate and may contribute to a higher frequency of transformation by reducing the damage inflicted on the recipient cells by projectiles that are too large. Microprojectile bombardment techniques are widely applicable, and may be used to transform virtually any plant species, including a plant of inbred spinach line SP6111. Agrobacterium -mediated transfer is another widely applicable system for introducing gene loci into plant cells. An advantage of the technique is that DNA can be introduced into whole plant tissues, thereby bypassing the need for regeneration of an intact plant from a protoplast. Agrobacterium transformation vectors are capable of replication in E. coli as well as Agrobacterium , allowing for convenient manipulations. Moreover, advances in vectors for Agrobacterium -mediated gene transfer have improved the arrangement of genes and restriction sites in the vectors to facilitate the construction of vectors capable of expressing various polypeptide coding genes. The vectors have convenient multi-linker regions flanked by a promoter and a polyadenylation site for direct expression of inserted polypeptide coding genes. Additionally, Agrobacterium containing both armed and disarmed Ti genes can be used for transformation. In those plant strains where Agrobacterium -mediated transformation is efficient, it is the method of choice because of the facile and defined nature of the gene locus transfer. The use of Agrobacterium -mediated plant integrating vectors to introduce DNA into plant cells, including spinach plant cells, is well known in the art (See, e.g., U.S. Pat. Nos. 7,250,560 and 5,563,055). Transformation of plant protoplasts also can be achieved using methods based on calcium phosphate precipitation, polyethylene glycol treatment, electroporation, and combinations of these treatments. A number of promoters have utility for plant gene expression for any gene of interest including but not limited to selectable markers, scoreable markers, genes for pest tolerance, disease resistance, nutritional enhancements and any other gene of agronomic interest. Examples of constitutive promoters useful for spinach plant gene expression include, but are not limited to, the cauliflower mosaic virus (CaMV) P-35S promoter, a tandemly duplicated version of the CaMV 35S promoter, the enhanced 35S promoter (P-e35S), the nopaline synthase promoter, the octopine synthase promoter, the figwort mosaic virus (P-FMV) promoter (see U.S. Pat. No. 5,378,619), an enhanced version of the FMV promoter (P-eFMV) where the promoter sequence of P-FMV is duplicated in tandem, the cauliflower mosaic virus 19S promoter, a sugarcane bacilliform virus promoter, a commelina yellow mottle virus promoter, the promoter for the thylakoid membrane proteins from spinach (psaD, psaF, psaE, PC, FNR, atpC, atpD, cab, rbcS) (see U.S. Pat. No. 7,161,061), the CAB-1 promoter from spinach (see U.S. Pat. No. 7,663,027), the promoter from maize prolamin seed storage protein (see U.S. Pat. No. 7,119,255), and other plant DNA virus promoters known to express in plant cells. A variety of plant gene promoters that are regulated in response to environmental, hormonal, chemical, and/or developmental signals can be used for expression of an operably linked gene in plant cells, including promoters regulated by (1) heat, (2) light (e.g., pea rbcS-3A promoter, maize rbcS promoter, or chlorophyll a/b-binding protein promoter), (3) hormones, such as abscisic acid, (4) wounding (e.g., wunl, or (5) chemicals such as methyl jasmonate, salicylic acid, or Safener. It may also be advantageous to employ organ-specific promoters. Exemplary nucleic acids which may be introduced to the multileaf trait spinach of this invention include, for example, DNA sequences or genes from another species, or even genes or sequences which originate with or are present in spinach species, but are incorporated into recipient cells by genetic engineering methods rather than classical reproduction or breeding techniques. However, the term “exogenous” is also intended to refer to genes that are not normally present in the cell being transformed, or perhaps simply not present in the form, structure, etc., as found in the transforming DNA segment or gene, or genes which are normally present and that one desires to express in a manner that differs from the natural expression pattern, e.g., to over-express. Thus, the term “exogenous” gene or DNA is intended to refer to any gene or DNA segment that is introduced into a recipient cell, regardless of whether a similar gene may already be present in such a cell. The type of DNA included in the exogenous DNA can include DNA which is already present in the plant cell, DNA from another plant, DNA from a different organism, or a DNA generated externally, such as a DNA sequence containing an antisense message of a gene, or a DNA sequence encoding a synthetic or modified version of a gene. Many hundreds if not thousands of different genes are known and could potentially be introduced into a plant of inbred spinach line SP6111. Non-limiting examples of particular genes and corresponding phenotypes one may choose to introduce into a spinach plant include one or more genes for insect tolerance, pest tolerance such as genes for fungal disease control, herbicide tolerance, and genes for quality improvements such as yield, nutritional enhancements, environmental or stress tolerances, or any desirable changes in plant physiology, growth, development, morphology or plant product(s). Alternatively, the DNA coding sequences can affect these phenotypes by encoding a non-translatable RNA molecule that causes the targeted inhibition of expression of an endogenous gene, for example via antisense- or cosuppression-mediated mechanisms. The RNA could also be a catalytic RNA molecule (i.e., a ribozyme) engineered to cleave a desired endogenous mRNA product. Thus, any gene which produces a protein or mRNA which expresses a phenotype or morphology change of interest is useful for the practice of the present invention. (See also U.S. Pat. No. 7,576,262, “Modified gene-silencing RNA and uses thereof” U.S. Pat. Nos. 7,230,158, 7,122,720, 7,081,363, 6,734,341, 6,503,732, 6,392,121, 6,087,560, 5,981,181, 5,977,060, 5,608,146, 5,516,667, each of which, and all documents cited therein are hereby incorporated herein by reference, consistent with the above INCORPORATION BY REFERENCE section, are additionally cited as examples of U.S. patents that may concern transformed spinach and/or methods of transforming spinach or spinach plant cells, and techniques from these US patents, as well as promoters, vectors, etc., may be employed in the practice of this invention to introduce exogenous nucleic acid sequence(s) into a plant of inbred spinach line SP6111 (or cells thereof), and exemplify some exogenous nucleic acid sequence(s) which can be introduced into a plant of inbred spinach line SP6111 (or cells thereof) of the invention, as well as techniques, promoters, vectors etc., to thereby obtain further plants of inbred spinach line SP6111, plant parts and cells, seeds, other propagation material harvestable parts of these plants, etc. of the invention, e.g. tissue culture, including a cell or protoplast, such as an embryo, meristem, cotyledon, pollen, leaf, anther, root, root tip, pistil, flower, seed or stalk. The invention further relates to propagation material for producing plants of the invention. Such propagation material comprises inter alia seeds of the claimed plant and parts of the plant that are suitable for sexual reproduction. Such parts are for example selected from the group consisting of seeds, microspores, pollen, ovaries, ovules, embryo sacs and egg cells. In addition, the invention relates to propagation material comprising parts of the plant that are suitable for vegetative reproduction, for example cuttings, roots, stems, cells, protoplasts. According to a further aspect thereof the propagation material of the invention comprises a tissue culture of the claimed plant. The tissue culture comprises regenerable cells. Such tissue culture can be derived from leaves, pollen, embryos, cotyledon, hypocotyls, meristematic cells, roots, root tips, anthers, flowers, seeds and stems. (See generally U.S. Pat. No. 7,041,876 on spinach being recognized as a plant that can be regenerated from cultured cells or tissue). Also, the invention comprehends methods for producing a seed of a “SP6111”-derived spinach plant comprising (a) crossing a plant of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758, with a second spinach plant, and (b) whereby seed of a “SP6111”-derived spinach plant form (e.g., by allowing the plant from the cross to grow to producing seed). Such a method can further comprise (c) crossing a plant grown from “SP6111”-derived spinach seed with itself or with a second spinach plant to yield additional “SP6111”-derived spinach seed, (d) growing the additional “SP6111”-derived spinach seed of step (c) to yield additional “SP6111”-derived spinach plants, and (e) repeating the crossing and growing of steps (c) and (d) to generate further “SP6111”-derived spinach plants. The invention additionally provides a method of introducing a desired trait into a plant of inbred spinach line SP6111 comprising: (a) crossing a plant of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758, with a second spinach plant that comprises a desired trait to produce F1 progeny; (b) selecting an F1 progeny that comprises the desired trait; (c) crossing the selected F1 progeny with a plant of inbred spinach line SP6111, to produce backcross progeny; (d) selecting backcross progeny comprising the desired trait and the physiological and morphological characteristic of a plant of inbred spinach line SP6111; and (e) repeating steps (c) and (d) three or more times in succession to produce selected fourth or higher backcross progeny that comprise the desired trait and all of the physiological and morphological characteristics of a plant of inbred spinach line SP6111, when grown in the same environmental conditions. The invention, of course, includes a spinach plant produced by this method. Backcrossing can also be used to improve an inbred plant. Backcrossing transfers a specific desirable trait from one inbred or non-inbred source to an inbred that lacks that trait. This can be accomplished, for example, by first crossing a superior inbred (A) (recurrent parent) to a donor inbred (non-recurrent parent), which carries the appropriate locus or loci for the trait in question. The progeny of this cross are then mated back to the superior recurrent parent (A) followed by selection in the resultant progeny for the desired trait to be transferred from the non-recurrent parent. After five or more backcross generations with selection for the desired trait, the progeny are heterozygous for loci controlling the characteristic being transferred, but are like the superior parent for most or almost all other loci. The last backcross generation would be selfed to give pure breeding progeny for the trait being transferred. When a plant of inbred spinach line SP6111, representative seed of which having been deposited under NCIMB Accession No. NCIMB 41758, is used in backcrossing, offspring retaining the combination of traits including medium bolting, fast growing, dark green leaf color at maturity, a round leaf tip, arrow shaped leafs, and resistance to downy mildew ( Peronospora farinose f.sp. spinaciae (Pfs)) races 1, 3, 5, 8, 9, and 11 are progeny within the ambit of the invention. Backcrossing methods can be used with the present invention to improve or introduce a characteristic into a plant of the invention, being a plant of inbred spinach line 6111. See, e.g., U.S. Pat. No. 7,705,206 (incorporated herein by reference consistent with the above INCORPORATION BY REFERENCE section), for a general discussion relating to backcrossing. The invention further involves a method of determining the genotype of a plant of inbred spinach line SP6111, representative seed of which has been deposited under NCIMB Accession No. NCIMB 41758, or a first generation progeny thereof, comprising obtaining a sample of nucleic acids from said plant and detecting in said nucleic acids a plurality of polymorphisms. This method can additionally comprise the step of storing the results of detecting the plurality of polymorphisms on a computer readable medium and/or transmitting the results of detecting the plurality of polymorphisms, e.g., by telephony or by means of computer (e.g., via email). The plurality of polymorphisms are indicative of and/or give rise to the expression of the morphological and physiological characteristics of inbred spinach line SP6111. Spinach leaves are sold in packaged form, including without limitation as prepackaged spinach salad or as canned spinach or as frozen spinach. Mention is made of U.S. Pat. No. 5,523,136, incorporated herein by reference consistent with the above INCORPORATION BY REFERENCE section, which provides packaging film, and packages from such packaging film, including such packaging containing leafy produce, and methods for making and using such packaging film and packages, which are suitable for use with the spinach leaves of the invention. Thus, the invention comprehends the use of and methods for making and using the leaves of the spinach of the invention, as well as leaves of spinach derived from the invention. The invention further relates to a container comprising one or more plants of the invention, or one or spinach plants derived from a plant of the invention, in a growth substrate for harvest of leaves from the plant in a domestic environment. This way the consumer can pick very fresh leaves for use in salads. More generally, the invention includes one or more plants of the invention or one or more plants derived from spinach of the invention, wherein the plant is in a ready-to-harvest condition, including with the consumer picking his own, and further including a container comprising one or more of these plants. Having thus described in detail preferred embodiments of the present invention, it is to be understood that the invention is not to be limited to particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope of the present invention.
Spinach, parts thereof, and the making and use thereof, including with respect to the inbred spinach line called SP6111 are disclosed.
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TECHNICAL FIELD OF INVENTION [0001] Invention presented aims to improve the efficiency of biomaterials and tissue engineering scaffolds by introducing precise control of surface topography in a 3D biomaterial or tissue engineering construct by using polymeric nano and micropatterned building blocks. BACKGROUND OF INVENTION [0002] As an alternative method to transplantation for remediation of tissue damage or loss, tissue engineering utilizes scaffolds which are permissive to cell growth and can be degraded and remodeled under in vivo conditions. Most tissue engineering scaffolds are designed to provide sufficient space for cells to grow in and have random porosity to allow diffusion of molecules and cells. It has been shown that remodeling process can be strongly affected if physical or chemical cues are presented to the cells on the surface of tissue engineering scaffolds. Responses of the cells range from cell orientation to aligned extracellular matrix secretion to more subtle changes such as degree of differentiation. For many tissues, intricate extracellular matrix structure is crucial for the functionality of the tissue, and tissue properties generally depend on the orientation of ECM molecules such as collagen and elastin and distribution of the cells. [0003] Natural tissues generally contain more than one cell type in each individual layer arranged in a specific spatial orientation with respect to each other. This orientation and separation is essential for the functionality of these tissues. As an example, cornea tissue contains 5 distinct layers and 3 different cell types, the spatial organization of which should be imitated in order to produce an artificial cornea. Thus, a tissue engineering scaffold for complex tissues with more than one cell type should provide necessary separations between different cell types and at the same time should allow interaction between different cell types through physical and chemical cues available. [0004] Most of the current tissue engineering scaffold designs either have homogeneous forms, such as foams with a random distribution of the pores, or have 2D or 3D features restricted to surface, which in turn can just affect 2D organization of the cells. Different cell types react to different range of topographies (type and magnitude) and accurate simulation of these differences on the tissue engineering scaffolds would improve their efficiency. For example, it has been demonstrated that responses of corneal epithelial and stromal cells to surface cues are distinctly different and the size of the optimal surface topographical feature for each type of cell are different. Thus, a 3D construct with lamella with unique 2D or 3D properties can provide different topographical features for each layer and allow the creation of a scaffold suitable for a complex, multilayer, multi-cell tissue. Thus biomaterials designed for tissue engineering and non-tissue engineering purposes will benefit from the construct developed. [0005] In addition cell free biomaterials with patterned layers and stacked to form multilayer constructs may also be preferable to single layer, unpatterned biomaterials due to their increased organization and thus mimicking more closely the tissue they mimic and/or replace. SUMMARY OF INVENTION [0006] The present invention describes a 3D multilamellar construct manufactured from preproduced individual lamella, of either natural or synthetic polymer origin, which have micro- or nano-scale surface features designed to affect biomaterial performance or cell behavior. This invention includes different methodologies developed for different polymers for preparation of 3D construct, and 3D scaffolds with different dimensions and designs both physical and chemical, with respect to the orientation of lamellae, and different size surface features and multilamellar structures of different thicknesses. It also relates to the application of these structures generally to biomaterials and specifically to tissue engineering of scaffolds for tissues, and especially for a specific target tissue, cornea. [0007] The exemplary demonstration of the present invention, is made with two different polymeric substances, 1) polyesters poly(L-lactide-co-D,L-lactide) ((P(L/DL)LA) and poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV), and 2) collagen. Briefly, collagen and P(L/DL)LA-PHBV membranes with topographical features at micro scale were produced by using photolithography and soft lithography techniques followed by solvent casting. Then solid membranes were brought together by heat application to specific contact points determined with careful consideration of the mechanical properties desired for the specific application. The second method developed is the application of an appropriate solvent in minute amounts to the contact points for local wetting followed by drying process. A third method includes the application of crosslinker solutions, in which the strength of attachment of two layers can be controlled by the concentration, amount and type of crosslinker. [0008] The following detailed description of an embodiment of the invention and related drawings, figures and their descriptions are only of exemplary nature and thus should not be regarded restrictive or illustrative. Further features and aspects of the presented invention will become apparent to those of ordinary skill in the art upon reading and understanding the following detailed description. BRIEF DESCRIPTION OF THE FIGURES [0009] The accompanying drawings, which are incorporated into and form a part of the specification, schematically illustrate one or more exemplary embodiments of the invention and, together with the general description given above and detailed description of the preferred embodiments given below, serve to explain the principles of the invention. [0010] FIG. 1 a . SEM micrograph of a patterned collagen film [0011] FIG. 1 b . Stereomicrograph of a patterned collagen film (Magnification ×30) [0012] FIG. 1 c . Stereomicrograph of a collagen film-based, 3D multilayer construct. In each layer the pattern direction is orthogonal to the subsequent layer. Because of the transparency of the collagen films lower layers can be seen. [0013] FIG. 1 d . Fluorescence micrograph (DAPI staining for cell nuclei) of a collagen film multilayer, seeded with human corneal keratocytes, after 14 days of incubation. [0014] FIG. 1 e . Fluorescence micrograph (DAPI staining for cell nuclei) of a single, patterned collagen film layer, seeded with another type of cell, D407 retinal pigment epithelium cells, after 7 days of incubation. [0015] FIG. 1 f . Fluorescence micrograph (Acridine orange staining for cell nuclei) of a single, patterned collagen film, seeded with human corneal keratocytes, after 7 days of incubation. [0016] FIG. 1 g . Fluorescence micrograph showing distribution of FITC-labeled phalloidin staining of cytoskeletal element (f-actin) and orientation of human corneal keratocytes on single layer of patterned collagen films after 7 days of incubation. [0017] FIG. 1 h . Proliferation rate of human corneal keratocytes on a 3 layered collagen film multilayer as determined by Alamar Blue assay. Tissue culture polystyrene was used as the control. [0018] FIG. 2 a . SEM micrograph of a bilayer of A3 patterned (P(L/DL)LA-PHBV films. Films were brought together in an orientation where the pattern axes were orthogonal to each other. [0019] FIG. 2 b . Fluorescence micrograph (Acridine orange staining for cell nuclei) of D407 retinal pigment epithelium cell-seeded, patterned (P(L/DL)LA-PHBV film after 1 day of incubation. [0020] FIG. 2 c . Fluorescence micrograph (Acridine orange staining for cell nuclei) of D407 retinal pigment epithelium cell-seeded patterned (P(L/DL)LA-PHBV film, after 7 days of incubation. Pattern dimensions are different than the others. [0021] FIG. 2 d . Fluorescence micrograph (DAPI staining for cell nuclei) of human corneal keratocyte seeded, patterned (P(L/DL)LA-PHBV films, after 21 days of incubation. [0022] FIG. 3 Enlarged perspective view of a template (A: Groove width, B: Ridge width, h: Groove depth, θ: Inclination angle) [0023] FIG. 4 a Light micrograph of template (micropatterned Si template—×350) (Sm: smooth-unpatterned region, MP micropatterned region) [0024] FIG. 4 b Light micrograph of polymeric film obtained from the template (micropatterned PHBV-P(L/DL)LA film—×100) (Sm: smooth-unpatterned region, MP micropatterned region) DETAILED DESCRIPTION OF THE INVENTION [0025] In the processes developed in this invention polymers of natural or synthetic origin were used. [0026] Solutions of collagen and solutions of blends of natural and synthetic origin polyesters in different ratios with different concentrations were prepared. [0027] As an example to polyesters, blends of P(L/DL)LA and PHBV were used. Solutions were poured onto patterned templates either produced on silicon wafers by photolithography or obtained by transferring the “parallel grooves and ridges” designs from primary templates made of silicon wafers onto secondary templates. Membrane structures which have inverse surface patterns of the template were produced by solvent casting. Template structure could be of any topographical feature, such as ridges or grooves connected by inclined surfaces of any inclination degree and varying ridge and groove dimensions. Any type of micropattern such as cobblestone, pillar, 2D stripes, square, circular, etc. could be obtained either by photolithography or for nano scale patterning by electron beam lithography or interference lithography or embossing or contact printing or AFM based lithography to accommodate the necessities of any 3D design. [0028] Since the 3D structure of natural polymers is generally very sensitive to harsh treatments a mild chemical method for construction of 3D collagen multilayer was invented. Collagen solution in acetic acid was poured onto micropatterned templates and after solution was air dried, the collagen films formed were peeled off. As the collagen solution different solutions can be used. As an example 0.2 mL, 15 mg/mL in 0.5 M acetic acid can be given. To stabilize these films a crosslinking procedure was carried out. Their crosslinking was achieved by incubation in EDC and NHS. As an example crosslinking can be achieved by incubation in 33 mM EDC and 6 mM NHS in 50 mM NaH 2 PO 4 buffer (pH 5.5) for 2 h at room temperature. Constructs were washed with Na 2 HPO 4 buffer (pH 9.1) for 1 h and then washed successively with 1 and 2 M NaCl. Attachment of several crosslinked films to each other was achieved by addition of a dilute solvent of collagen, 0.1% acetic acid. Solvent addition causes localized dissolution to a certain extent depending on the concentration and the amount of the solvent. Subsequent air drying creates a contact between the membranes due to simultaneous dissolution and drying at the locations which come into contact with the solvent. [0029] A second technique for attaching collagen films, involving collagen solution and a concentrated crosslinking solution, was developed. Collagen solution was applied at the desired contact points to act as a glue between the two layers, and after addition of the collagen solution a concentrated crosslinking solution consisting of EDC/NHS was added to attach the collagen in the solution to the two membranes. With this method, the strength of the contact can be finely adjusted by changing parameters such as concentrations of collagen and crosslinker solution. [0030] P(L/DL)LA-PHBV membranes were formed by solvent casting of a solution of P(L/DL)LA and PHBV in organic solvents such as chloroform or dichloromethane to produce micropatterned membranes with pattern dimensions inverse of those of the template. Micropatterned silicon templates with different dimensions and geometries were produced by photolithography and subsequent chemical etching. The formed membranes were removed by peeling (average film thickness 42 μm) and attached to each other by heat application to 4 corners, melting the polymer films at these points. Alternatively, attachment can be made as in the case of collagen constructs, by placing a droplet of solvent at the corners which causes local dissolution of the polymer to a certain extent depending on the amount of solvent. Air drying of the structure creates a contact between two membranes due to simultaneous dissolution and drying at the points which come into contact with the solvent. [0031] The number of adhesion/contact points, the relative orientation of the surface topographical features, size and geometry of the features, dimensions of each film layer and number of layers can be adjusted during the manufacturing process according to the specific necessities of the target tissue. If a layer of tissue with each layer having a different organization and cell is required than multilayers of different orientations can be separately prepared and then brought together to create a construct with a multilayer, multiorientation structure. If an enhanced level of interaction is necessary between the different cell types present, or if an increased permeability for transference of solutes, growth factors, bioactive agents is needed films can be rendered partially porous by addition of appropriate solute particles of desired dimensions and their subsequent dissolution by a proper solvent which only dissolves these particles and not the film material. Similar property may be achieved by pore formation upon exposure to particulates and electromagnetic radiation. If gradual provision of bioactive agents such as growth factors are needed these agents could be dissolved in the membrane. Example Film Preparation [0032] Three types of films, 1) Patterned (P(L/DL)LA-PHBV films on Type I pattern, 2) Patterned (P(L/DL)LA-PHBV films on Type II pattern, and 3) Patterned collagen films on inverse Type I pattern, were obtained. Films were produced by solvent casting as described previously and the geometry and dimensions of the patterns are given in Table 1. [0000] TABLE 1 Geometry and dimensions of the patterns used Ridge Groove Inclination Geometry of Groove width depth angle Template template width (μm) (μm) (μm) (degree) Type I Parallel 2 10 30 54.7 channels Type I Parallel 10 2 30 54.7 inverse channels Type II Alternating 4 20/10 1 90 square pits Multilayer Preparation [0033] Patterned (P(L/DL)LA-PHBV films were brought together by heat treatment at the edges of the films. By this method up to 8 layers of (P(L/DL)LA-PHBV films were brought together successfully. [0034] Patterned collagen films were brought together by application of collagen and EDC/NHS solutions successively. Up to 3 layers of collagen films were stuck to each other by this method. [0035] Since these 3D constructs were prepared especially for cornea tissue engineering purposes, orientation of the patterns with respect to each other was perpendicular in order to mimic natural corneal stroma structure. [0036] Multilayers were sterilized by immersing in sterile EtOH (70%) for 2 h at 4° C. Constructs were then washed 4 times with phosphate buffer saline (PBS). In Vitro Studies [0037] Human keratocytes culturing was started at passage 2 of a primary cell line and propagated until passage 8. In all experiments keratocytes between passages 4-8 were used. The composition of the keratocyte medium for 500 mL was as follows: 225 mL of DMEM high glucose, 225 ml of Ham F12 medium, 50 mL of new born calf serum, 10 ng/mL human recombinant b-FGF, amphotericin (1 μg/mL), streptomycin (100 μg/mL) and penicillin ( 100 UI/mL) at 37° C., 5% CO 2 in a carbon dioxide incubator. The cells were passaged using 0.05% trypsin-EDTA solution. [0038] D407 retinal pigment epithelium cells (passage 5 to 15) were cultivated in high glucose DMEM supplemented with 5% fetal bovine serum (FBS), 100 units/mL penicillin and 100 units/mL streptomycin at 37° C., 5% CO 2 in a carbon dioxide incubator. The cells were passaged using 0.05% trypsin-EDTA solution. [0039] Keratocytes and D407 cells were detached from the tissue culture flasks by using 0.05% trypsin for 5 min at 37° C., then centrifuged for 5 min at 3000 rpm and resuspended in their respective media. Cell number was counted using NucleoCounter (ChemoMetec A/S, Denmark). 50 000 cells/20 μL were seeded on each construct and the constructs were not disturbed for 30 min to allow cell attachment. After 30 min, 500 μL of media was supplemented to each construct. They were incubated in a CO 2 incubator (5% CO 2 , 37° C.) for 21 days. The medium was refreshed every day. Tissue culture polystyrene (TCPS) was used as the control. SEM Characterization [0040] For SEM, specimens were washed with cacodylate buffer (0.1 M, pH 7.4) and distilled water and freeze dried. Samples were examined with SEM after being sputter coating with gold. Fluorescence Stainings [0041] For fluorescence microscopy (IX 70, Olympus, Japan), specimens were first fixed with glutaraldehyde (2.5%) for 2 h and then washed twice with phosphate buffered saline (PBS) (10 mM, pH 7.4). The samples to be stained with Acridine orange were washed with HCl (0.1 M) for 1 min and Acridine orange was added. After 15 min, Acridine orange was removed and the sample was washed with distilled water. The cells were observed under the fluorescence microscope at the excitation wavelength range of 450-480 nm. [0042] For DAPI and Phalloidin staining, cells on the films were fixed with 4% formaldehyde for 15 min and washed twice with PBS. Then the cells treated with 1% Triton-X-100 for 5 min in order to permeabilize the cell membrane and washed again by PBS 3 times. Samples were then incubated in a blocking solution (1% BSA (bovine serum albumin) in PBS) for 30 min at room temperature and in staining solution for 1 h at 37° C. Staining solution was 1% Phalloidin and 0.1% DAPI in 0.1% BSA in PBS solution. After incubation, samples were washed with PBS and examined under fluorescence microscope at excitation wavelengths of 450-480 nm for Phalloidin and 330-385 nm for DAPI. Cell Proliferation Assay [0043] To determine the cell proliferation rate, Alamar Blue cell proliferation assay was performed. At time points 1, 4, 7, and 10 days for keratocyte seeded multilayers, medium was discarded and samples were washed several times with sterile PBS. Then 5%, 500 μL, Alamar Blue solution was added and samples were incubated in a CO 2 incubator (5% CO 2 , 37° C.) for 1 h. After incubation, Alamar Blue containing media were collected and their absorbance at 570 and 600 nm were determined by a UV-Visible spectrophotometer. Percent reduction of the dye by the metabolic activity of the cells was then determined by using the absorption coefficients of the reduced and the oxidized dye. Cell number was then determined by using a calibration curve constructed using the reduction percentage of the dye in the presence of known cell numbers. Brief Explanation of the Process [0044] In this invention different methodologies have been developed for different polymers for the preparation of biomaterials and/or 3D scaffolds with different dimensions and designs, both physical and chemical, with respect to the orientation of lamellae, and different size surface features and multilamellar structure of different thickness. [0045] The main steps of these methodologies are; Solutions of collagen, and solution of blends of P(L/DL)LA and PHBV with different concentrations are prepared. Polymer solutions are poured onto patterned templates either produced on silicon wafers by photolithography or obtained by transferring the “parallel grooves and ridges” or “alternating square pits” designs from primary templates made of silicon wafers onto secondary templates. Membrane structures which have same or inverse surface patterns of the template are produced by solvent-casting. Template structure could be of any topographical feature, such as ridges or grooves connected by inclined surfaces of any inclination degree and varying ridge and groove dimensions. Any type of micropattern such as cobblestone, pillar, 2D stripes, square, circular, etc. could be obtained either by photolithography or for nano scale patterning, by electron beam lithography or interference lithography photolithography or embossing or contact printing or AFM based lithography to accommodate the necessities of any 3D design. When the polymer used is collagen, a mild chemical method for construction of 3D collagen multilayers is developed; the 3D structure of natural polymers is generally very sensitive to harsh treatments. Collagen solution (in acetic acid) having a concentration of 2-25 mg/mL (preferably 15 mg/mL) is poured onto micropatterned templates. Low end of concentration range is due to extremely low thickness and low mechanical property whereas the high end is due to the excessive viscosity that hinders proper processing. The amount of collagen solution poured onto template is 50 μL-1 mL per square cm of template surface; not lower than 50 microliter to prevent too thin films with insufficient thickness and mechanical strength and not higher than 1 mL because it will not be possible to maintain higher volumes on such a small area and also the resultant films would be too thick, too rigid and of low transparency. After the solution is dried, the collagen films formed are peeled off. Drying is achieved in between 10 to 24 hours at room temperature without any gas or air circulation. Drying duration may be shortened when the temperature is higher, when there is air or gas circulation or when heated or when solution volume used is lower. To stabilize these films a crosslinking procedure is carried out. The crosslinking is achieved by incubation in 33 mM EDC and NHS in buffer preferably phosphate buffer (preferably pH 5.5) for 2 h at room temperature. The pH value of buffer is between 4 and 6 due to the decreased reactivity of EDC outside this pH range. Duration of cross linking is in between 30 minutes and 4 hours, depending on the degree of crosslinking required, and at temperatures between +4 to 37° C., where the upper limit is due to the denaturation of collagen at the temperatures above 37° C. Cross linking can be achieved by glutaraldehyde, genipin, dendrimers and others. Constructs are washed with buffer, preferably phosphate buffer, for 1 h and then washed successively with 1 and 2 M NaCl. Buffer is preferably Na 2 HPO 4 and its pH value is preferably 9.1. Attachment of several crosslinked films to each other is achieved by application of drops a dilute solvent of collagen, 0.1% acetic acid, Solvent application causes localized dissolution to a certain extent depending on the concentration and the amount of the solvent. Subsequent drying creates a contact between the membranes due to simultaneous dissolution and drying at the locations which come into contact with the solvent. The solutions of blends of polyesters in different ratios with different concentrations in organic solvents are prepared, The polyesters are preferably P(L/DL)LA and PHBV. The films were formed by solvent casting of a solution P(L/DL)LA and PHBV in organic solvents to produce micropatterned membranes with pattern dimensions inverse of those of the template. Organic solvents may be chloroform, dichloromethane and the like. The polymer solution concentration is 2-10%, preferably 4%, in an organic solvent; not lower than 2% to achieve sufficient thickness and mechanical strength and not higher than 10% to achieve proper viscosity for proper film formation. Micropatterned silicon templates with different dimensions and geometries were produced by photolithography and subsequent chemical etching. P(L/DL)LA and PHBV blend ratio may be varied between 1:0 to 0:1 preferably 1:1 to achieve films of different transparency and rigidity. P(L/DL)LA and PHBV solution poured onto template is 50 μL-1 mL per square cm of template surface; not lower than 50 μL to prevent too thin films with insufficient thickness and mechanical strength and not higher than 1 mL because it will not be possible to maintain higher volumes on such a small area and also the resultant films would be too thick, too rigid and of low transparency. Drying is achieved in 10 or more hours at room temperature without any gas or air circulation or vacuum application or heating. Shorter duration would lead to solvent retention and improper performance. When the temperature is higher, when there is air or gas circulation, when vacuum is applied or when the solution volume used is lower then the drying duration may be shortened. The formed membranes were removed by peeling (average film thickness 42 micrometers) and attached to each other by heat application to 4 corners, melting the polymer films at these points. Alternatively, attachment can be made by placing a droplet of solvent at the corners which causes local dissolution of the polymer to a certain extent depending on the amount of solvent. Drying of the structure creates a contact between two membranes due to simultaneous dissolution and drying at the points which come into contact with the solvent. Brief Explanation of the Alternatives of the Process [0072] A second technique for attaching collagen films involving collagen solution and a concentrated crosslinking solution was developed. Collagen solution was applied at the desired contact points to serve as a glue between two successive layers After addition of the collagen solution a concentrated crosslinking solution consisting of EDC/NHS was added to attach the collagen in the solution to the two membranes. With this method, the strength of the contact can be finely adjusted by changing parameters such as concentration of collagen and crosslinker solution. [0076] A third technique for attachment of subsequent collagen film layers to each other is application of an adhesive such as fibrin glue or cyanoacrylate. [0077] The number of adhesion/contact points, the relative orientation of the surface topographical features, size and geometry of the features, dimensions of each film layer and number of layers can be adjusted during the manufacturing process according to the specific requirements of the target tissue. [0078] The template structure is any type of micropattern such as cobblestone, pillar, 2D stripes, square, circular. [0079] The templates could be obtained either by photolithography or electron beam lithography or interference lithography or embossing, or contact printing or AFM based lithography to accommodate the necessities of any 3D design. [0080] The designs on the templates could be at nano or micro level. [0081] The constructs may be seeded with cells that are appropriate for the target tissue. [0082] The constructs may be seeded with one or more than one cell type according to the cell population of the target tissue. [0083] If layers of tissue, where each layer has a different organization and cell, is required then multilayers of different orientations can be separately prepared and brought together to create a multilayer, multiorientation, and multicell construct. [0084] If an enhanced level of interaction is necessary between the different cell types present, or if an increased permeability for transference of solutes, growth factors, bioactive agents is needed then the films can be rendered partially porous by leaching off solute particles of desired dimensions contained in a proper solvent which only dissolves these particles and not the film material. Creation of pores may also be achieved through application of electromagnetic or particulate radiation [0085] If gradual provision of bioactive agents such as growth factors are needed these agents could be dissolved in the films. [0086] The process is applied to natural and synthetic polymers such as chitosan, NIPAM, PDMS, PCL, hyaluronic acid, chondroitin sulfate or blends of biodegradable and nondegradable polymers.
Stacked, lamellar constructs comprised of, synthetic or natural, polymeric membrane structures which are brought together to form 3D scaffolds for biomaterial and guided tissue engineering applications have been developed. Each layer can have 2D or 3D nano and micro topographical features similar to or different than each other which can be arranged during the construction of each lamellae and their orientation can be adjusted during construction phase of the 3D structure. Such a construct was utilized in the development of an artificial cornea with human primary cells, in which patterned surface of the components of the lamellar structure mimics the oriented collagen structure inherent in natural cornea. Similar exploitation of the 3D patterned structure can be made for tissues where aligned ECM architecture is crucial, such as ligaments, bone, tendon, skin.
2
FIELD OF THE INVENTION This invention relates to methods of playing games and methods of amusement; in particular, this invention relates to methods of playing wagering games, especially wagering games in the context of a casino or other commercial venue; most particularly this intention relates to methods of playing card games at tables in a casino or other commercial venue and virtual card games in self contained games in the casino environment. STATE OF THE ART The card game known as Blackjack or Twenty-One is a common card game played for recreation in every conceivable venue, including homes, dormitory rooms, lunch rooms and, of course, in casinos and other organized venues for the promotion of wagering throughout the world. In Twenty-One the outcome is determined by either the player or the dealer having the highest hand value that does not total more than twenty one as defined by the numerical amounts of the cards in the hand value. The hand value is defined by the numerical value of the cards dealt with two exceptions: a) the face cards are all defined to have a value of ten, and b) the ace may have a value of either one or eleven at the player's option. The best hand is called the blackjack, and consists of a two card hand totaling twenty one, which is a hand comprising an ace and a ten. As the game is typically played, insurance, doubling down, and splitting a pair are the only side bets normally allowed, when “side bet” is defined as a bet that requires an additional wager, and is based on an occurrence that may or may not affect the ultimate outcome of the game. The two traditional side bets mentioned illustrate the concept. When the dealer shows an ace a player may place a second bet to ‘insure’ that the dealer doesn't have a ten as his down card. If the dealer has some other card than a ten, the player loses the wager for the insurance, play continues for that hand, and the player may still win the hand. Similarly, the player may double down by placing a second bet after the first two cards have been dealt that the next card dealt to him will give him a better hand than the dealer—that is, his three card hand will beat the hand the dealer eventually will wind up with. Splitting a pair is not quit a side bet as herein defined, since the player splits a pair of cards, for example a 9-9, and then player plays both of the two hands to the conclusion of the game, each hand containing a 9 from his original hand. He may usually split the next hand if he gets a third 9. Of course the rules for these side bets may vary from casino to casino. The need for casinos to attract more customers, particularly the casual player who may not fully understand the table games, has caused a recent upsurge in interest in developing new easy to understand and play side-bets for established table games such as Twenty-One. The need has resulted in several innovations in table games found in casinos. Some have filled the need admirably, but the average life time for a variant side bet game is short enough that there remains a continuing need for candidate games. SUMMARY OF THE INVENTION A card game that can be a side bet or an adjunct to the casino card game of twenty-one is played by placing a wager that the face up card of a dealer will be a value of ten; dealing to at least one player the first two cards of a twenty-one game from at least one randomly shuffled deck of cards containing at least one standard playing card deck of fifty two cards; dealing to a dealer two cards, the first of said cards being dealt one face up, and the second of said cards, a hole card, being dealt face down; determining if the dealers face up card is a card with a value of ten: which is a ten card, a jack card, a queen card or a king card; then depending on the value of the face up card following one of two courses of action, if there is no ten, jack, queen or king showing, collecting the money bet the ten wager, then continuing to deal the twenty-one game until its resolution; if the dealer has a ten card showing, paying the wager at a first predetermined amount if his hole card is an Ace, paying the wager at a second predetermined amount if his hole card is a ten, paying the wager at a third predetermined amount if he has anything other than an ace or a ten; then continuing to deal the twenty-one game until its resolution This invention provides a method for playing a modified form of blackjack or twenty-one played with at least one standard deck of at least fifty two cards consists of wagering whether the dealer has a winning hand based on the observation that the dealer has dealt himself a ten as an up card. In particular this invention provides a card game comprising the method of: Placing a wager that the face up card of a dealer will be a value of ten; Dealing to at least one player the first two cards of a twenty-one game from at least one randomly shuffled deck of cards containing at least one standard playing card deck of fifty two cards; Dealing to a dealer two cards, the first of said cards being dealt one face up, and the second of said cards, a hole card, being dealt face down; Determining if the dealers face up card is a card with a value of ten: a ten crd, a jack card, a queen card, or a king card; If the dealers face up card is not a ten, jack, queen or king, collecting the money bet the ten wager, then continuing to deal the twenty-one game until its resolution; If the dealer has a ten card showing, paying the wager at a first predetermined amount if his hole card is an Ace, paying the wager at a second predetermined amount if his hole card is a ten, and paying the wager at a third predetermined amount if he has anything other than an ace or a ten value card; then continuing to deal the twenty-one game until its resolution. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Blackjack or twenty one is defined herein as a game wherein a first participant, hereinafter the ‘dealer’, who plays for the house, deals two cards apiece to a second participant, hereinafter the ‘player’, and himself. The player is therefore really playing against the house. The point of the game is for the player to match or beat the dealer's cards without going over twenty one points, called going ‘bust.’ Points are determined by the number of the card: that is a 2 is worth two points, a 3, three points and so forth, up to a 10 being worth ten points. The face cards, that is the Jacks, Queens, and Kings, are all worth ten points and an ace is worth either one point (which is used in what is termed a ‘hard’ hand) or eleven points (which is used in a ‘soft’ hand). The best hand is twenty one points, which can be achieved by any number of cards but the two card hand of an ace, counted here as an eleven, and any card worth ten points, which hand is called a Blackjack, is considered the best. Herein, a deck of cards will considered to be a deck containing a minimum of fifty two cards including an ace (A), 2, 3, 4, 5, 6, 7, 8, 9, 10, Jack (J), Queen (Q), and King (K) in the four suits of clubs, spades, hearts and diamonds. J, Q, and K are defined as the face cards; and face cards and ten cards have a value of ten in the game of twenty one. A two card hand will herein be denoted as, for example, 2-7 for a hand containing a two, of any suit, and a seven, of any suit. Other cards may be added to the deck, such as jokers or the like, so the total number of cards may well be higher than fifty two. Moreover, from one to seven or more extra decks may be added to the original first deck. However, the “deck” as defined herein will always contain at least the fifty two cards of the standard deck, and those fifty two cards will always be randomly shuffled before being dealt to the player. As used herein, a “card” can be a physical elongate paper or plastic item with a numerical value printed thereon, or it can be a virtual card, which is defined herein is any representation of a playing card that may look identical to the numerical side of a physical card or may be abbreviated, having, for example, only a number and a suit identified thereon. Virtual cards are used in conjunction with a computer, or similar digital processing means, which will display the virtual card on a video display monitor or other active display device. As used herein, the term “video monitor” includes CRT video monitors and all equivalents of CRT video monitors such as LED screens and plasma screen displays of any sort that displays graphical images of digital information. If virtual cards are used then the “dealer” will usually be a virtual dealer. The virtual dealer is a computer, specifically the processor of the computer. The processor calculates the values of the hands as they are played and displays the hands to the player on a display device. In general, the player will activate the processor by dropping a coin into a slot and pressing a button. However, strictly computer driven games, that include no possibility of money changing hands are also contemplated by the invention—for example, games played at home and the like strictly for amusement or for practice for actual play in a casino. If one uses a computer style of game, the dealer's role remains unchanged from what it would be if the dealer was a live person standing or sitting at the gaming table. Therefore, as used herein, the term “dealer” will includes both live dealer and the virtual dealer created by the processor. The dealer does not normally participate beyond dealing in most twenty one games, but the person playing the dealer may be rotated in and out, and the dealer may play hands against himself—thereby lowering the likelihood of a player winning any given hand. There may be between one to as many as seven players in the normal casino version of the blackjack or twenty one game, although, in theory, the number of players could be much greater. This invention is a method of playing the game of twenty-one between either a live dealer or a virtual dealer. The dealer may be dealing either real cards or virtual cards. The dealer, live or virtual, will deal to at least one live twenty-one player. The player will place a first wager on whether the twenty-one player or the dealer will win the twenty-one game. This is the standard bet in Twenty-one. The player may then place a second bet if the dealer shows a ten that the dealer will win the hand. That is, if the player knows the dealer has deal himself a 10, he may place a wager that the dealer will win the hand, or, the player may place the bet at the same time he makes the wager on the twenty one hand. The dealer deals to the player the first two cards of a twenty-one game from at least one randomly shuffled deck of cards containing at least one standard playing card deck of fifty two cards. The dealer also deals himself two cards, one face up, and one face down. The face down card is the “hole” card. It will be appreciated that if the dealer is a virtual dealer, the deck of cards is formed by shuffling 52 numbers, each representing a card using any of several standard algorithms. Images of the randomly shuffled cards are then presented on the video monitor. Once the first two cards are dealt, if the dealer has a ten card showing, he will resolve the first wager, if he does not, he will collect the money wagered for the ten wager, then he will continue to deal the twenty-one game until its resolution. It will be realized that this game can be played without any monetary wager or bet being made. All that needs be done is that the player have some means of indicator means to indicate whether he wants to play this form of cards, and an indication or indicator proving that he has won or he lost the hand. If the dealer has a ten card showing, he will pay 6 to one if his hole card is an Ace, 3 to one if his hole card is a ten, and 1 to 1 if he has anything other than an ace or a ten. The wager described is on the first two cards dealt only, that is to say, if the dealer draws a ten for any other card he may deal to himself, there is no money to be paid to the player. A preferred mode of playing this game includes an optional bonus bet as part of the payout for the side bet, where if the dealer has a ten card, and his face down or hole card is also a ten card (the ten cards here being the card between a nine and a jack ONLY) the player receives an enhanced bonus, usually about 40 to one. This invention has been described in detail with reference to specific embodiments of the invention and examples thereof. Alterations, modifications, and other changes to those embodiments and examples will invariably suggest themselves to those of ordinary skill in the art relating to this invention. Therefore, it is intended that the scope of this invention should be determined solely by reference to the appended claims, which appended claims encompass all such alterations, modifications, and changes.
A side bet for Blackjack also known as twenty-one is disclosed. The player places a side wager that the dealer's up card will be a ten-value card. If the dealer's up card is a ten-value card, then the player is paid 1 to 1. Potential additional side payoffs include whether the dealer's hole card is a ten-value card, in which case the player wins 3 to 1 or whether the dealer's hole card is an ace, in which case the player is paid 6 to 1. Other potential side payoffs are also disclosed.
0
FIELD OF THE INVENTION [0001] This invention relates to organic chemical synthesis and compounds useful therein. More specifically, it relates to processes for synthesizing the class of pharmaceutically active products known as tetrahydrocannabinols, as exemplified by dronabinol, and to chemical compounds useful as intermediates in such processes. BACKGROUND OF THE INVENTION [0002] Tetrahydrocannabinols are the active constituents of marijuana (hashish). The major active form, the Δ 1 -3,4-trans isomer of chemical formula: known as Δ 9 -THC, or by the generic name dronabinol, has approved pharmaceutical applications as an anti-emetic, e.g. for enhancing appetite in patients suffering side effects of chemotherapy, suffering from AIDS or anorexia. Its synthesis on a commercial scale presents particular difficulties, however, because the compound possesses several stereoisomeric forms, only one of which, the Δ 1 -3,4-trans isomer (dronabinol), is significantly active. Synthetic processes which lead to the production of a mixture of stereoisomers require a step of separation of the stereoisomers, which is difficult and tedious and tends to render such a process economically unattractive Extraction of dronabinol from its natural plant source presents similar difficulties, since other stereoisomers are naturally present. BRIEF REFERENCE TO THE PRIOR ART [0003] Handrick et al., Tetrahedron Letters 1979, pages 681-684 report a synthetic process for dronabinol which starts from a readily available monoterpene, namely p-menth-2-ene-1,8-diol, of formula: This is reacted with olivetol, 1,3-dihydroxy-5-pentylbenzene, to produce compounds with the desired dibenzopyran ring structure of dronabinol, but along with substantial amounts of other products that then require to be separated. [0004] Evans et al. Journal of the American chemical Society, 1999, volume 121, pages 7582-7594, report a total synthesis of ent-Δ 1 -tetrahydrocannabinol, the enantiomer of dronabinol. The process involves a step of coupling olivetol to the allylic alcohol 1-methyl-3-hydroxy-4-(2-hydroxyprop-2-yl)cyclohex-1-ene in which the substituents at the 3-and 4-positions of the cyclohexene ring are in the trans configuration. The resulting coupled product is cyclized and reportedly produces the unnatural enantiomer of dronabinol. [0005] U.S. Pat. No. 5,227,537 Stoss describes a process of reacting cis-p-menth-2-ene-1,8-diol with olivetol to prepare 6,12-dihydro-6-hydroxycannabidiol (alternative nomenclature 1,3-dihydroxy-2-[6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-yl]-5-pentylbenzene), followed by cyclization thereof to trans-Δ 9 .tetrahydrocannabinol. The intermediate 6,12-dihydro-6-hydroxycannabidiol is reportedly readily purified by crystallization. SUMMARY OF THE INVENTION [0006] It has now been discovered that dronabinol can be prepared, in relatively high yield and high stereoselectivity, by reaction of a cis-configured cyclohexene diol, namely cis-(1S,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-ol of formula II; (hereinafter sometimes cis-menth-1-ene-3,8-diol), with olivetol to produce the appropriate aryl substituted cyclohexene which has the trans configuration of the hydroxyisopropyl and aryl substituents on the cyclohexene ring required for dronabinol. The desired trans compound is crystalline, and so it can be readily purified by recrystallization. The simple cyclization of this trans-configured intermediate, which has the formula: to form the dibenzopyran ring structure of dronabinol retains the stereochemistry of the intermediate, and produces dronabinol in high purity and in good, commercially acceptable yields. [0007] Cis-menth-1-ene-3,8-diol is a known compound—see for example Tetrahedron 1987, 43, pages 5537-5543. [0008] Thus according to the present invention, from one aspect, there is provided a process for preparing 1,3-dihydroxy-2-[(1R,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-yl]-5-pentylbenzene, of chemical formula: the hydroxyisopropyl group at position 5 and the aryl group at position 6 of the cyclohexene ring being disposed trans to one another, which comprises reacting cis-(1S,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-ol of formula: (the hydroxy and the hydroxyisopropyl substituents being disposed cis to one another), with olivetol (1,3-dihydroxy-5-n-pentylbenzene), of formula: BRIEF REFERENCE TO THE DRAWINGS [0009] FIG. 1 of the accompanying drawings depicts the chemical reactions of the final two steps of the preferred process of the present invention for preparing dronabinol; [0010] FIG. 2 of the accompanying drawings depicts the preferred overall chemical synthesis according to the present invention, and illustrates novel intermediates. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0011] The reaction of cis-(1S,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-ol (II) with olivetol (IV) is conducted using reagents and conditions which have been previously used with analogous starting materials—see for example the aforementioned paper by Handrick et al. The reaction can be conducted in solution in an organic solvent, e.g. methylene chloride, benzene, diethyl ether, and in the presence of the Lewis acid catalyst such as boron trifluoride, zinc chloride, zinc bromide or stannic chloride. A chiral catalyst is not required, to obtain the desired stereoisomers, thereby avoiding significant costs associated with some prior art processes. The reaction takes place over a period of 2-8 hours, at room temperature, preferably with dropwise addition of cis-menth-1-ene-3,8-diol. The resulting trans-configured intermediate (III) can be recovered in relatively pure form by crystallization, and then cyclized to form dronabinol in a subsequent step. Alternatively, the cyclization process can be conducted on the reaction product mixture from the coupling step, without recovering and isolating compound (11), to produce pure dronabinol, essentially free of other stereoisomers. This step of cyclization is known in the art, and can be conducted by known procedures—see for example the aforementioned paper by Evans et al. It may be conducted in solution in any of the previously mentioned solvents, in the presence of a Lewis acid such as zinc chloride or zinc bromide. [0012] These processes are illustrated in accompanying FIG. 1 of the drawings. Cis-menth-1-ene-3,8-diol (compound II) is reacted with olivetol (compound IV) under conditions as described above, resulting in the formation of intermediate (III), which has the trans configuration, in contrast with the cis configuration of compound (II). It is believed that this trans configuration is assumed to minimize steric interactions between substituents on the cyclohexene ring as arylation of compound (II) takes place. The resulting intermediate III is then cyclized to dronabinol (I), maintaining the trans configuration of the intermediate. [0013] From another aspect, the present invention in its preferred embodiment provides a novel process for preparing enantiomerically enriched cis-menth-1-ene-3,8-diol (compound 11), in a stereospecific manner. Whilst as noted cis-menth-1-ene-3,8-diol is a known compound, it is not easily available in significantly enantiomerically enriched form, in contrast with the corresponding trans isomer (isolatable according to the procedure described by Evans et. al. in the aforementioned paper). The process of the preferred embodiment of the invention involves several steps, and produces several novel chemical compounds as intermediates in the synthesis. Each of these novel intermediates constitutes a further aspect of the preferred embodiments of this invention. [0014] The starting materials for the overall process are 2-methyl-3-butyn-2-ol ( FIG. 2 , compound 10), which is commercially available. This is converted to 1-acetoxy-3-methyl-1,3-butadiene (compound 12), by reaction with acetic anhydride under strongly acidic conditions, e.g. in the presence of phosphoric acid, followed by a rearrangement catalyzed by a transition metal ion, e.g. silver(I) or copper (I). Next, the recovered and purified diene 12 is subjected to a Diels-Alder reaction to form a 2-substituted 4-methylcyclohex-3-ene carboxylic ester of general formula: in which R represents lower (C 1 -C 6 ) acyl, lower alkyl, silyl, hydrogen, lower alkylsulfonyl, arylsulfonyl, lower alkoxysulfonyl or lower alkoxyphosphoryl, and R′ represents hydrogen or lower alkyl This is a novel class of chemical compounds, constituting a further aspect of the present invention. The class is exemplified by methyl 2-acetoxy-4-methylcyclohex-3-ene carboxylate, compound 14, illustrated on FIG. 2 . The Diels-Alder reaction can be accomplished by reaction with methylacrylate in the presence of a polymerization inhibitor such as hydroquinone in solution in inert organic solvent such as toluene or isopropyl acetate, at elevated temperatures. The reaction initially yields a mixture of cis and trans isomers, isolated as a racemate by solvent extraction e.g. with hexane. Upon cooling, e.g. to −20° C., a precipitate is formed, which consists of essentially pure racemic cis isomer. The cis carboxylate 14 is then hydrolyzed with alkali metal hydroxide to yield the free hydroxy acid 16, another novel product, as a racemate. Next, the substituted cyclohexene of formula V as exemplified by 2-hydroxy-4-methylcyclohex-3-ene carboxylic acid 16 is resolved to isolate the desired (1R,2S) enantiomer. This can be achieved using a chiral amine resolving agent, e.g. one of the enantiomers of methylbenzylamine, to form an addition salt of the chiral amine and compound V, such as the benzylamine addition salt illustrated at 18. Such addition salts constitute another class of novel compounds. The salt can be isolated by precipitation, essentially as a single enantiomer. The simple step of basic extraction followed by acidification of an aqueous solution of this chiral salt, e.g. with hydrochloric acid, yields the free hydroxy acid, compound 20, another novel compound, as a single enantiomer, having a cis configuration of the hydroxy and carboxylic acid ring substituents. [0015] Compound 20, (1R,2S)-2-hydroxy-4-methyl cyclohex-3-ene carboxylic acid, in its cis form, is then esterified e.g. by reaction with methanol/acid, methyl iodide or dimethylsulfate, to form the corresponding methyl ester, compound 22. Whilst the methyl ester is the chosen ester, any other lower alkyl or similar ester could be prepared at this stage. The cis configuration is retained. This ester 22 is next converted to cis-(1S,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-ol, compound II, cis-menth-1-ene-3,8-diol, e.g. by reaction with a methyl magnesium halide at low temperature in solution in tetrahydrofuran. [0016] The process steps of the invention are further described, for illustrative purposes, in the following specific example, a stepwise synthesis of dronabinol according to the preferred embodiment of the invention. Step 1: Synthesis of 1-acetoxy-3-methyl-1,3-butadiene (12) [0017] A solution of 2-methyl-3-butyn-2-ol (84 g; 1 mol) was added to a stirred solution of phosphoric acid (1.75 g; 0.02 mol) in acetic anhydride (152 g; 1.5 mol) over fifty minutes at room temperature under nitrogen. This reaction is exothermic. To minimize the exothermic of the reaction, the rate of addition of 2-methyl-3-butyn-2-ol was controlled so that the reaction temperature remained in the range of 46° C.-50° C. The solution was stirred at room temperature for 1 hour. TLC showed complete consumption of starting material. The reaction mixture was heated to 70° C. and a slurry of 0.5 g (0.003 mol) of silver carbonate and 3.18 g (0.03 mol) of sodium carbonate in 10 ml of acetic anhydride was added over a period of 30 minutes. The solution was heated at 120° C. for 3½ hours. [0018] Sodium chloride (30 g; 0.5 mol) was then added to the mixture, once it had cooled to 70° C., and heating at 120° C. was continued for 6 hours. The cooled mixture was poured into a mixture of water and tert butyl methyl ether (750 ml each). The organic extract was washed three times with sodium carbonate (200 ml each). The organic extract was dried over a mixture of anhydrous magnesium sulphate and anhydrous potassium carbonate. The solvent was evaporated and the product collected by fractional distillation (60-74° C./36 torr) to give 40.28 g (32%) of 1-acetoxy-3-methyl-1,3-butadiene. Step 2: Synthesis of methyl 2-acetoxy-4-methylcyclohex-3-ene carboxylate (14) [0019] A mixture of 1-acetoxy-3-methyl-1-butadiene (15.08 g; 0.12 mol), methyl acrylate (11.2 g; 0.13 mol) and hydroquinone (13 mg; 0.12 mmol)) in toluene (30 ml) was heated for 8 hours at 120° C. The solvent was removed under vacuo. 25 ml of hexane was added into the crude product mixture and the upper layer was decanted and stored in the freezer over night. The resulting crystals were filtered and washed with 10 ml of cold hexane and dried at 20° C. for 3 hours to give 11.65 g (47%) of methyl 2-acetoxy-4-methylcyclohex-3-ene carboxylate. Step 3: Synthesis of 2-hydroxy-4-methylcyclohex-3-ene carboxylic acid (16) [0020] A 100 mL round-bottom flask equipped with a magnetic stir bar and nitrogen inlet was charged with the acetate ester 14 (5.306 g, 25 mmol) and a solution of LiOH (8.392 g, 200 mmol) in 53 mL of H 2 O. The reaction was stirred for 3 h at room temperature. TLC (2:1:0.5 Hexane:EtOAc:HOAc) indicated reaction was complete. 20 mL of MTBE was added and the aqueous phase removed to a separate flask. The aqueous solution was cooled to ˜5-10° C. and acidified to pH˜2 with concentrated HCl. A small amount of precipitate was removed by filtration at room temperature. The filtrate was extracted with 3×40 mL of MTBE and the combined organic layers dried over sodium sulphate and rotovaped to a yellow oil that solidified upon cooling to give 2.798 g (72%) of the hydroxy acid 16. Step 4: Resolution of 2-hydroxy-4-methylcyclohex-3-ene carboxylic acid [0000] Part A [0021] A 100 mL round-bottom flask equipped with a magnetic stir bar and nitrogen inlet was charged with the hydroxy acid 16 (2.40 g, 15 mmol) and 24 mL of acetone. (+)-methylbenzylamine (1.96 mL, 15 mmol) was added and the white dispersion became clear. After ˜0.5 h at room temperature, a white precipitate formed. The reaction was stirred for an additional 1 h at room temperature and the precipitate was collected by vacuum filtration and dried in a vacuum oven to give 1.305 g (31%) of the corresponding chiral salt 18. [0000] Part B [0022] A 200 mL round-bottom flask equipped with a magnetic stir bar, nitrogen inlet, and thermometer was charged with chiral salt (2.795 g, 10 mmol) and 56 mL of saturated aqueous sodium bicarbonate. The solution was stirred to dissolve all solids and then transferred to a separatory funnel and washed with 28 mL of MTBE. The aqueous phase was returned to the flask and cooled to −5° C. 6N HCl was added dropwise until pH=2.00. The temperature did not exceed 0° C. during addition. The solution was transferred to a separatory funnel and the product extracted with 3×28 mL of MTBE. The combined organic phases were washed with brine, dried over sodium sulphate and concentrated to give 1.220 (79%) of the hydroxy acid 20 as a white solid. Step 5: Synthesis of methyl 2-hydroxy-4-methylcyclohex-3-ene carboxylate (22) [0023] A 100 mL round-bottom flask equipped with a magnetic stir bar and nitrogen inlet was charged with the hydroxy acid (0.781 g, 5 mmol), potassium carbonate (1.037 g, 7.5 mmol) and 20 mL of acetone. Dimethyl sulphate (0.52 mL, 5.5 mmol) was added and the reaction was stirred at room temperature for 48 h. The reaction was filtered and concentrated to a clear oil. The crude product was purified by flash column chromatography (1:1 hexane:ethylacetate) to yield 0.797 g (92%) of pure hydroxy ester 22 as a clear oil. This product stays as a clear oil until placed under vacuum, at which point fine, needle-like crystals form at the top of the flask (possible sublimation). Seeding the remaining oil with one of these crystals gives the product as a white crystalline solid. Step 6: Synthesis of 6-(1-Hydroxy-1-methylethyl)-3-methylcyclohex-2-en-1-ol (II) [0024] A 100 mL round-bottom flask equipped with a magnetic stir bar and nitrogen inlet was charged with the hydroxy ester 22 (0.797 g, 4.7 mmol) and 20 mL of THF and then cooled to −78° C. Methylmagnesium bromide (7.80 mL, 23.4 mmol) was added dropwise and the reaction was allowed to warm to room temperature. After stirring at room temperature for 3 h, the reaction was quenched with 10 mL of saturated ammonium chloride. The product was extracted with 2×20 mL of ethyl acetate and the combined organic layers were then dried over sodium sulphate and concentrated to give 0.763 g (95%) of the diol II as a pale yellow oil. Step 7: Synthesis of 1,3-Dihydroxy-2-[6-hydroxy-1-methylethyl)-3-methylcyclohex-2-en-1-yl]-5-pentylbenzene (III) [0025] A 2000 mL round-bottom flask equipped with a magnetic stir bar and nitrogen inlet was charged with dichloromethane (600 mL), olivetol (20.00 g, 111 mmol) and 2.60 g of Camphorsulfonic acid. A solution of diol (20.00 g, 118 mmol) in dichloromethane (600 mL) was added dropwise over a period of 3 hours, and stirring was continued for another 3 h. The reaction was quenched by pouring into 700 mL of saturated sodium bicarbonate, the layers were separated and the aqueous phase was extracted with 2×200 mL of dichloromethane. The combined organic layers were then dried over magnesium sulphate, filtered and concentrated under vacuum to give a brown oil. Crystallization from hexane gives 14.3 g (39%) of the intermediate III as a white solid. Step 8: Synthesis of Dronabinol (I) [0026] A 1000 mL round-bottom flask equipped with a magnetic stir bar, reflux condenser and nitrogen inlet was charged with dichloromethane (200 mL), zinc chloride (5.30 g, 39 mmol) and magnesium sulfate (28.30 g, 235 mmol). The solvent was brought to reflux, and a solution of intermediate II (13.00 g, 39 mmol) in dichloromethane (200 mL) was added in one portion. The resulting suspension was refluxed for 50 minutes, after which the reaction mixture was quickly cooled in an ice-water bath and then quenched by pouring into 400 mL of saturated sodium bicarbonate. The layers were separated and the aqueous phase was extracted with 2×200 mL of dichloromethane. The combined organic layers were washed once with brine, then dried over magnesium sulfate, filtered and concentrated under vacuum to give a yellow oil. Purification by column chromatography (1:100 ethyl acetate:hexane) gave 6.00 g (49%) of dronabinol as a colorless oil. REFERENCES [0000] 1) Snider, B. B; Amin, S. G. Synth. Commun. 1978, 8, 117. 2) Banks et al. J. Chem. Soc., Perkin Trans. 1 1981, 1096-1102 3) Benn, W. R. J. Org. Chem. 1968, 33, 3113. 4) Parsons et al. J. Chem. Soc., Chem. Commun. 1980, 197. 5) Schlossarczyk et al. Helv. Chem. Acta 1973, 56, 875.
Dronabinol, the tetrahydrocannabinol compound which comprises the active constituent of marijuana and is pharmaceutically useful as an antiemetic, is prepared by a process involving reaction of cis-menth-1-enc-3,8-diol with olivetol to form 1,3-dihydroxy-2-[(1R,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-yl]-5-pentylbenzene; and cyclizing the 1,3-dihydroxy-2-[(1R,6R)-6-(2-hydroxyprop-2-yl)-3-methylcyclohex-2-en-1-yl]-5-pentylbenzene so formed to obtain dronabinol. A novel synthesis of cis-menth-1-ene-3,8-diolis also provided.
2
This is a division of application No. 08/030,630 filed Mar. 12, 1993, now abandoned. FIELD OF THE INVENTION This invention relates to polymeric mordants for dyes, inks, and the like and more particularly, it relates to various types of polymeric mordants based upon poly(vinylpyridines), poly(N-vinylimidazoles), and poly(meth)acrylates. BACKGROUND OF THE ART The basic polymeric mordants useful to mordant a dye in a hydrophilic colloidal layer between a base and a photographic emulsion layer disclosed in U.S. Pat. No. 4,695,531 comprise repeating units of formula: ##STR1## wherein: R 1 is hydrogen or a methyl group; A is a --COO--or a --COO--alkylene group, e.g., --COOCH 2 --, --COOCH 2 CH 2 --, --COOCHOHCH 2 --; R 2 is a hydrogen or a lower alkyl group having from 1-4 carbon atoms; and X is an anion, e.g., acetate, oxalate, sulfate, chloride, or bromide. Mordant I can comprise units derived from vinylic monomers, for example, acrylates, acrylamides, vinylacetates, styrenes, vinyl ethers, vinyl ketones, vinyl alcohols, unsaturated chlorides, and nitriles with the proviso that such copolymerizable units be in a quantity of 10-20% by weight. Similar mordants with the exclusion of A in I are also disclosed in GB Patent No. 850,281. Polymeric mordants with N-heteroarocyclic vinyl aromatic, e.g., methylvinylpyridine (picoline) are also known in the art (see, for example, Italian Patent No. 931,270). Polyvinylpyridine-based mordant, e.g., II ##STR2## is also known in the art (see U.S. Pat. No. 4,695,531). Non-diffusive mordants based on poly(N-vinylimidazolc) of the type IIl are known in the art (see U.S. Pat. No. 4,500,631) and have been used in certain radiographic image-forming processes wherein the mordants were coupled with water-soluble dyes. ##STR3## Polymeric mordants of the type III as well IV are also disclosed in Japanese PubIn. No. 63-307979. SUMMARY OF THE INVENTION The present invention provides classes of novel polymeric mordants for dyes and the like. The inventive polymeric mordants are based upon poly(vinylpyridines), poly(N-vinylimidazoles), and poly(meth)acrylates. In accordance with the present invention the following classes of inventive polymeric mordants are provided: (In all cases A to I, each X.sup.⊖ independently represents any anion or mixture of anions.) ##STR4## wherein: X represents any anion, preferably CH 3 SO 3 , Br, NO 3 , CI, CF 3 COO, p-MePhSO 3 , CIO 4 , F, CF 3 SO 3 , BF 4 , C 4 F 9 SO 3 , FSO 3 , PF 6 , CISO 3 , or SbF 6 ; and n represents an integer of 2 or greater. ##STR5## wherein: X preferably represents CH 3 SO 3 , p-MePhSO 3 , CF 3 SO 3 , BF 4 , PF 6 , or SbF 6 ; and n represents an integer of 2 or greater. ##STR6## wherein: X preferably represents CH 3 SO 3 , Br, NO 3 , CI, CF 3 COO, p-MePhSO 3 , CIO 4 , F, CF 3 SO 3 , BF 4 , C 4 F 9 SO 3 , FSO 3 , PF 6 , CISO 3 , or SbF 6 ; and n represents an integer of 2 or greater. ##STR7## wherein: X preferably represents CH 3 SO 3 , p-MePhSO 3 , CF 3 SO 3 , BF 4 , PF 6 , or SbF 6 ; and n represents n integer of 2 or greater. ##STR8## wherein: X preferably represents the same counterions as recited for Class A earlier herein; and n represents an integer of 2 or greater. ##STR9## wherein: X preferably represents the same counterions as recited for Class A earlier herein; and n represents an integer of 2 or greater. ##STR10## wherein: X preferably represents the same counterions as recited for Class A earlier herein; and n represents an integer of 2 or greater. ##STR11## wherein: X preferably represents the same counterions as recited in Class A earlier herein; and n represents an integer of 2 or greater. ##STR12## wherein: R 1 represents H or CH 3 ; R 2 represents a C 1 -C 4 alkyl group; X preferably represents the same counterions as recited for Class A earlier herein; and n represents an integer of 2 or greater. The inventive classes of polymeric mordants A to I are believed to be novel and not to have been previously disclosed in the literature. The inventive classes of polymeric mordants are useful in a variety of applications such as in ink-jet formulations to control or stop ink-bleeding into ink-jet and photographic films. Other aspects of the present invention are apparent from the detailed description, the examples, and the claims. DETAILED DESCRIPTION OF THE INVENTION The synthesis of different polymeric mordants of Class A is shown in Reaction Scheme 1. ##STR13## The following examples illustrate the preparation of the mordants in Class A. EXAMPLE 1 These examples illustrate the preparation of poly(vinylpyridines). (a) A solution of 25 g 4-vinylpyridine in 50 ml methanol contained in a two-neck flask was flushed with dry nitrogen. After adding 0.5 g azobis(isobutyronitrile), the system was refluxed for 24 hours when a viscous material resulted. The polymer was precipitated from ether/hexane and dried in vacuo. Molecular weight: M w =140,609, M n =50285, P d =2.8 (b) The procedure in (a) was repeated for both 4-vinyl- and 2-vinylpyridines using THF instead of methanol. Poly(4-vinylpyridine) was precipitated from THF during the reaction whereas poly(2-vinylpyridine) was not. The latter was precipitated from ether/hexane as described above. EXAMPLE 2 The following examples (with reference to Reaction Scheme 1) describe the preparations of various hydrazones from chloroacetone and appropriate salts of aminoguanidine. (a) To a mixture of 30 g water and 30 g methanesulfonic acid, 20 g aminoguanidine bicarbonate was slowly added in portions at room temperature to obtain a clear solution of the corresponding methanesulfonate salt. The solution was warmed to about 40° C. and 15 ml chloroacetone was added dropwise. The solution was heated to about 50° C. for 15 minutes, cooled to room temperature, and then left at ice-temperature for 4-6 hours. The crystalline hydrazone was filtered and washed first with ice-cold isopropyl alcohol and then with diethyl ether. The hydrazone salt of methanesulfonate was dried in vacuo at about 60° C. (b)-(h) The methanesulfonic acid in Example 2(a) was replaced successively by an equivalent amount of HBr, HNO 3 , HCI, CF 3 COOH, pMePhSO 3 H, HCIO 4 , and HF and the procedure was repeated as described in 2(a) to obtain the hydrazone salts from (b)-(h). (i) The methanesulfonic acid in Example 2(a) was replaced by trifluoromethanesulfonic (triflic) acid and the procedure was repeated as described in Example 2(a). The hydrazone salt, on overnight cooling, could be precipitated/crystallized, but was redissolved during filtration. The salt, however, was extracted in methylene chloride and then dried over anhydrous magnesium sulfate. Removal of solvent gave the hydrazone salt of trifluoromethanesulfonate as a thick liquid/semi-solid. (j)-(o) The procedure in Example 2(i) was repeated by replacing the triflic acid by HBF 4 , C 4 F 9 SO 3 H, FSO 3 H, HPF 6 , CISO 3 H, and HSbF 6 to obtain the hydrazone salts from (j)-(o). EXAMPLE 3 The following examples (with reference to Reaction Scheme 1) illustrate the preparation of various polymeric mordants. (a) To a solution of 10 g poly(4-vinylpyridine) in 80 ml methanol, a solution of 21 g chloroacetonehydrazone-aminoguanidinium methanesulfonate (2a) in 30 g methanol was added and the mixture was heated to 50°-55° C. for 4-6 hours. On cooling the mixture to room temperature, the polymeric mordant with two counterions (first CI - counterion with the ring quaternary nitrogen; second CH 3 SO 3 - counterion with the side chain iminium quaternary nitrogen) was precipitated from acetone, filtered, and dried in vacuo. The material is Polymeric dye Mordant A(X=CH 3 SO 3 - / CI - ) (b)-(o) The procedure in (3a) was repeated using chloroacetonehydrazone-aminoguanidinium salts of counterions (b)-(o) to obtain the mordants from (b)-(o). EXAMPLE 4 This example (with reference to Reaction Scheme 1) illustrates the preparation of a Polymeric Mordant of Class A wherein X═CI - . (a) Preparation of vinyl pyridine polymer: a reaction vessel fitted with a condenser, a mechanical stirrer, a dropping funnel, and a nitrogen system was charged with 200 parts of 4-vinyl pyridine and 300 parts of isopropanol. The solution was purged with nitrogen for 10 min. then kept under a slow flow of nitrogen throughout the reaction. The solution was heated to 83° C. and then a solution of 2.0 parts of AIBN in 100 parts of isopropanol was added through the dropping funnel. The solution was heated at 83° C. for 5 hours. A quantitative polymerization reaction was obtained as evidenced by % solids and G.C. analysis. Molecular weight: M w =37,202, M n =22,547, p=1.65. (b) Hydrazones from chloroacetone: a reaction vessel fitted with a mechanical stirrer and a condenser was charged with 162.5 parts of aminoguanidine hydrochloride (NH 2 --NH--C(NH 2 )=N.sup.⊕ H 2 CI.sup.⊖ and 598.3 parts of methanol. The solid aminoguanidine hydrochloride was partially soluble in methanol. To the vessel 135.15 parts of chloroacetone was added and the solution was stirred for 1 hour at which time it became an homogeneous solution. A small portion of the reaction solution was taken out for analysis. I.R. and 1 H NMR spectra analysis revealed a quantitative reaction. (c) Polymeric mordant A: a reaction vessel was fitted with a mechanical stirrer, a condenser and a dropping funnel. To the vessel a 20% solids solution of p-vinyl pyridine (20% solids solution was made by dilution of Example 4(a) with methanol) was charged, a 32.8% solids solution of hydrazones of chloroacetone from Example 4(b) was then added slowly from the dropping funnel with vigorous agitation. A solid polymeric product started to precipitate out immediately. After the completion of the addition of the all reactants, the mixture was stirred for 1 hour at room temperature. Then 500.0 parts of acetone was added and stirred for 10 min. The organic solvent was removed by vacuum suction. The solid product was washed with 500.0 parts of acetone and the acetone was removed by vacuum suction. The solid mordant was dissolved in deionized water to make 20% solids solution of the mordant. The synthesis of different polymeric mordants of Class B is illustrated in Reaction Scheme 2. ##STR14## The following examples (with reference to Reaction Scheme 2) illustrate the preparation of various polymeric mordants of Class B. EXAMPLE 5 To a solution of 10 g polymeric mordant 3d in 30 ml methanol, two equivalents of sodium methanesulfonate was added with stirring. The solution was heated to 60° C. for 15 mins, filtered, and the mordant 4a was precipitated from ether and dried in vacuo. EXAMPLE 6 Mordants 4f-4o were prepared by the same procedure as in Example 5 by using appropriate equivalents of alkali metal salts of respective counterions. Synthesis of different Class C mordants based on poly(N-vinylimidazole) is shown in Reaction Scheme 3. ##STR15## X represents the same counterions as in Reaction Scheme 1. EXAMPLE 7 To a solution of 10 g poly(N-vinylimidazole) 5 in 30 ml methanol, a solution of 28 g chloroacetonehydrazone-aminoguanidinium trifluoroacetate 2e (X=CF 3 COO) in 30 ml methanol was added. The mixture was heated to 50° C. for 15 min. and cooled to room temperature. Mordant 6e was precipitated from acetone or ether and dried in vacuo. Preparation of different Class D mordants is illustrated in Reaction Scheme 4. ##STR16## EXAMPLE 8 To a solution of 10 g 6d in 30 ml methanol two equivalents of potassium triflate were added with stirring. The mixture was heated to 50° C. for 15 rains, cooled to room temperature, and then filtered. Mordant 7i was precipitated from ether and dried in vacuo. Synthesis of different Class E mordants is shown in Reaction Scheme 5. ##STR17## EXAMPLE 9 This example shows the preparation of multiple iminium component 9 (Reaction Scheme 5). To a suspension of 10 g guanidinobenzimidazole in 30 g water 13 g conc. HCI was added dropwise to obtain a di-quarternary iminium hydrochloride salt. To this mixture was added dropwise 3.3 ml chloroacetonc on heating which was maintained for 0.5 hour. The off-white flocculent precipitate was separated from the mixture and dried in vacuo to obtain the diquarternary iminium hydrochloride as a semicarbazone salt. EXAMPLE 10 (a) This example shows the preparation of Mordant 11. To a solution of 4 g poly(4-vinylpyridine) 10a in 30ml methanol was added a solution of 12 g 9 in 20ml methanol. The solution was heated to about 50° C. for 4 hours. The mordant was precipitated from acetone, filtered, and dried in vacuo. (b) The procedure in 9 was repeated by replacing poly(4vinylpyridine) with poly(N-vinylimidazole) to obtain the corresponding mordant of Class F. Synthesis of different Class G Mordants is shown in Reaction Scheme 6. ##STR18## EXAMPLE 11 This example shows the preparation of a quarternary ammonium component. To a solution of 10 g 2-([2-(dimethylamino)ethyl]methylamino)ethanol and 2.2 g methanol in 25 ml methylene chloride was added dropwise 17 g thionyl chloride in 20 ml methylene chloride at ice temperature. The addition of thionyl chloride was followed by brief heating of the mixture for 0.5 hour. The white precipitate was filtered, washed with methylene chloride, and dried in vacuo. 1 H NMR showed the material to be a di-quarternary ammonium salt of the starting material. The synthesis of Class I mordants is illustrated in Reaction scheme 7. ##STR19## EXAMPLE 12 A reaction vessel fitted with a mechanical stirrer, a condenser, and a dropping funnel was charged with 100 parts of DMAEMA (N,N-dimethylaminoethyl methacrylate). A solution of 117.1 parts of chloroacetone hydrazone-aminoguanidinium hydrochloride in 285 parts of methanol was added to the vessel slowly from the dropping funnel in such a rate that the reaction exotherm does not exceed 50° C. After completion of the addition the reaction solution was stirred for two hours. Then the solvent was removed by rotary evaporation under vacuum at about 40° C. A white solid was obtained. Monomer 15 was characterized by its 1 H NMR spectrum. In a reaction vessel 50 g of 15, 50 g water and 0.23 g of V-50 (2,2'-azobis(2-amidinopropane)di -hydrochloride), available from Wako Chemical Co. were mixed. The solution was purged for 20 rains. Then the solution was heated at 50° C. for 2 hours. A viscous polymer solution was obtained. Proton NMR spectrum and % solid analyses revealed quantitative polymerization of 15 to 16. Reasonable modifications and variations are possible from the foregoing disclosure without departing from either the spirit or scope of the invention as defined in the claims.
Novel classes of polymeric mordants based upon poly(vinylpyridine), poly(N-vinylimidazoles), and poly(meth)acrylates are disclosed. The polymeric mordants contain N-heterocycles which are N-quaternized by different types of alkylated hydrazones, semicarbazones, and multiple-quaternized alkylated salts serving as pendant groups.
2
BACKGROUND OF THE INVENTION [0001] Silicon has increasingly been used in optical applications. Currently such optical components as waveguides, beam splitters, detectors, lasers, and the like can all be formed in silicon. Forming such components from silicon enables small high frequency response, lower energy components as well as large scale manufacturing using semiconductor fabrication methods. [0002] Recently, thin silicon oxide layers have been grown on silicon components to form antireflective coatings on silicon in order to achieve a desired light path. In order to function properly, antireflective coatings must have a thickness matched to the wavelength of light used in the optical system. Any variation in the thickness of the antireflective coating can introduce unwanted reflections, attenuation, and other irregularities. Inasmuch as the optical spectrum is from 400 to 700 nanometers, achieving a specified antireflective coating requires extremely accurate manufacturing processes. [0003] Silicon is a face centered cubic (FCC) crystal structure having 100, 110, and 111 plans, and permutations thereof. In the presence of oxygen, oxide layers will grow on facets parallel to the 100 and 111 planes at different rates. Accordingly, two facets on the same substrate that are parallel to the 100 and 111 planes, respectively, will have oxide layers of different thicknesses after having been exposed to oxygen for the same period of time. As a result, the facets will not bear oxide layers suitable for suppressing reflection of light at the same wavelength. [0004] For example, FIG. 1 illustrates a substrate 10 having a faceted upper surface having facets 12 a - 12 c parallel to the 100 plane 14 of the silicon substrate and facets 16 a , 16 b parallel to the 111 plane 18 . For purposes of the disclosure the 100 plane 14 may mean any of the permutations of the 100 planes of an FCC material including the 100, 010, and 001 planes. Other facets formed on the substrate 10 may be parallel to the 110 plane and the 101 and 011 permutations thereof. [0005] The substrate 10 is exposed to an oxidizing environment such that an oxide layer 20 is grown on the silicon substrate 10 will have a thickness 22 on facets 12 a - 12 c that is less than a thickness 24 on facets 16 a , 16 b due to the faster growth rate of the 111 plane 18 . Oxide layers grown on the 110 plane may likewise have a thickness different than the thicknesses 22, 24. [0006] In view of the foregoing it would be an advancement in the art to provide a system and method for growing uniform oxide layers over both the 100 and 111 planes. Such a system and method should be capable of use in large scale manufacturing of silicon optical components. BRIEF SUMMARY OF THE INVENTION [0007] The present invention includes methods and systems for growing uniform oxide layers evenly over a silicon substrate. One method includes growing a first layer of oxide on first and second facets of the substrate, with the first facet having a faster oxide growth rate. The oxide is then removed from the first facet and a second oxide layer is grown on the first and second facets. Removing the oxide from the first facet includes shielding the second facet and exposing the substrate to a condition suitable for removing the oxide layer, such as a wet etching process. The second facet is then exposed to receive and a second oxide layer is grown on the first and second facets. Shielding the second facet includes applying a photoresist to the substrate and removing the photoresist from the first facet. Shielding may also include selectively metallizing the second facet. [0008] Growing the first and second oxide layers includes exposing the silicon substrate to an oxidizing environment for first and second periods, respectively. The first period has a duration sufficient to grow oxide having a thickness about equal to S*(1−X/Y), where S is a final thickness of oxide grown on the second facet for a total period about equal to a sum of the first and second periods, X is a first growth rate for the second facet, and Y is a second growth rate of the first facet. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING [0009] The preferred and alternative embodiments of the present invention are described in detail below with reference to the following drawings. [0010] FIG. 1 is side cross-section view of a silicon substrate having multiple facets and an oxide layer formed thereon; [0011] FIG. 2 is process flow diagram of a method for uniform oxide layer formation, in accordance with an embodiment of the present invention. [0012] FIG. 3 is a side cross-section view of the silicon substrate having portions of the oxide layer selectively removed from faster-growth facets, in accordance with an embodiment of the present invention [0013] FIG. 4 is a side cross-section view of the silicon substrate having a second oxide layer formed thereon, in accordance with an embodiment of the present invention; [0014] FIG. 5 is a chart of values for a parabolic rate constant B used to calculate oxide growth times, in accordance with an embodiment of the present invention; [0015] FIG. 6 is a chart of values for a linear rate constant B/A used to calculate oxide growth times, in accordance with an embodiment of the present invention; [0016] FIG. 7 is a process flow diagram of an alternative method for uniform oxide layer formation, in accordance with an embodiment of the present invention; [0017] FIG. 8 is a side cross-section view of the silicon substrate having shielded slower-growth portions, in accordance with an embodiment of the present invention; [0018] FIG. 9 is a process flow diagram of an alternative method for uniform oxide layer formation, in accordance with an embodiment of the present invention; [0019] FIG. 10 is a side cross-section view of the silicon substrate having a photoresist layer being irradiated through a mask exposing faster-growth facets, in accordance with an embodiment of the present invention; [0020] FIG. 11 is a process flow diagram of an alternative method for uniform oxide layer formation, in accordance with an embodiment of the invention; [0021] FIG. 12 is a side cross-section view of the silicon substrate being metallized through a mask exposing slower-growth facets, in accordance with an embodiment of the present invention; [0022] FIG. 13 is process flow diagram of a method for growing multiple-thickness oxide layers, in accordance with an embodiment of the present invention; [0023] FIG. 14A-14D are side cross-section views of the silicon substrate undergoing the method of FIG. 13 , in accordance with an embodiment of the present invention; [0024] FIG. 15 is a plot illustrating a means for timing shielding application in order to achieve a specific oxide layer thickness, in accordance with an embodiment of the present invention; and [0025] FIG. 16 is a process flow diagram illustrating an alternative method for growing multiple-thickness oxide layers, in accordance with an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION [0026] FIGS. 2 through 4 illustrate a method 26 for growing a uniform layer on a substrate notwithstanding the differences in growth rates. At block 28 a first layer, such as an oxide layer 20 , is grown on the substrate 10 . At block 30 , the layer is removed from faster-growth facets, such as facets 16 a , 16 b , as shown in FIG. 3 . Removing the layer from the faster-growth facets 16 a , 16 b may include removing the first silicon oxide layer 20 by means of a wet-etching process, or other such process. [0027] At block 32 , a second oxide layer 34 is grown in addition to the first oxide layer 16 , as shown in FIG. 4 . Oxidation in silicon proceeds inwardly into the bulk of the substrate. Accordingly, the second oxide layer 34 formed at block 32 is below the first oxide layer 20 . In other applications of the present invention, layers are deposited on the substrate 10 which are deposited at different rates over different planes. In such embodiments, the oxide layer 34 will be above the layer 16 . [0028] The method 26 illustrated in FIGS. 2 through 4 provides a means for equalizing growth rates across the slower-growth facets 12 a - 12 c and the faster growth facets 16 a , 16 b . In one embodiment, a uniform layer thickness across multiple planes is achieved by adjusting the thickness of the first oxide layer 16 . The first oxide layer has a thickness T 1 equal to the equation S*(1−X/Y), where S is the combined thickness of the first oxide layer 20 and the second oxide layer 34 , X is the slower growth rate, such as on the 100 plane 14 , and Y is the faster growth rate, such as on the 111 plane 18 . The second oxide layer 34 has a thickness T 2 equal to S−T 1 . [0029] The thicknesses of the first oxide layer 20 and second oxide layer 34 may be controlled by adjusting the length of time that the substrate 10 is subject to an oxidizing environment. Accordingly, the first oxide layer 20 may be formed by exposing the substrate 10 to the oxidizing environment for a first period t 1 whereas the second oxide layer 34 is formed by exposing the substrate 10 to the oxidizing environment for a second period t 2 . The ratio of the second period relative to the sum of the first and second period (t 2 /(t 1 +t 2 )) will be equal to X/Y in order to achieve a uniform thickness. [0030] For oxide layers having large thickness, such as above 5,000 Angstroms, the rate of oxide layer growth becomes significantly non-linear. Accordingly, the first and second periods may be adjusted to accommodate this nonlinearity. Equation 1 accommodates nonlinearity in oxide growth rates. A description of nonlinearity in silicon-oxide growth rates may be found in “Semconductor Materials and Process Technology Handbook for Very Large Scale Integration and Ultra Large Scale Integration” (ed. Gary E.McGuire, Noyes Publications, Park Ridge, N.J.). E ⁢ quation ⁢   ⁢ 1 ⁢ : ⁢   t = x o 2 - x i 2 B + x o - x i B A [0031] Where t is the time required to form an oxide layer of thickness x 0 over a silicon substrate bearing an oxide layer having a thickness x i . B is a parabaolic rate constant and B/A is a linear rate constant used to describe oxide growth. B and B/A are calculated according to Equations 2 and 3 or Equations 4 and 5. Alternatively, B and B/A may be determined by referencing measured values illustrated in FIGS. 5 and 6 . Equation ⁢   ⁢ 2 ⁢ : ⁢     ⁢ A = 2 ⁢ D eff ⁡ ( 1 k + 1 h ) Equation ⁢   ⁢ 3 ⁢ :   ⁢ B = 2 ⁢ D eff ⁢ C k N 1 [0032] Where D eff is the effective oxidant diffusion constant in oxide, k and h are rate constants at the Si—SiO 2 and gas-oxide interfaces, C k is an equilibrium concentration of the oxide species in the oxide, N 1 is the number of oxidant molecules in the oxide unit volume. Equation ⁢   ⁢ 4 ⁢ : ⁢   ⁢ ⁢ B = C 1 ⁢   ⁢ ⅇ E 2 kT Equation ⁢   ⁢ 5 ⁢ : ⁢   ⁢ ⁢ B A = C 2 ⁢   ⁢ ⅇ E 2 kT [0033] Where T is the temperature at which the oxidation takes place expressed in degrees Kelvin and k is a rate constant at the Si—SiO 2 and gas oxide interfaces. [0034] For the 111 plane of silicon under dry oxidation conditions C 1 = 7.72 × 10 2 ⁢ μ ⁢   ⁢ m 2 hr , C 2 = 6.23 × 10 6 ⁢ μ ⁢   ⁢ m 2 hr , E 1 = 1.23 ⁢ eV , E 2 = 2.0 ⁢   ⁢ eV . [0035] For the 111 plane of silicon under wet oxidation conditions C 1 = 3.68 × 10 2 ⁢ μ ⁢   ⁢ m 2 hr , C 2 = 1.63 × 10 8 ⁢ μ ⁢   ⁢ m 2 hr , E 1 = 0.78 ⁢   ⁢ eV , E 2 = 2.05 ⁢   ⁢ eV . [0036] For the 100 plane of silicon C 2 ⁢ ( 100 ) = C 2 ⁢ ( 111 ) 1.7 . [0037] In one embodiment of the method 26 the Equation 1 is used to calculate a time t 1 used at block 28 for the duration of oxide growth during formation of the first oxide layer 20 , such that when the second oxide layer 34 is grown thereunder at block 34 for a time t 2 all facets 12 a - 12 c and facets 16 a , 16 b will have substantially uniform thickness. The thickness of the first oxide layer 20 grown on the slower-growth facets 12 a - 12 c is used as x i in Equation 1 as applied to the slower growth facets 12 a - 12 c to determine a time t 2 for oxide growth forming the second oxide layer 34 at block 32 . Equation 1 is used to calculates a time t 2 for growing a second oxide layer at block 32 such that the thickness x 0 on the faster growth planes 16 a , 16 b and the thickness x 0 on the slower growth planes 12 a - 12 c bearing the first oxide layer 20 of thickness x 1 are equal to one another at a desired thickness. [0038] For example, to achieve a thickness of about 10,150 Angstroms on both the slower growth facets 12 a - 12 c and the faster growth facets 16 a , 16 b for a wet oxidation process carried out at 900° C., t 1 is equal to about 2.8 hours and t 2 is equal to about 10 hours. [0039] FIGS. 7 and 8 illustrate a method 36 which is an alternative embodiment of the method 26 for uniform layer formation. In the method 36 , the substrate 10 is oxidized at block 38 by exposing the substrate to an oxidizing environment to yield a first layer, as in FIG. 1 . The oxidizing environment may include the presence of oxygen at an elevated temperature. At block 40 , the slower growth facets are shielded, such as by a shielding layer 42 shown in FIG. 8 . The shielding layer 42 may be a layer of photoresist, metal, or the like. The oxide is removed from the faster growth facets 16 a , 16 b at block 44 , as shown in FIG. 3 . The shielding layer 42 is then removed at block 46 to expose the slower-growth facets 12 a - 12 c and the substrate 10 is again oxidized at block 48 to yield the uniform thickness layer of FIG. 4 . [0040] In order to achieve oxide thicknesses varying locally the first oxide layer 20 is removed in areas where the oxide layer is to be thinner. The steps of oxidizing, shielding, and locally removing oxide, exposing, and oxidizing again may be repeated, selectively shielding different portions each iteration to achieve oxide layers having a broad range of thicknesses on a single substrate 10 . [0041] FIGS. 9 and 10 illustrate a method 50 that is an alternative embodiment of the method 36 . In the method 50 , a first oxide layer 20 is grown on the substrate at block 52 . A photoresist layer 54 is then applied at block 56 . The slower-growth facets 12 a - 12 c are masked at block 58 , such as by a mask 60 interposed between the substrate 10 and a light source. The substrate 10 is then irradiated through the mask 60 at block 62 . For positive photoresist, exposing the photoresist to light weakens the photo resist, making it readily removable. The steps recited for blocks 56 , 58 , 62 assume use of a positive photoresist compound that is weakened by exposure to light. Other embodiments may use a negative photoresist compound that remains in a weakened state unless hardened by exposure to light. In such embodiments, the faster-growth facets 16 a , 16 b are masked in order to weaken the photoresist coating them. [0042] For both types of photoresist, the weakened photoresist is then removed at block 64 to expose the faster-growth facets 16 a , 16 b . The oxide on the faster-growth facets 16 a , 16 b is then removed at block 66 . The hardened photoresist is removed at block 68 and a second oxide layer 34 is grown at block 70 . [0043] FIGS. 11 and 12 illustrate a method 72 that is an alternative embodiment of the method 36 . In the method 72 , the first oxide layer 20 is grown at block 74 . The faster growing facets are then masked at block 76 . The exposed areas of the substrate 10 are then metallized at block 78 to create a metal layer 80 over the slow-growth facets as shown in FIG. 12 . Metallization at block 78 may be accomplished by E-beam evaporation, sputtering, chemical vapor deposition (CVD), or the like, through a mask 82 exposing the slower-growth facets 12 a - 12 c . Oxide is removed from the unmetalized, faster-growth facets 16 a , 16 b at block 84 by plasma etching, wet etching, or the like chosen such that the metal layer 80 is not removed thereby. The metal layer 80 is then removed at block 86 , such as by wet chemical etching, and a second oxide layer is grown at block 88 . [0044] FIG. 13 illustrates a method 90 for forming oxide layers having locally varying thicknesses according to a specific criteria, rather than uniform layers. At block 92 a first oxide layer 94 is formed, as illustrated in FIG. 14A . At block 96 a first area 98 is shielded and the oxide in unshielded areas is removed at block 100 , leaving the substrate 10 as illustrated in FIG. 14B . At block 102 , shielding is removed and at block 104 , a second oxide layer 106 is grown, as illustrated in FIG. 14C . At block 108 , the first area 98 an a second area 110 are shielded and at block 112 , the oxide layer is removed from unshielded areas of the substrate 10 . At block 114 , the first and second areas are unshielded, leaving the substrate as shown in FIG. 14D having a first area 98 , a second area 108 , and a third area 116 each having a unique oxide layer thickness. The method 90 of FIG. 13 may use any of the methods 32 , 50 , 72 for shielding areas of the substrate during removal of the oxide layer. [0045] Referring to FIG. 15 , the pattern illustrated in FIGS. 13 and 14 A- 14 D may be repeated for any number of oxide layers and areas. For example, a manufacturing process includes multiple iterations of the process including the steps of growing an oxide layer, shielding certain areas, and removing unshielded portions of the oxide layer. The lower axis 118 of FIG. 15 indicates the number of the iteration and the upper axis 122 indicates the thickness of the oxide layer. In order to achieve an area having a desired oxide layer thickness, one first determines the thickness of the area having the thickest oxide layer and performs sufficient iterations to achieve the desired thickness, 5,500 Angstroms in the illustrated scenario. Areas to have the greatest thickness will be shielded during each iteration. Areas to have a lesser thickness are left unshielded during initial iterations until the number of remaining iterations is sufficient to grow an oxide layer of the appropriate thickness. The lesser-thickness area is then shielded for all remaining iterations. For example, an area may begin to be shielded during oxide layer removal at iteration six in order to achieve an oxide layer thickness of 3000 Angstroms, whereas another area begins to be shielded at iteration seven in order to achieve an oxide layer thickness of 2500 Angstroms. Areas where no oxide layer is to be formed are left unshielded for all iterations. [0046] Referring to FIG. 16 , the thickness of the oxide layer grown during each iteration need not be the same for each iteration. For example, a silicon substrate 10 may have areas A 0 through A N , with A 0 having the thickest oxide layer and A N having the thinnest oxide layer. An area A i of the areas A 0 through A N need not be contiguous. The difference in thickness between each area A i and A i+1 , is t i , except t N is simply equal to the thickness of the thinnest layer of oxide. [0047] A method 122 for forming a multi-thickness oxide layer includes setting a counter i to zero at block 124 . A first oxide layer having a thickness ti is grown at block 126 . At block 128 , areas A i through A 0 are shielded. At block 130 oxide is removed from all exposed areas. At block 132 , the value of i is compared to variable N representing the total number of thicknesses being formed on the substrate 10 . If i is equal to N, the method ends. If i is less than N, than i is incremented at block 134 . Areas where no oxide is to be formed are left unshielded during the entire method 122 . [0048] While the preferred embodiment of the invention has been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is not limited by the disclosure of the preferred embodiment. Instead, the invention should be determined entirely by reference to the Claims that follow.
Methods and systems for growing uniform oxide layers include an example method including growing a first layer of oxide on first and second facets of the substrate, with the first facet having a faster oxide growth rate. The oxide is removed from the first facet and a second oxide layer is grown on the first and second facets. Removing the oxide from the first facet includes shielding the second facet and exposing the substrate to a deoxidizing condition. The second facet is then exposed to receive the second oxide layer. Areas having differing oxide thicknesses are also grown by repeatedly growing oxide layers, selectively shielding areas, and removing oxide from exposed areas.
7
This invention relates to a novel creeping bentgrass (Agrostis palustris (stolonifera)), a variety used primarily as commercial golf course turf. BACKGROUND There are over 100 species of Bentgrass (Agrostis) but only two are used to any great extent as golf course turf. Bentgrass is well adapted to close mowing due to its prostrate growth habit. They grow best in moist uncompacted soils and have broad temperature hardiness. Creeping bentgrass (Agrostis palustris) is so named due to its ability to creep laterally by stolons. The stolons are able to root at the nodes producing a new plant. Creeping bentgrass is the plant of choice for fairways, tees and greens where the height of cut is below one-half inch. Creeping bentgrass (Agrostis palustris) is a perennial cool season grass that forms a dense mat. The grass spreads by profuse creeping stolons and basal tillers and possesses rather vigorous, shallow roots. Stems, or stolons, are decumbent (creeping) and slender and produce long narrow leaves. Leaf blades are smooth on the upper surface and ridged on the underside, are approximately 1 to 3 mm wide and bluish green in appearance. The ligule is long, membranous, finely toothed or entire and rounded, auricles are absent. Developing new grass species is difficult, time consuming, and expensive. The developer must sift through thousands of prospective grasses listed in botanical literature, identify promising grasses, and often travel thousands of miles to locate, isolate, identify, transport, quarantine, grow, test, and breed these grasses. This process can take more than 10 years to develop acceptable cultivars. Furthermore, as it turns out, most prospective grasses in nature have no commercial turf value, due to their inability to generate an acceptable ground cover when mowed. The vast majority of natural grasses cannot produce a plush lawn under continuing defoliation. Yet another complexity facing the plant developer is the unresponsiveness of many wild grasses to plant breeding. The vast majority of wildland grasses lack genetic potential for refinement into desirable turfgrass cultivars. Only after considerable investment in collection and breeding does the developer discover which grass species can be successful bred and which cannot. The Agrostis genus--better known as the bentgrasses--is comprised of over 100 species, several of which have been developed into successful turfgrasses. One Agrostis in particular, A. stolonifera or creeping bentgrass, has become the preeminent grass for golf course putting greens the world over. Another Agrostis species, colonial bentgrass (A. tenuis Sibth.), has been bred into a golf course grass useful on tees and fairways in cooler regions. Two or three other Agrostis species find minor turf application, mostly for golf, tennis courts, bowling greens, or an occasional home lawn. The Agrostis genus is widely distributed throughout the world with representative species found on all of the northern continents. However, of the present-day bentgrass species in use as turfgrasses, all originated from Europe. The original seed of these plants was brought to the US during colonial times. America has an abundance of native bentgrass species (A. S. Hitchcock, 1951, Manual of the grasses of the United States. USDA Misc. Publ. 200) but none are commercially useable as turf grass. Agrostis palustris (stolonifera) is found in nature throughout the mountains of New Mexico, Arizona, and California, along the Rockies, and north to Fairbanks, Ak. Commercial bentgrass species (creeping bentgrass, colonial bentgrass, etc.) all possess stolons (above-ground running stems) and/or rhizomes (below ground running stems). Hitchcock describes Agrostis palustris (stolonifera) as follows: Culms slender, tufted, 10 to 30 cm tall, leaves mostly basal, the blades narrow; panicle loosely spreading, 5 to 10 cm long, the branches capillary, flexuous, minutely scabrous; spikelets 1.5 to 2.5 mm long; lemma about 1.3 mm long, awnless; palea minute. Differs from A. scabra in the smaller spikelets and in the narrower panicle with shorter flexuous branches. Piper and Beattie (Charles V. Piper and R. Kent Beattie, 1914, Flora of Southeastern Washington and adjacent Idaho, New Era Printing Co., Lancaster, Pa.) studied the natural occurrence of Agrostis palustris (stolonifera). They found it common to the alpine woods of the Craig Mountains. Their botanical description is as follows: Delicate, loosely-tufted, glabrous, perennial, 10-30 cm high; blades flat, narrow, 1-6 cm long; panicle loose, green or purple, 5-10 cm long; rays capillary; spikelets about 1.5 mm long; lower glume scabrous on the keel, slightly larger than the upper; lemma truncate, awnless, 1 mm long; palea minute. Correll and Correll (D. S. Correll and H. B. Correll, 1972, Aquatic and wetland plants of the Southwestern United States, Stanford Univ. Press, Stanford, Calif.) reported that Agrostis palustris (stolonifera) is an important native wetland species in moist mountain meadows, swamps, shallow water of ponds, lakes, along streams, and on sand-gravel bars in river beds throughout the West. DeBenedetti and Parsons (S. H. DeBenedetti and D. J. Parsons, 1984, Postfire succession in a Sierran subalpine meadow, Amer. Midland Naturalist 111:118-125) concluded that Agrostis palustris (stolonifera) was the most important native grass species present in post-fire succession of subalpine grasslands in California. Its tenacious growth under adverse conditions makes it a valuable forage for wildlife. SUMMARY OF THE INVENTION The present invention provides for the development of a novel cultivar of bentgrass species never before exploited for turf purposes. Cultivars developed from this species demonstrate extremely dense and fine textured turfgrass properties, including improvements in disease tolerance, fineness of leaf, low height of cut, drought and heat tolerance, deeper rooting and overall turfgrass quality. More specifically, the present invention relates to an Agrostis palustris (stolonifera) plant having the characteristics of an average leaf blade width of less than 1 mm under turf putting green-maintained conditions. DEFINITIONS In the description and tables which follow, a number of terms are used. In order to provide a clear and consistent understanding of the specification and claims, including the scope to be given such terms, the following definitions are provided for either mature plants or in putting green turf plots: Average leaf blade width: As used herein, the term average leaf blade width means the leaf blade width as measured in millimeters and is determined as follows: Turf plots are grown and maintained in the manner described for evaluation of turf quality. After one year of growth and maintenance, sections of sod 3.08 cm by 12.7 cm are cut and removed from the plot by randomly selecting a representative surface area. Four plugs are removed per plot. Blade width of the second and third youngest subtended leaves per tiller (vertical shoot) are measured on all plants in the sample plug. The youngest leaf occurs at the top of the tiller, with older ones successively down the shoot. The leaf blade width is measured in millimeters across the widest part of the blade, with any creasing of the blade pressed out. Average shoot density: As used herein, the term average shoot density means the number of grass shoots measured in four plugs. During the process of blade width measurement, the number of grass shoots for each genotype are counted in the plugs. A grass shoot is defined as an autonomous unit possessing a vertical sheath segment, and a minimum of two leaves, including the vertical or bud leaf. Shoot counts per plug are converted numerically into shoots per dm 2 , based on the exact measured area of the plug. Bottom Whorl Branches: The term bottom whorl branches means verticullate having three or more branches at the same point on the bottom of the inflourescence. Brown patch: The term brown patch means the level of disease on the plants. Brown patch is a foliar plant disease incited by the Rhizoctonia solani fungus. Brown patch severity is evaluated visually on a 1 to 9 integer rating scale, in a manner similar to turfgrass quality. Symptoms are evaluated during a naturally occurring field disease epidemic. With brown patch evaluation, a rating of 1 would indicate complete necrosis from the disease, 5 would be moderate damage, and 9 would be complete resistance to the disease. Ratings are taken when the turf is actively growing, when regular mowing is taking place, and when no stresses such as drought or other diseases are apparent. Density: The term density refers to the number of tillers per square decimeter. Dollarspot: The term dollarspot refers to the disease Sclerotinia homeocarpa. Flag Leaf Length and Width: Flag leaf length and width are the dimensions of the first leaf below the seed head (inflourescence). Head Count: The term head count refers to the number of seed heads per unit area or per plant. Leaf color: The term leaf color means that the leaf color is evaluated visually on a 1 to 9 integer rating scale, in a manner similar to turfgrass quality. With leaf color evaluation, a rating of 1 would equate to yellow-green turf, 5 to average green turf, and 9 to intensely dark green turf color. Ratings are taken when the turf is actively growing, when regular mowing is taking place, and when no stresses such as drought or disease are apparent. Leaf texture: The term leaf texture means that the leaf texture is evaluated visually on a 1 to 9 integer rating scale, in a manner similar to turfgrass quality. With leaf texture evaluation, a rating of 1 would equate to coarse, broad-bladed turf, 5 to turf of an average blade width and 9 to turf of extremely fine blade width. Ratings are taken when the turf is actively growing, when regular mowing is taking place, and when no stresses such as drought or disease are apparent. Moss: The term moss refers to a Bryophyte contaminant in turf. Net blotch: The term net blotch disease is incited by the Drechslera/Bipolaris spp. fungi. Net blotch severity is evaluated visually on a 1 to 9 integer rating scale, in a manner similar to turfgrass quality. Symptoms are evaluated during a naturally occurring field disease epidemic. With net blotch evaluation, a rating of 1 would indicate complete necrosis from the disease, 5 would be moderate damage, and 9 would be complete resistance to the disease. Ratings are taken when the turf is actively growing, when regular mowing is taking place, and when no stresses such as drought or other diseases are apparent. Panicle Length: The term panicle length means the distance from the lowest branch to the tip of the inflourescence. Plant Height: The term plant height is the distance from the soil surface to the tip of the inflourescence. Pythium blight: The term Pythium blight refers to the disease incited by Pythium spp. Seedling vigor: the term seedling vigor means the level of emergence and vigor expressed by the seedlings. Seedling vigor is evaluated visually on a 1 to 9 integer rating scale, in a manner similar to turfgrass quality. With seedling vigor evaluation, ratings are taken 4 weeks after seed establishment, approximately 14 days from the date when the first seedlings are observed protruding above the soil surface. A rating value of 1 would equate to the complete lack of seedling emergence, 5 would indicate an average emergence value, and 9 would indicate extremely vigorous seedling establishment--essentially a complete ground coverage by the turf. Ratings are taken when the turf is actively growing, when no stresses such as drought or disease are apparent. It is assessed just prior to the stand's first mowing. Snow Mold: As used herein, the term snow mold refers to the disease Fusarium nivale (Pink Snow Mold). Putting green turfgrass quality: As used herein, the term putting green turfgrass quality means that to evaluate turfgrass quality, grasses are seeded into plots 4 by 6 feet or larger, at a seeding rate of 5 grams per m 2 (seed grams per square meter) equal to commercial rates listed in turf textbooks. Plots are maintained under fertilization and watering to minimize stress, and 6-7 times weekly mowings at 3 to 5 mm height of cut plus aerated and topdressed as necessary. Three plots of Variety A are planted in a randomized complete block design arrangement with three plots of Variety B, C, D, etc. Visual ratings are taken monthly during the growing season on a 1 to 9 rating scale, with 1 equal to bare ground, 2 equal to thin, brown turf, 3 equal to substandard turf, 4 equal to marginally acceptable turf, 5 equal to average turf, 6 equal to slightly above average turf, 7 equal to dense, robust turf, 8 equal to turf of exception recorded and 9 is equal to ideal turf quality. Ratings are conducted by a university-trained specialist with a graduate degree in Turfgrass Science. Monthly data ratings are analyzed using a statistical procedure known as the analysis of variance or t-test at the 0.05 level of probability. A significant analysis indicates the two varieties, A and B, are different, and that the difference is not due to random error or natural plant and soil variability. A non-significant analysis would indicate that the varieties A and B were indistinguishable in turf quality or mature plant parameters. Vegetative propagules: As used herein, the term vegetative propagules means sprigs, plugs, stolons and sod. DETAILED DESCRIPTION OF THE INVENTION The variety PENN G-1 (experimental designation PSU G-1) is based on a single segregated plant selected on the Par-3 course from the Augusta National Golf Club, Augusta, Ga. in 1984. Eight similar types were selected from two greens originally seeded to Penneagle bent and overseeded with Penncross. The selections were based on a dense upright growth habit, very fine leaf texture, minimum spiking from golf shoes and ability to spread as segregates compared to the greens bent population, thereby, attracting attention. These selections were designated in the breeding program as the "G: series in contrast to the "A" series from the main course which were selected with similar criteria. Both G and A series selections were cloned, pot planted and induced to flower in a growth chamber. Isolated crossing blocks were established in the greenhouse from which 250 plants each were nursery space planted in isolated field blocks. The first cycle of reselection consisted of chemically roguing all but 30-50 plants of each sibline based on vegetative and flowering stage appearance prior to anthesis. Three lines were eliminated due to degree of segregation. Re-selected clones were pot planted and again induced to flower in a growth chamber to save a reproductive year, and placed in isolated greenhouse crossing blocks. Following seed harvest, 300 seedlings were field planted for the next reselection cycle. Seed from the first cycle plants was used to establish a pilot putting green turf planting to conform the fine texture and dense qualities of the original parents. The second cycle of reselection consisted of 40-50 plants of each experimental lines of both the G and A series. Selected clones were sent to Oregon for seed set and any further reselection under production state conditions. Clones of each line were replicated and isolated planted. The G series now consisted of G-1, G-2, and G-6 and were further reselected to 20-30 replicated plants each in Oregon. These clones constitute breeder planting stock and the first generation seed used for seed yield trials and subsequently certified seed production. Due to inherent heterogeneity of this tetraploid species, production of G-1 and associated cultivars shall be limited to a two generatation system, breeders and certified to maintain optimum stability. Uniformity and stability of PENN G-1 was ascertained by inspection of seed yield plantings in both and reproductive stages of growth. The variants in PENN G-1 as well as G-2, G-6, A-1, A-2 and A-4 were quite similar. The normal growth habit is semi-erect with variants in the vegetative stage consisting of a few more spreading decumbent or semi-decumbent types, and nonspreading fine-leaved "ball types." In the reproductive stage, the low types produce decumbent seed heads that protrude laterally at plant perimeter with no heads arising from the center of plants. The fine and very dense ball nonspreading ball types produce either few or no flowers. These variants are estimated to constitute approximately 0.5% of the total population. A PVP nursery was established at the Pure Seed Testing Research Farm in Hubbard, Oregon in 1995 consisting of 20 creeping bent cultivars with four replications of 25 space plants each including new Penn State varietal releases Penn A-1, Penn A-2, Penn A-4, Penn G-1, Penn G-2, Penn G-6, Seaside II and 12 commercial bents. Morphological character measurements are shown in Table 1 and visual rating to the closest 10% by three individual raters in Table 2. From Table 2, character ratings with a minimum of 20% difference were used to separate varieties. Penn G-1 significantly differed from other bent variety characteristics as follows: Penn G-2: Flagleaf length, flagleaf width, head count, leaf anthocyanin, and ligule shape. Penn G-6: Flagleaf width, leaf anthocyanin, ligule shape, ligule margin, panicle type, panicle anthocyanin, branches at anthesis and fruit. Penn A-1: Panicle length, flagleaf width, leaf anthocyanin, ligule shape, panicle type and panicle anthocyanin. Penn A-2: Panicle length, number of bottom whorls, head count, leaf anthocyanin, ligule shape, panicle anthocyanin, branches at anthesis and branch surface. Penn A4: Flagleaf width, leaf anthocyanin, ligule shape, ligule pubescence, ligule margin, panicle anthocyanin and branches at anthesis. Seaside II: Flagleaf width, leaf anthocyanin, ligule shape, panicle type, panicle anthesis, branches at anthesis and fruit and the branch surface. Seaside: Panicle length, leaf anthocyanin, ligule shape, ligule margin and panicle type. Southshore: Panicle length, flagleaf length and flagleaf width. Crenshaw: Flagleaf length, flagleaf width, number of panicle bottom whorls and head count. Providence: Panicle length, flagleaf length and flagleaf width. Regent: Panicle length and head count. Putter: Panicle length and head count. Lopez: Panicle length, flagleaf length and width, number of panicle bottom whorls and plant count. SR-1020: Panicle length, flagleaf length and width. ProCup: Panicle length, flagleaf width, number of panicle bottom whorls and head count. Penncross: Panicle length, flagleaf length and width and head count. Cato: Flagleaf width. Pennlinks: Plant height, panicle length and flagleaf length and width. Based on space plant morphology Penn G-1 is most similar to Cato but is further differentiated in characteristics under close cut turf conditions as shown in Tables 3 and 4 for leaf texture and density. In a close height of cut managed at 3.2 mm, PENN G-1 creeping bent is unique in producing a very fine and dense putting green turf. Measured leaf textures in three locations show a significantly narrow blade width ranging from 0.65 to 0.72mm as shown in Table 3. Unique high density stands under putting green management are supported by measured turf shoot densities ranging from 1996 to 2612 per square decimeter compared to 765 to 1509 for commercial bents in Augusta, Ga. and Turin, Italy as shown in Table 4, and visual ratings shown in Tables 5, 6, and 7. Superior turf quality performance is illustrated in evaluations for three locations shown in Tables 8, 9 and 10 and resistance to moss invasions is shown in Table 11. PENN G-1 also shows only a slight amount of winter purple coloring under frosting conditions in Georgia as shown in Table 12. Although more limited in turf testing than co-developed varieties due to a contamination of seed supply, PENN G-1 showed good resistance to brownpatch and leafspot and moderate susceptibility to snowmold, dollarspot and pythium as shown in Tables 5, 7 and 13. __________________________________________________________________________ 1. Species: Creeping Bentgrass (Agrostis palustris) 2. Adaptation: Northeast - Adapted Southeast - Adapted North Central - Adapted Pacific Northwest - Adapted 3. Maturity: (At first anthesis) 3 days earlier than Penncross 2 days later than Pennlinks 4. Height: (Average of longest 10 shoots from soil surface to top of head) Height at maturity: 53 cm10 cm shorter than SeasideSame as Providence10 cm taller than Penncross 5. Growth Habit: 1% Decumbent 99% Geniculate 6. Vegetative Reproduction: Rhizomes: Absent Stolons: Present - 100% Stolons 7. Leaf Blade: Texture (fineness): Very fine (Kingstown) Width (Flag leaves): 48 mm Length: (Flag Leaves): 92 cm 8. Leaf Sheath: Anthocyanin: Present Red Sheaths: 100% 9. Ligule: (Lower and Middle Leaves): Shape at Apex: Acute - 50% Rounded - 20% Truncate - 30% Pubescence: Glabrous - 100% Margins: Entire - 20% Toothed - 80% 10. Lemma: Shape: 100% Lanceolate Color: 100% Silvery Texture: 100% Smooth Pubescence: 100% Glabrous Basal Hairs: 100% Absent Awns: 100% Absent Width: 39 mm Length (exclusive of awn): 15 mm 11. Panicle: Type (in anthesis): 20% Open 80% Compact Anthocyanin: 80% Absent 20% Present Branches (in anthesis): 90% Appressed 10% Ascending Branches (in fruit): 90% Appressed 10% Ascending Branch Surface: 90% Smooth 10% Scabrous Seed: .076 grams per 1000 seed 13. Spring Green Up: Medium (Astoria) 14. Environmental Resistance: Cold: Resistant Heat: Resistant 15. Disease Resistance: Red Leaf Spot - Drechslera erythrospila: Resistant Pythium Blight - P. Aphanidermatum: Susceptible Fusarium Patch - Pink Snow Mold (F. Nivale): Susceptible Dollar Spot (Sclerotinia homoeocarpa): Susceptibie Pythium Blight (P. Ultimum): Susceptibie Brown Patch (Rhizoctonia solani): Resistant Variety That Most Closely Resembles Submitted Variety: (Degree of resemblance is rated as follows: 1 = Submitted variety is less than, lighter, or inferior to similar variety, 2 = Same as, 3 = More than, darker or superior.) Growth Habit: Pennlinks - 2 Cold Resistance: Pennlinks - 2 Brown Patch: Pennlinks - 3 Leaf color: Pennlinks - 2 Panicle Type: Pennlinks - 2 Turf Fineness: Pennlinks - 3 Heat Resistance: Pennlinks - 2 Moss Resistance: Pennlinks - 3__________________________________________________________________________ TABLES The tables listed below show comparisons with the instant invention and other known bentgrass cultivars. Table 1 shows the measurements for plant height, panicle length, flag leaf length, flag leaf width, bottom whorl branches and head count. Table 2 shows morphological characteristics for leaf sheath anthocyanin, ligule shape, ligule pubescence, ligule margins, panicle type, panicle anthocyanin, branches in anthesis, branches in fruit, and branch surface. Table 3 shows the leaf texture of bentgrass cultivars maintained as putting green turf in University Park, Pennsylvania, Augusta, Ga. and Turin, Italy. Table 4 shows the shoot density in Augusta, Ga. and Turin Italy. Table 5 shows the density evaluations for 1992, 1993 and 1994 and disease statistics for Dollarspot and Snowmold. Table 6 is a 1991 evaluation for density, texture, growth habit, leafspot and brownpatch using a scale of 1 to 9 with 9 being best. Table 7 is a density evaluation and disease statistics for Pythium at Loxahatchee Country Club in West Palm Beach, Fla. These figures use a scale of 1 to 9 with 9 being best. Table 8 shows quality ratings at Augusta National Golf Club from 1992 to 1995. Table 9 indicates the seasonal turf quality in winter, spring, summer and fall, 1992 at the Turf Seed Research at Rolesville, N.C. These figures use a scale of 1 to 9 with 9 being best. Table 10 is the mean annual turf quality at Turin, Italy for 1992, 1993 and 1994 also using the scale of 1 to 9 with 9 being best. Table 11 is the percent of moss present in Turin, Italy during 1993 and 1994. Table 12 shows winter purple color ratings at Augusta National Golf Club, Georgia in 1993-1994. Table 13 shows mean Rhizoctonia brownpatch ratings for 1992 in Rolesville, N.C. TABLE 1__________________________________________________________________________Morphological Character MeasurementsPlant Height Panicle Length Flag Leaf Length Flag Leaf Width # Bottom Whorl (cm) (cm) (cm) (mm) Branches Head Count__________________________________________________________________________Seaside II 63.8 Penn A-1 13.1 Penn G-1 9.25 Providence 4.82 Penn A-1 7.3 Seaside 373 Seaside 63.1 Seaside 13.0 Seaside II 9.03 Seaside II 4.57 Penn A-2 7.0 Providence 370 Penn A-1 62.5 Southshore 12.8 Seaside 8.90 Lopez 4.53 Procup 7.0 Penn G-1 264 Southshore 60.2 Crenshaw 12.3 Regent 8.47 Crenshaw 4.52 Crenshaw 6.7 Seaside II 22 Penn G-2 57.1 Cato 12.2 Procup 8.26 Penn A-1 4.45 Lopez 6.6 Cato 213 Crenshaw 54.1 Penn G-1 11.7 Penn A-1 7.98 Cato 4.40 Putter 6.4 Penn A-1 193 Providence 53.1 Penn G-6 11.7 Putter 7.91 Procup 4.37 VNS 6.4 Penn AA 181 Penn G-1 53.0 Seaside II 11.6 Penn G-6 7.82 Penncross 4.32 Pennlinks 6.4 Pennlinks 178 Penn A-2 52.2 Penn A-4 11.6 Cato 7.78 Penn G-6 4.17 Penn G-6 6.3 Southshore 170 Regent 51.4 Penn G-2 11.4 Penn A-2 7.73 Southshore 4.17 Penncross 6.3 SR 1020 154 Putter 49.9 Putter 11.2 Crenshaw 7.48 Penn G-2 3.95 Providence 6.3 Penn G-6 153 Lopez 47.5 Pennlinks 11.0 Penn G-2 7.43 Pennlinks 3.83 5R1020 6.0 Crenshaw 133 Penn AA 46.7 Regent 11.0 Lopez 7.13 SR 1020 3.82 Cato 5.8 VNS 132 VNS 46.0 VNS 11.0 Penncross 7.06 Penn A-4 3.77 Penn G-2 5.6 Penn G-2 129 5R1020 44.3 Procup 10.8 Southshore 7.06 Putter 3.75 Regent 5.6 Regent 123 Procup 44.3 Lopez 10.5 VNS 6.87 VNS 3.62 Penn G-1 5.6 Penncross 10 Penn G-6 43.2 Providenc e 10.2 SR 1020 6.86 Seaside 3.43 Southshore 5.5 Putter 100 Penncross 43.2 SR 1020 10.0 Providence 6.68 Penn G-1 2.83 Seaside II 5.4 Penn A-2 95 Cato 42.3 Penncross 10.0 Pennlinks 6.50 Penn A-2 2.58 Seaside 4.8 Lopez 81 Pennlinks 37.8 Penn A-2 9.9 Penn AA 5.90 Regent 2.38 Penn AA 4.6 Procup 59 LSD 13.8 0.6 1.56 0.96 0.9 119__________________________________________________________________________ TABLE 2__________________________________________________________________________Morphological Characteristics Seaside Seaside II Penn A-1 Penn A-2 Penn A-4 Penn G-1 Penn G-2 Penn G-6__________________________________________________________________________Leaf sheath anthocyanin Present 40 0 0 0 0 100 0 0 Absent 60 100 100 100 100 0 100 100 Ligule shape Acute 20 60 80 20 10 30 20 100 Truncate 60 40 20 80 90 30 80 0 Round 20 0 0 0 0 20 0 0 Ligule pubescence Glabrous 100 100 100 100 0 100 100 90 Pubescence 0 0 0 0 100 0 0 10 Ligule margins Entire 50 30 30 20 100 20 20 90 Toothed 50 70 70 80 0 80 80 10 Panicle type Open 40 40 50 30 30 20 30 10 Compact 60 60 50 70 70 80 70 90 Panicle anthocyanin Present 0 30 0 70 0 20 30 90 Absent 100 70 100 30 100 80 70 10 Branches in anthesis Appressed 80 70 80 70 60 90 80 100 Ascending 10 30 20 30 40 10 20 0 Spreading 10 0 0 0 0 0 0 0 Branches in fruit Appressed 90 50 80 70 80 90 80 100 Ascending 5 50 20 30 20 10 20 0 Spreading 5 0 0 0 0 0 0 0 Branch surface Smooth 90 70 90 100 90 90 80 90 Scabrous 10 30 10 0 10 10 20 10__________________________________________________________________________ TABLE 3______________________________________Leaf texture of bentgrass cultivars maintained as putting green turf in three locations (mm) University Park, PA Augusta, GA Turin, Italy______________________________________Penn G-2 0.61 Penn A-2 0.63 Penn G-2 0.63 Penn G-6 0.63 Penn A-1 0.65 Penn G-6 0.70 Penn A-1 0.63 Penn G-2 0.65 Penn A-1 0.70 FHG-1 0.63 Penn G-1 0.68 Penn G-1 0.72 Penn G-1 0.65 Penn A-4 0.69 Seaside II 0.79 Penn A-2 0.67 Penn G-6 0.71 Pennlinks 0.80 Penn A-4 0.69 Crenshaw 0.79 SR 1020 0.80 Seaside II 0.74 Cato 0.80 Southshore 0.84 Pennlinks 0.77 Seaside II 0.80 Penncross 0.85 SR 1020 0.80 Penncross 0.99 Providence 0.85 Providence 0.81 Putter 0.86 Penneagle 0.85 Cobra 0.88 Putter 0.89 National 0.90 Carmen 0.93 Seaside 0.90 Cobra 0.95 Penneagle 0.95 Penncross 0.99 Emerald 0.96 Emerald 1.12 LSD (.05) 0.04 0.06 0.10______________________________________ TABLE 4______________________________________Bentgrass shoot density/dm.sup.2 Augusta, GA and Turin, Italy Augusta, GA Turin, Italy 1992 1993 1992 1993______________________________________Penn A-2 2376 2392 Penn G-1 1574 2612 Penn A-1 1815 2145 Penn G-2 1080 2546 Penn G-1 1881 1996 Penn G-6 1065 2378 Penn G-2 2079 1963 Penn A-1 1075 2240 Penn A-4 1617 1917 Seaside II 1043 2058 Penn G-6 1683 1838 Southshore -- 1509 Crenshaw 1617 1419 Pennlinks 1000 1504 Cato 1254 1287 Providence 914 1425 Penncross 1122 1270 SR 1020 1017 1419 Seaside II 1419 1056 Putter 1091 1272Penneagle 980 1241Cobra 1170 1196National 908 1013Emerald 915 1010Seaside 591 765 LSD (.05) 180 214 258 178______________________________________ TABLE 5______________________________________1992-94 Density Evaluations, 1992 Dollarspot and 1994-95 Snowmold--Penn State University Density Dollarspot 1992 1993 1994 sq. Ft. Snowmold______________________________________PSU G-2 8.9 8.5 8.5 1.7 5.7 PSU A-4 8.7 8.3 8.4 3.7 5.7 PSU A-2 8.9 8.7 8.1 2.0 7.7 PSU 115 8.9 8.8 8.5 2.3 3.2 PSU A-1 8.9 8.7 8.0 0.7 5.5 PSU G-6 8.4 8.7 8.3 2.7 5.5 PSU G-1 8.5 8.5 8.2 7.0 6.5 PPSU DF-1 8.2 7.8 8.1 1.7 7.3 Pennlinks 7.8 7.7 7.6 1.0 7.7 Providence 7.8 7.8 7.3 0.3 6.7 88CBE 7.7 6.7 7.7 1.7 7.3 Cato 7.5 7.8 6.5 3.0 8.2 Crenshaw 6.8 7.8 7.0 18.7 5.3 Regent 7.8 6.7 6.7 3.0 7.5 SR1020 7.5 7.5 7.2 7.7 6.7 Putter 7.6 6.3 6.7 5.3 7.3 Cobra 7.0 6.7 6.5 2.0 7.3 ProCup 7.0 6.5 6.2 3.0 7.3 Lopez 7.0 6.5 6.2 3.0 6.5 Penncross 6.0 5.0 5.2 5.7 7.3 LSD (0.05) 1.2 1.1 1.2 1.1 2.4______________________________________ TABLE 6______________________________________1991 Evaluation for Density, Texture, Growth Habit, Leafspot and Brownpatch (Scale 1 to 9--9 = Best--Penn State University Growth Density Texture Habit Leafspot Brownpatch______________________________________PSU G-1 8.5 8.3 8.3 7.3 8.0 PSU G-2 8.5 8.7 8.5 8.7 8.2 PSU G-3 8.6 8.3 8.5 8.7 7.7 PSU G-6 8.5 8.7 8.3 8.5 8.3 PSU A-1 8.4 8.7 8.2 7.8 7.7 PSU A-2 8.6 8.3 8.5 6.2 9.0 PSU A-4 8.4 8.3 8.3 5.0 8.8 PSU DF-1 8.6 8.3 8.5 7.3 8.0 FH G-1 8.4 8.7 8.2 7.8 8.7 Pennlinks 8.0 8.0 7.7 7.5 7.0 Penncross 7.2 4.5 5.0 6.7 7.3 Penneagle 7.6 7.3 7.7 6.7 8.3 Providence 8.0 7.7 7.7 7.8 8.2 Carmen 6.7 4.5 6.3 7.0 5.3 Cobra 6.3 4.5 7.7 7.0 8.3 Putter 7.8 5.7 7.2 6.7 7.6 SR 1020 8.2 7.8 8.0 7.0 7.0 Emerald 5.7 4.0 5.0 4.0 7.1 LSD (0.05) 1.2 0.9 1.0 2.0 2.2______________________________________ TABLE 7______________________________________Loxahatchee Country Club, West Palm Beach, Florida 1991 Bent Test Density 1 to 9--9 = Best Pythium 1992 1993 1994 Avg 1992______________________________________PSU G-2 8.5 7.7 7.3 7.8 5.7 PSU A-1 7.8 7.3 7.5 7.5 5.7 PSU G-6 7.3 7.6 7.6 7.5 6.0 PSU A-2 7.9 7.4 6.8 7.4 5.7 PSU A-4 6.5 7.4 7.2 7.1 5.7 Crenshaw 7.3 6.4 6.5 6.7 4.3 Seaside II 7.3 6.2 6.5 6.7 3.7 PSU G-1 8.3 7.3 6.3 6.6 5.3 Cato 6.3 5.9 6.5 6.2 5.7 Pennlinks 5.9 6.6 5.4 6.0 6.0 SR 1020 5.9 6.6 5.3 6.0 4.7 Providence 5.1 6.3 5.9 5.8 7.7 Syn-1 4.7 4.3 5.2 4.7 4.0 Penncross 4.4 4.6 4.5 4.5 5.3 LSD (.05) 0.4 0.5 0.5 0.4______________________________________ TABLE 8__________________________________________________________________________Augusta National Golf Club 1991 Nursery Test Quality: 1 to 9.9 = best7-92 10-92 2-93 4-93 7-93 1-94 7-94 8-94 10-94 6-95 Avg__________________________________________________________________________PSU G-28.0 8.5 8.0 8.5 8.0 8.5 8.2 8.0 8.0 8.0 8.2 PSU A-1 7.0 8.0 8.0 8.2 8.0 8.2 8.0 8.7 8.0 8.0 8.0 PSU G-1 7.0 7.0 8.2 8.2 8.2 9.0 8.5 7.7 8.2 8.2 8.0 PSU A-4 8.0 7.0 7.8 8.5 8.0 8.5 8.0 8.5 8.0 8.0 8.0 PSU A-2 7.0 8.0 8.2 8.5 8.2 7.2 7.7 8.5 8.2 8.2 8.0 PSU G-6 7.0 7.5 7.5 7.7 7.5 6.0 7.5 7.5 7.8 7.8 7.4 Cato 6.0 6.0 6.5 6.5 6.5 6.2 6.0 7.0 6.5 6.5 6.4 Crenshaw 6.0 6.0 6.5 7.0 6.5 6.0 5.5 6.7 6.0 5.5 6.2 PSU DF-1 6.0 6.0 6.0 5.0 4.0 6.5 5.5 6.0 5.5 5.5 5.6 Penncross 5.0 5.0 4.0 4.5 6.0 3.0 4.5 5.0 6.0 6.5 4.9__________________________________________________________________________ TABLE 9______________________________________Seasonal turf quality for 1992 Turf Seed Research, Rolesville, NC Winter Spring Summer Fall Average______________________________________PSU G-6 5.8 5.9 8.1 8.0 7.0 PSU A-2 6.1 7.0 7.9 6.7 6.9 PSU A-4 6.7 7.2 7.3 6.5 6.8 PSU A-1 4.8 6.3 8.2 7.7 6.7 PSU G-2 5.4 5.9 7.8 7.2 6.6 PSU G-1 5.4 5.5 6.6 6.8 6.1 Cobra 6.2 6.5 5.7 5.0 6.0 Providence 5.4 5.8 6.3 5.8 5.9 ProCup 6.1 6.0 5.4 6.0 5.9 PSU DF-1 5.5 6.4 5.6 5.7 5.8 Penneagle 5.7 6.1 5.4 5.7 5.7 88 CBE 5.7 6.1 5.7 5.3 5.7 SR 1020 6.0 6.3 5.1 5.3 5.7 Regent 5.0 5.5 6.1 5.5 5.5 Pennlinks 4.7 5.7 5.3 5.7 5.4 PREF 4.8 5.6 4.9 5.8 5.3 Putter 5.2 5.3 5.4 5.0 5.2 Lopez 4.4 4.7 5.8 5.5 5.1 PREC 4.7 5.2 4.7 5.5 5.0 Penncross 6.8 5.6 3.2 3.3 4.7 LSD (0.05) 1.1 1.2 1.1 1.2 1.2______________________________________ TABLE 10______________________________________Mean annual turf quality Turin, Italy 1992-1994 Quality 1 to 9--9 = Best 1992 1993 1994 Average______________________________________Penn G-1 7.4 7.4 6.9 7.2 Penn A-1 7.3 7.3 6.6 7.1 Penn G-6 7.2 6.8 6.7 6.9 Penneagle 7.0 6.4 6.4 6.6 Providence 7.0 6.2 6.2 6.5 Penn G-2 6.5 6.3 6.5 6.4 Putter 7.1 6.2 5.9 6.4 Pennlinks 6.9 6.2 5.9 6.3 Penncross 7.0 5.7 5.8 6.2 Southshore -- 6.5 5.5 6.0 Cobra 6.7 5.6 5.7 6.0 Seaside II 6.4 5.8 5.5 5.9 SR 1020 6.7 5.3 5.2 5.7 National 6.2 4.8 4.9 5.3 Emerald 6.3 4.3 4.5 5.0 Seaside 4.8 3.5 3.9 4.1______________________________________ TABLE 11______________________________________Presence of moss in 1993 and 1994 Turin, Italy % Moss--1993 % Moss--1994______________________________________Penn G-1 0.10 1.93 Penn A-1 0.05 1.14 Penn G-6 0.33 3.64 Southshore 0.72 3.67 Penneagle 2.55 5.19 Penn G-2 0.55 2.64 Putter 3.94 6.67 Pennlinks 3.19 7.19 Providence 2.86 3.00 Penncross 3.36 12.29 Seaside II 3.80 7.36 Cobra 3.58 11.19 SR 1020 4.08 8.67 National 11.17 18.81 Emerald 9.33 17.76 Seaside 31.67 26.78 Astoria 24.77 35.57 LSD (.05) 10.20 6.81______________________________________ TABLE 12______________________________________Winter purple color ratings Augusta National Golf Club, Georgia 1993-94 Percent Winter Purple Color 1993 1994 Avg.______________________________________Penn A-1 12 3 7.5 Penn A-4 6 10 8.0 Penn G-2 3 15 9.0 Penn G-1 15 5 10.0 Penn A-2 2 20 11.0 Seaside II 10 40 25.0 Penncross 25 30 27.5 Cato 30 40 35.0 Penn G-6 40 50 45.0 Crenshaw 60 50 55.0______________________________________ TABLE 13______________________________________Mean Rhizoctonia brownpatch ratings for 1992 Turf Seed Research, Rolesville, NC Scale: 1 to 9.9 = best Average______________________________________ PSU A-1 8.7 PSU G-6 8.3 PSU G-1 8.0 PSU G-2 7.3 PSU A-2 6.7 Lopez 6.3 Cobra 5.3 88 CBE 5.3 Regent 5.0 PSU DF-1 5.0 Pennlinks 4.7 ProCup 4.7 PSU A-4 4.7 Penneagle 4.7 Providence 4.3 Syn PREF 3.7 Putter 3.3 Syn PREC 3.0 SR 1020 2.3 Penncross 1.0 LSD (0.05) 3.8______________________________________ DEPOSIT INFORMATION Agrostis palustris (stolonifera) seed of this invention has been placed on deposit with the American Type Culture Collection (ATCC), Manapaar, Va. under Deposit Accession Number 203435 on Nov. 6, 1998. Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the invention, as limited only by the scope of the appended claims.
An Agrostis palustris (stolonifera) turfgrass variety is disclosed. The invention relates to the seeds, the plants, and to methods of producing an Agrostis plant having the characteristic of average leaf blade width of less than one mm wide.
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CROSS-REFERENCE TO RELATED PATENT APPLICATIONS This application is a Division of U.S. application Ser. No. 11/181,531, filed Jul. 14, 2005, which is a Division of U.S. application Ser. No. 10/225,084, filed Aug. 20, 2002, and incorporated herein by reference in its entirety. FIELD OF THE INVENTION The present invention relates to amine-reactive acridinium labeling reagents. In a particular aspect, the present invention relates to acridinium labeling reagents having one or more hydrophilic substituents thereon. In another aspect, the present invention relates to conjugates containing invention acridinium labeling reagents, kits containing same, and assays employing same. BACKGROUND OF THE INVENTION The following description of the background of the invention is provided simply as an aid in understanding the invention and is not admitted to describe or constitute prior art to the invention. Chemiluminescence immunoassays which employ acridinium labels have advantages of high throughput and high analytical sensitivity for low-level analytes of clinical significance. Usually it is desirable to use labeled antibodies with a large number of chemiluminescent tags, which produce high luminescence counts, which, in turn, allows one to achieve lower detection limits. This holds true provided that non-specific binding can be minimized. During conjugation of antibodies with presently available labeling reagents at relatively high reagent-to-protein ratios, low recoveries of the labeled proteins are often obtained. In most of these labeling reactions, protein precipitation and/or formation of protein aggregates have been observed. Presumably, the precipitates and aggregates are the result of protein molecules with higher degree of labeling than the immunologically active conjugates, which remain in solution. The tendency towards precipitation and aggregation can be attributed to the hydrophobic nature of the four-ring aromatic acridinium ester label. Accordingly, there is a need in the art for acridinium labeling reagents which have a reduced propensity to cause protein precipitation and/or promote formation of protein aggregates. BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, it has been discovered that introduction of hydrophilic sulfoalkyl substituents and/or hydrophilic linkers derived from homocysteic acid, cysteic acid, glycine peptides, tetraethylene oxide, and the like, offset the hydrophobicity of the acridinium ring system to produce a more soluble label which can be attached to an antibody at higher loading before precipitation and aggregation problems are encountered. Additional compounds described herein contain linkers derived from short peptides and tetraethylene oxide which increase aqueous solubility due to hydrogen bonding with water molecules. The present invention also embraces reagents for multiple acridinium labeling for signal amplification composed of a peptide bearing several acridinium esters with sulfonate groups at regularly spaced intervals for increased solubility. In accordance with another aspect of the present invention, there are provided assays for the presence of an analyte in a sample, said assay comprising: contacting an analyte with an invention conjugate, inducing chemiluminescence by decay of an intermediate formable in the presence of a peroxide or molecular oxygen, and measuring chemiluminescence therefrom to assay the analyte. In accordance with still another aspect of the present invention, there are provided improved diagnostic assays for the detection of an analyte using a chemiluminescent label conjugated to a specific binding material, the improvement comprising employing an invention compound as the chemiluminescent label compound. The summary of the invention described above is not limiting and other features and advantages of the invention will be apparent from the following detailed description of the preferred embodiments, as well as from the claims. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 provides a reaction scheme for preparation of exemplary hydrophilic chemiluminescent compounds according to the invention, useful as labeling reagents. FIG. 2 provides a reaction scheme for preparation of 2,6-(dimethyl)-3-chlorosulfonylphenyl-N-(3-sulfopropyl)-acridinium-9-carboxylate (“SPAE”). FIG. 3 provides a reaction scheme for preparation of SPAE-(Lys-HCA) 5 -PFP. FIG. 4 provides a reaction scheme for preparation of exemplary acridinium-protein conjugates according to the invention. FIG. 5 provides reaction schemes describing the formation of exemplary acridinium-protein conjugates using NHS esters ( FIG. 5 a ) and pentafluorophenyl esters ( FIG. 5 b ) according to the invention. FIG. 6 presents the chemical structures of several acridinium labeling reagents (e.g., MeAE and SPAE derivatives). DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, there are provided chemiluminescent compounds having the structure: wherein: X═O, S or NR′, wherein R′ is H or alkyl or substituted alkyl; Y═O or S; Z=alkyl, sulfoalkyl, alkenyl, or sulfoalkenyl; Ar=aryl or heteroaryl bearing at least one —SO 2 L substitutent, wherein L is halogen or NHQ, wherein Q is a linker bearing an amine reactive group; R=sulfoalkyl or sulfoalkenyl; A − is an optional suitable counter-ion; and n=0-3; provided that if L is halogen, Z is sulfoalkyl or sulfoalkenyl. Thus, in one aspect of the present invention, there are provided amine-reactive acridinium labeling reagents comprising: 1) a chemiluminescent acridinium ester, 2) a hydrophilic substituent such as a sulfoalkyl group and/or a hydrophilic linker such as those derived from a sulfonated amino acid such as cysteic acid or homocysteic acid or a short peptide such as diglycine, triglycine or tetraglycine or a peptide containing cysteic acid or homocysteic acid with multiple acridinium labels or a linker containing tetraethylene oxide and 3) a reactive group such as sulfonyl chloride, succinimidyl ester (NHS ester) or pentafluorophenyl ester. A variety of structures and commonly used designations therefor, together with the prior art chemiluminescent reagent, MeAE, are shown in FIG. 1 . As employed herein, “alkyl” refers to saturated straight or branched chain hydrocarbon radical having in the range of 1 up to about 20 carbon atoms. “Lower alkyl” refers to alkyl groups having in the range of 1 up to about 5 carbon atoms. “Substituted alkyl” refers to alkyl groups further bearing one or more substituents selected from hydroxy, alkoxy (of a lower alkyl group), mercapto (of a lower alkyl group), cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen, trifluoromethyl, cyano, nitro, nitrone, amino, amido, —C(O)H, acyl, oxyacyl, carboxyl, carbamate, dithiocarbamoyl, sulfonyl, sulfonamide, sulfuryl, and the like. As used herein, “sulfoalkyl” refers to substituents having the structure: —(CR″ 2 ) q —SO 3 − , wherein: each R″ is independently H, lower alkyl, substituted lower alkyl; and q=1-6. Thus, the term sulfoalkyl embraces such groups as sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, sulfohexyl, and the like. A presently preferred sulfoalkyl group according to the invention is sulfopropyl. As used herein, “sulfoalkenyl” refers to substituents having the structure: —(CR″ 2 ) r —C(R″)═C(R″)—(CR″ 2 ) r —SO 3 − , wherein: each R″ is independently H, lower alkyl, substituted lower alkyl and each r is independently 0-4. Thus, the term sulfoalkenyl embraces such groups as sulfoethenyl, sulfopropenyl, sulfobutenyl, sulfopentenyl, sulfohexenyl, and the like. A presently preferred sulfoalkenyl group according to the invention is sulfopropenyl. As employed herein, “aryl” refers to aromatic groups having in the range of 6 up to 14 carbon atoms and “substituted aryl” refers to aryl groups further bearing one or more substituents as set forth above. In one aspect of the invention, aryl is a 2,6-dialkyl substituted phenyl, such as, for example, 2,6-dimethylphenyl, 2,6-diethylphenyl, and the like. A presently preferred aryl contemplated for use in the practice of the present invention is a group having the structure In accordance with another preferred aspect of the present invention, Ar has the structure: wherein Q is polyoxyalkylene, poly-L-lysine, poly-(lysine-homocysteic acid), poly-(lysine-cysteic acid), polyglycine, aminodextran, or the like. As employed herein, “heteroaryl” refers to aromatic groups having in the range of 4 up to about 13 carbon atoms, and at least one heteroatom selected from O, N, S, or the like; and “substituted heteroaryl” refers to heteroaryl groups further bearing one or more substituents as set forth above. Exemplary heteroaryl compounds contemplated for use in the practice of the present invention include pyridyl, pyrimidyl, pyrazinyl, triazolyl, isooxazolyl, isothioazolyl, imidazolyl, and the like. As employed herein, “halogen” refers to fluoride, chloride, bromide or iodide atoms. As employed herein, “suitable counter-ion”, A − , refers to halogen ions, sulfate ions, nitrate ions, carboxylate ions, triflate ions, fluorosulfonate ions, difluorosulfonate ions, and the like. The use of a counter-ion is optional, in that certain molecules may use an internal “counter-ion”; for example, when Z is sulfoalkyl or sulfoalkenyl, the sulfo-moiety provides a suitable counter-ion. Linkers bearing an amine reactive group, Q, contemplated for use in the practice of the present invention include succinimidyl esters (e.g., N-hydroxysuccinimide esters or NHS esters), N-hydroxyphthalimide esters, pentafluorophenyl esters, tetrafluorophenyl esters, 2-nitrophenyl esters, 4-nitrophenyl esters, dichlorotriazines, isothiocyanates, and the like. In one aspect of the invention, compounds wherein X is O are presently preferred. In another aspect of the present invention, compounds wherein Y is O are also preferred. In a particularly preferred aspect of the invention, both X and Y are O. Exemplary compounds contemplated by the present invention include compounds wherein: X is O, Y is O, Z is sulfoalkyl, Ar is 2,6-dimethyl-3- or 4-chlorosulfophenyl, R is not present, A − not present, and n is 0. Especially preferred compounds are those having the above-described substitution pattern and wherein Z is sulfopropyl. Additional preferred compounds are those wherein Ar is 2,6-dimethyl-3-chlorosulfophenyl or 2,6-dimethyl-4-chlorosulfophenyl. Additional exemplary compounds according to the present invention are set forth in FIG. 6 , e.g., 2,6-(dimethyl)-3-chlorosulfonylphenyl-N-(3-sulfopropyl)-acridinium-9-carboxylate (“SPAE”), SPAE-(polyethyleneoxide) 4 -pentafluorophenyl ester (“SPAE-PEO4-PFP”), 2,6-(dimethyl)-3-chlorosulfonylphenyl-N-methyl-acridinium-9-carboxylate triflate (“MeAE”), and MeAE-(polyethylene oxide) 4 -N-hydroxysuccinimide ester (“MeAE-PEO4-NHS”). In accordance with another aspect of the present invention, there are provided chemiluminescent conjugates comprising a chemiluminescent compound as described herein, conjugated with a specific binding material. “Specific binding material” means herein any material which will bind specifically by an immunoreaction, protein binding reaction, nucleic acid hybridization reaction, and any other reaction in which the material reacts specifically with a restricted class of biological, biochemical or chemical species. Specific binding materials contemplated for use in the practice of the present invention include antibodies, enzymes and substrates therefor, antibodies and antigens therefor, avidin-biotin, nucleic acids, and the like. Invention chemiluminescent compounds are useful in a broad range of specific binding assays for the presence of analyte in a sample. “Presence” shall mean herein the qualitative and/or quantitative detection of an analyte. Such assays may be directed at any analyte which may be detected by use of the improved chemiluminescent compound in conjunction with specific binding reactions to form a moiety thereon. These assays include, without limitation, immunoassays, protein binding assays and nucleic acid hybridization assays. In a typical immunoassay, the analyte is immunoreactive and its presence in a sample may be determined by virtue of its immunoreaction with an assay reagent. In a typical protein binding assay, the presence of analyte in a sample is determined by the specific binding reactivity of the analyte with an assay reagent where the reactivity is other than immunoreactivity. Examples of alternative specific binding reactions for use in assays include enzyme-substrate recognition and the binding affinity of avidin for biotin. In the typical nucleic acid hybridization assay, the presence of analyte in a sample is determined by a hybridization reaction of the analyte with an assay reagent. Analyte nucleic acid (usually present as double stranded DNA or RNA) is usually first converted to a single stranded form and immobilized onto a carrier (e.g., nitrocellulose paper). The analyte nucleic acid may alternatively be electrophoresed into a gel matrix. The immobilized analyte may then be hybridized (i.e., specifically bound) by a complementary sequence of nucleic acid. The foregoing specific binding assays may be performed in a wide variety of assay formats. These assay formats fall within two broad categories. In the first category, the assay utilizes an invention chemiluminescent conjugate which comprises a chemiluminescent moiety of the invention attached to a specific binding material. In this category of assays, the invention chemiluminescent conjugate participates in a specific binding reaction and the presence of analyte in the sample is proportional to the formation of one or more specific binding reaction products containing the invention chemiluminescent conjugate. The assay is performed by allowing the requisite specific binding reactions to occur under suitable reaction conditions. The formation of specific binding reaction products containing the invention chemiluminescent conjugate is determined by measuring the chemiluminescence of such products containing the invention chemiluminescent conjugate or by measuring the chemiluminescence of unreacted or partially reacted invention chemiluminescent conjugate not contained in such products. This first category of assay formats is illustrated by sandwich assays, competitive assays, surface antigen assays, sequential saturation assays, competitive displacement assays and quenching assays. In a sandwich format, the specific binding material to which the chemiluminescent moiety is attached is capable of specifically binding with an analyte of interest. The assay further utilizes a reactant which is capable of specifically binding with the analyte to form a reactant-analyte-chemiluminescent conjugate complex. The reactant may be attached to a solid phase, including without limitation, dip sticks, beads, tubes, paper, polymer sheets, and the like. In such cases, the presence of analyte in a sample will be proportional to the chemiluminescence of the solid phase after the specific binding reactions are completed. Such assay formats are discussed further in U.S. Pat. Nos. 4,652,533, 4,383,031, 4,380,580 and 4,226,993, which are incorporated herein by reference in their entirety, including all figures, tables, and claims. In a competitive format, the assay utilizes a reactant which is capable of specifically binding with the analyte to form an analyte-reactant complex and with the specific binding material, to which a chemiluminescent moiety of the invention is attached, to form a chemiluminescent conjugate-reactant complex. The reactant may be attached to a solid phase, or alternatively reaction products containing the reactant may be precipitated by use of a second antibody or by other known means. In this competitive format, the presence of analyte is “proportional,” i.e., inversely proportional, to the chemiluminescence of the solid phase or precipitate. A further discussion of this assay format may be found in the immediately above mentioned U.S. patents. In another assay format, the analyte may occur on or be bound to a larger biological, biochemical or chemical species. This type of format is illustrated by a surface antigen assay. In this format, the specific binding material is capable of specifically binding with the analyte and the presence of analyte is proportional to the analyte-chemiluminescent conjugate complex formed as a reaction product. This is illustrated by attaching a chemiluminescent moiety of the invention to an antibody which is specific to a surface antigen on a cell. The presence of the cell surface antigen will be indicated by the chemiluminescence of the cells after the completion of the reaction. The cells themselves may be used in conjunction with a filtration system to separate the analyte-chemiluminescent conjugate complex which is formed on the surface of the cell from unreacted chemiluminescent conjugate. This is discussed further in U.S. Pat. No. 4,652,533. Chemiluminescent moieties of the invention may be used in additional assay formats known in the art including without limitation sequential saturation and competitive displacement, both of which utilize a chemiluminescent conjugate where both (1) the specific binding material, to which the moiety is attached, and (2) the analyte, specifically bind with a reactant. In the case of sequential saturation, the analyte is reacted with the reactant first, followed by reaction of the chemiluminescent conjugate with the remaining unreacted reactant. In the case of competitive displacement, the chemiluminescent conjugate competitively displaces analyte which has already bound to the reactant. In a quenching format, the assay utilizes a reactant which is capable of specifically binding with (i) the analyte to form an analyte-reactant complex, and (ii) with the specific binding material to which the chemiluminescent moiety is attached to form a chemiluminescent conjugate-reactant complex. A quenching moiety is attached to the reactant. When brought into close proximity to the chemiluminescent moiety, the quenching moiety reduces or quenches the chemiluminescence of the chemiluminescent moiety. In this quenching format, the presence of analyte is proportional to the chemiluminescence of the chemiluminescent moiety. A further discussion of this format may be found in U.S. Pat. Nos. 4,220,450 and 4,277,437, which are incorporated herein by reference in their entirety, including all figures, tables, and claims. In consideration of the above discussed assay formats, and in the formats to be discussed below, the order in which assay reagents are added and reacted may vary widely as is well known in the art. For example, in a sandwich assay, the reactant bound to a solid phase may be reacted with an analyte contained in a sample and after this reaction the solid phase containing complexed analyte may be separated from the remaining sample. After this separation step, the chemiluminescent conjugate may be reacted with the complex on the solid phase. Alternatively, the solid phase, sample and chemiluminescent conjugate may be added together simultaneously and reacted prior to separation. As a still further alternative, the analyte in the sample and the chemiluminescent conjugate may be reacted prior to addition of the reactant on the solid phase. Similar variations in the mixing and reaction steps are possible for competitive assay formats as well as other formats known in the art. “Allowing under suitable conditions substantial formation” of specific binding reaction products shall herein include the many different variations on the order of addition and reaction of assay reagents. In the second category of assay formats, the assay utilizes an unconjugated chemiluminescent compound of the invention. The presence of analyte in the sample is proportional to the formation of one or more specific binding reaction products which do not themselves contain the chemiluminescent moiety. Instead, the chemiluminescent compound chemiluminesces in proportion to the formation of such reaction products. In one example of this second category of assays, the assay utilizes a reactant capable of binding with the analyte to form an analyte-reactant complex which causes the chemiluminescent compound to chemiluminesce. This is illustrated by a simple enzyme-substrate assay in which the analyte is the substrate glucose and the reactant is the enzyme glucose oxidase. Formation of the enzyme-substrate complex triggers the chemiluminescent compound. Such enzyme-substrate assay for glucose is disclosed in U.S. Pat. Nos. 3,964,870 and 4,427,770, which are incorporated herein by reference in their entirety, including all figures, tables, and claims. This enzyme-substrate assay is a specific binding assay in the sense that the substrate specifically binds to the active site of the enzyme in much the same way that an antigen binds to an antibody. In this assay, the enzyme specifically binds with the substrate which results in the production of peroxide which, in turn, causes the chemiluminescent compound to chemiluminesce. Also included in the second category of assays are those assays in which the formation of the reaction products promotes or inhibits chemiluminescence by the chemiluminescent compound in a less direct manner. In this assay, a first reactant, which is cross reactive with the analyte, is attached to an enzyme such as glucose oxidase close to its active site. A second reactant which is specific for both the analyte and the immunoreactive material is added to the sample and the altered enzyme in the presence of the substrate (i.e., glucose). When the second reactant binds to the first reactant located near the active site on the enzyme, the second reactant blocks the active site in a way that the substrate cannot bind to the enzyme at the active site, or the binding of the substrate at the active site is significantly decreased. The second reactant blocking the enzyme in this manner inhibits the enzyme from producing peroxide which, in turn, would have triggered the chemiluminescent moiety. Analyte in the sample, however, will tie up the second reactant, thus preventing the second reactant from inhibiting the production of peroxide. The presence of analyte will be proportional to the chemiluminescence of the compound. The assays contained in the above two categories of assay formats may be heterogeneous or homogeneous. In heterogeneous assays, the reaction products, whose formation is proportional to the presence of analyte in the sample, are separated from other products of the reaction. Separation can be achieved by any means, including without limitation, separation of a liquid phase from a solid phase by filtration, microfiltration, double antibody precipitation, centrifugation, size exclusion chromatography, removal of a solid phase (e.g., a dip stick) from a sample solution or electrophoresis. For example, in a sandwich assay the reactant-analyte-chemiluminescent conjugate complex is separated from unreacted chemiluminescent conjugate. In a surface antigen assay, the analyte-chemiluminescent conjugate complex is separated from unreacted chemiluminescent conjugate. In a competitive assay, the reactant-chemiluminescent conjugate complex is separated from unreacted chemiluminescent conjugate. In a sequential saturation assay and in a competitive displacement assay, the reactant-chemiluminescent conjugate complex is separated from unreacted chemiluminescent conjugate. Alternatively, in homogeneous assays the reaction products are not separated. After the assay reagents have been allowed to react, the chemiluminescence may be measured from the whole assay mixture whether such mixture is in solution, on a solid phase or distributed between various membrane layers of a dip stick or other solid support. The glucose assay using glucose oxidase and a chemiluminescent moiety illustrates a simple homogeneous assay in which separation is unnecessary. The quenching assay illustrates a more complex homogeneous assay in which separation is unnecessary. Finally, “measuring the chemiluminescence” shall include, where relevant, the act of separating those specific binding reaction products, the formation of which are proportional to the presence of analyte in the sample, from other reaction products. It shall also include, where relevant, the acts of (i) treating the chemiluminescent moiety with acid to cleave an acid labile group from the moiety, and/or (ii) triggering the chemiluminescent moiety to chemiluminesce in the case of those assay formats in which the formation of the reaction products does not itself trigger the chemiluminescent moiety. In accordance with yet another aspect of the present invention, there are provided chemiluminescent assay kits comprising a conjugate as described herein. Such kits preferably comprise one or more assay components as described above, including at least one chemiluminescent assay component comprising chemiluminescent moiety of the invention, and may optionally include one or more of: instructions for performing the detection; reagents, such as buffers, for use in performing the detection; pipets for liquid transfers; etc. The invention will now be described in greater detail by reference to the following non-limiting examples. Example 1 Preparation of Hydrophilic Chemiluminescent Acridinium Labeling Reagents The relatively hydrophobic compound MeAE [2,6-(dimethyl)-3-chlorosulfonylphenyl-N-methyl-acridinium-9-carboxylate triflate] was prepared from 2,6-(dimethyl)phenylacridine-9-carboxylate by N-methylation with methyl triflate followed by reaction to form the sulfonyl chloride [U.S. Pat. No. 5,284,952]. This compound was converted to hydrophilic acridinium esters by reaction with a hydrophilic amino acid or peptide followed by formation of the N-hydroxysuccinimide (NHS) or pentafluorophenyl (PFP) ester according to the scheme in FIG. 1 . The synthesis of exemplary compounds is described in additional detail below. Example 2 MeAE-PEO4-NHS To a stirred solution of 130 mg (0.34 millimole) tetraethyleneglycol amino propionic acid, TFA and 190 mg (1.4 millimole) diisopropylethylamine in 4 ml dry acetonitrile was added three portions of MeAE in dry DMF [total amount=100 mg (0.17 millimole) in 1.5 ml]. The mixture was stirred in the dark under argon at room temperature for 2.5 hrs. The mixture was acidified by addition of 2 M aqueous trifluoroacetic acid to pH 3 on a wet pH strip. The volatiles were removed on a rotary evaporator and then the residue was redissolved in 10% acetonitrile-90% aqueous 50 mM acetic acid. The mixture was passed through a Sephadex G10 gel filtration column using 10% acetonitrile/90% aqueous 50 mM acetic acid as eluting solvent. The amount of product was 47.5 micromole (28% yield) as determined by UV-vis absorbance. The solution collected from the gel filtration was acidified to pH 2 by addition of 2 M aqueous methanesulfonic acid. The volatiles were removed by vacuum to produce the yellow solid MeAE-PEO4-COOH. ESI mass spec. Positive mode m/z=669 (acridinium ion carboxylic acid), m/z=691 (sodium salt). Negative mode m/z=781 (acridinium trifluoroacetate carboxylate). The MeAE-PEO4-COOH was dried by azeotropic evaporation with 1 ml pyridine followed by vacuum dessication. To a solution of 48 micromole MeAE-PEO-COOH and 0.52 millimole pyridine in 0.5 ml dry DMF was added 61 mg (0.24 millimole) solid disuccinimidyl carbonate. The reaction was allowed to proceed for 6 hrs with stirring at room temperature under argon. Dry ether (5 ml) was added to precipitate the MeAE-PEO4-NHS product. The supernatant was removed by aspiration and then the solid was redissolved in DMF, reprecipitated by addition of ether, washed with ether and dried. ESI mass spec. Positive mode m/z=766 (acridinium ion NHS ester). Example 3 MeAE-HCA-NHS A mixture composed of 293 mg (1.6 mmole) homocysteic acid, 0.5 ml water, 2.8 ml of 1 M NaOH, 4 ml of 0.2 M carbonate buffer pH 9.3 and 1 ml DMF was cooled externally in an ice bath. A freshly prepared solution of 40 mg (0.2 mmole) MeAE in 0.5 ml DMF was added with stirring. More carbonate buffer pH 9.3 (3 ml of 0.2 M) was added. Another portion of freshly prepared MeAE (40 mg (0.2 mmole) in 0.5 ml DMF) was added to the stirred cooled mixture. Carbonate buffer pH 9.3 (0.5 ml of 0.2 M) and DMF were added to the stirred mixture. The mixture was stirred in the ice bath for 30 min and then at room temperature for 30 min. The mixture was acidified to pH 2 by addition of 1 M aqueous methanesulfonic acid. After removal of volatiles on a rotary evaporator, the product was extracted from the solid residue into three 20-ml portions of hot methanol. The methanol extract was filtered and then concentrated to dryness to produce a yellow solid. The solid was recrystallized twice by dissolving in hot methanol followed by addition of ethyl acetate to produce 92 mg (78% yield) of MeAE-HCA product. ESI negative mode using DMSO/MeCN as solvent: m/z=603 (pseudobase sulfonate anion). Negative mode using MeOH/H 2 O as solvent: m/z=617 (methoxy adduct sulfonate anion), m/z=308 (methoxy adduct sulfonate carboxylate dianion). Trifluoroacetic acid in acetonitrile (2 ml of 2 M solution) was added to solid MeAE-HCA (25 mg, 43 micromole) to convert the pseudobase to acridinium. The volatiles were removed in vacuum and then the yellow solid was dried in vacuum for 2 hrs. A mixture of the dry MeAE-HCA, 41 μl pyridine 0.51 mmole) and 66 mg (0.26 mmole) disuccinimidyl carbonate was stirred under argon at room temperature for 5 hrs. Ether (10 ml) was added to precipitate the product and then the supernatant was removed by aspiration. The product was dried in vacuum, redissolved in 1.5 ml DMF, reprecipitated by addition of 6 ml ether, collected and dried in vacuum. The ether precipitation was repeated to produce 31.7 mg (100%) of MeAE-HCA-NHS product. ESI mass spec, positive mode: m/z=684 (acridinium NHS ester sulfonic acid), m/z=706 (acridinium NHS ester sodium sulfonate). Example 4 C. MeAE-Gly2-NHS A mixture of glycylglycine (264 mg, 2 mmole), water (1 ml), 1.8 ml of 1 M NaOH, 4 ml of 0.2 M carbonate buffer pH 9.3 and 1 ml DMF was cooled externally in an ice bath. Three aliquots of freshly prepared solution of MeAE (total amount=120 mg (0.20 millimole) in 3 ml DMF) were added with stirring. After stirring for 30 min in the ice bath, 1 M aqueous methanesulfonic acid was added to acidify the mixture to pH 2.5. The volatiles were removed in vacuum and then the product was extracted from the yellow solid by treatment with three 15-ml portions of hot 2-propanol. The solution was filtered and concentrated to dryness to produce 123 mg of yellow solid. The solid was recrystallized from hot 2-propanol-ethyl acetate to produce 32 mg (25% yield) of MeAE-Gly2 product. ESI mass spec, positive mode: m/z=536 (acidinium carboxylic acid), m/z=558 (acridinium sodium carboxylate), m/z=590 (acridinium potassium carboxylate). A mixture of 20 mg (32 micromole) MeAE-Gly2, 30 μl (0.3 mmole) pyridine and 49 mg (0.19 mmole) disuccinimidyl carbonate in 0.8 ml dry DMF was stirred in the dark overnight at room temperature under argon. The volatiles were removed in vacuum and then the residue was redissolved in 0.5 ml dry DMF and then the product was precipitated by addition of 3 ml dry ether. After drying in vacuum, the steps of dissolving in DMF, precipitating with ether and drying in vacuum were repeated three times to produce 8.7 mg (37% yield) of MeAE-Gly2-NHS product. ESI mass spec, positive mode: m/z=633 (NHS acridinium ion). Example 5 MeAE-Gly3-NHS A mixture composed of 96 mg (0.51 mmole) triglycine, 4 ml 0.5 M carbonate buffer pH 9.5, and 1 ml DMF was cooled externally in an ice bath. Three aliquots of freshly prepared solution MeAE in DMF (total amount=100 mg (0.17 mmole) in 1.5 ml) were added with stirring five minutes apart. The mixture was stirred for 15 min in the cold and 30 min at room temperature. The mixture was acidified to pH 2.5 by addition of 2 M aqueous methanesulfonic acid and then concentrated to dryness to produce a yellow solid. The product was extracted with three 40-ml portions of 2-propanol, filtered and concentrated to dryness. The 2-propanol extraction was repeated to produce 96 mg (80% yield) of yellow solid MeAE-Gly3 product. ESI mass spec, positive mode: m/z=593 (acridinium carboxylic acid). A mixture composed of 47 mg (67 micromole) MeAE-Gly3, 64 μl (0.79 mmole) of pyridine and 103 mg (0.40 mmole) disuccinimidyl carbonate in 2 ml dry DMF was stirred for 5 hr in the dark at room temperature under argon. The product was isolated by ether precipitation following the same procedure as in the MeAE-Gly2-NHS preparation to produce 23.9 mg (45% yield) of MeAE-Gly3-NHS product. ESI mass spec, positive mode: m/z=690 (acridinium NHS ester). Example 6 SPAE The compound SPAE [2,6-(dimethyl)-3-chlorosulfonylphenyl-N-(3-sulfopropyl)-acridinium-9-carboxylate] is a hydrophilic acridinium ester and has the following structure: This compound was synthesized from 2,6-(dimethyl)phenylacridine-9-carboxylate according to the scheme in FIG. 2 . The synthesis of this compound is described in additional detail below. 2,6-Dimethylphenyl 9-acridinecarboxylate (0.654 g, 2.0 mmole) and molten 99+% 1,3-propane sultone (2.4 g, 20 mmole) was placed in an oven-dried 20-ml glass vial. The mixture was microwaved at 70% power in a Sanyo Carousel Model R-230-BK microwave oven for two 15-second periods followed by one 10-second period with swirling between microwaving periods. Total microwaving time=40 seconds. To hydrolyze sulfonate ester groups, 5 ml of 50% methanol. 50% aqueous 0.2 M hydrochloric acid was added and then the black mixture was heated with magnetic stirring in a 80° C. oil bath for 5 hours. The product was purified by preparative HPLC through a 250 mm×21.2 mm Phenomenex Luna 5 micron C18(2) column using isocratic mobile phase with 60% A and 40% B at 8 ml/min flow rate. (Solvent A=0.1% aqueous trifluoroacetic acid, Solvent B=acetonitrile). For each of 30 chromatographic runs, 200 microliters of sample was injected. The product with a retention time between 14 to 15 min was collected when the absorbance at 430 nm was greater than 0.2. The combined collected 14-15 min fraction was concentrated to dryness on a rotary evaporator to produce 0.49 g of yellow solid. The 2,6-(Dimethyl)phenyl-N-(3-sulfopropyl)acridine-9-carboxylate product was recrystallized from hot 1:1 acetonitrile/methanol with addition of ethyl acetate to produce 401 mg of crystals. The mother liquor was concentrated to produce a second crop (76 mg). Yield=53%. ESI mass spec in methanol. Positive mode: m/z=450 (acridinium sulfonic acid) and 472 (acridinium sodium sulfonate). Negative mode: m/z=480 (methoxy adduct sulfonate anion) and 466 (pseudo base sulfonate anion). UV-visible spectrum in 100 mM phosphate pH 2.0: λ max =370 and 430 nm. To a stirred suspension of 2,6-(dimethyl)phenyl-N-(3-sulfopropyl)acridine-9-carboxylate (180 mg, 0.40 mmole) in 12 ml dry dichloromethane in a 25-ml oven-dried flask under argon, was added 400 microliters of 99+% chlorosulfonic acid (0.70 g, 6.0 mmole). The chlorosulfonation was allowed to proceed overnight under argon at room temperature. The small amount of insoluble brown solid was allowed to settle and then the yellow supernatant was added dropwise from a Pasteur pipet to a flask containing stirred 100 ml of anhydrous ether under argon. The product was collected on a sintered glass funnel under a blanket of argon under a large inverted funnel and then washed with about 30 ml of dry ether. The yellow solid SPAE product (212 mg, 97% yield) was dried overnight in vacuum over phosphorus pentoxide. ESI mass spec in methanol. Positive mode: m/z=548 and 550 (acridinium sulfonyl chloride). Negative mode: m/z=578 and 580 (sulfonyl chloride methoxy adduct sulfonate anion). UV-visible spectrum in 100 mM phosphate pH 2.0: λ max =371 and 431 nm (acridinium ion). UV-visible spectrum in 100 mM carbonate pH 9.6: λ max 287 and 320 nm (pseudo base). Specific chemiluminescence activity in 0.4% BSA in phosphate buffer pH 6.0 using the Berthold chemiluminometer=3.8×10 19 relative luminescence units per mole. Example 7 F. SPAE-PEO4-PFP The hydrophilicity of SPAE can be further enhanced by attachment to a linker such as a hydrophilic amino acid or peptide followed by conversion to the NHS or PFP ester. For example, SPAE-PEO4-PFP was prepared which has the following structure: A freshly prepared solution of 5.8 mg (10.6 micromole) SPAE in 0.5 ml anhydrous methanol was added to a stirred solution of 32 mg (82 micromole) of tetraethylene glycol amino propionic acid and 32 μl (0.18 mmole) of diisopropylethylamine in 0.2 ml methanol. The reaction was allowed to proceed for 1 hr in the dark at room temperature under argon. The mixture was acidified by addition of 20 μl of glacial acetic acid and then concentrated to 0.2 ml. Water (0.4 ml) was added and then the product was purified by HPLC through a 10 mm×250 mm Phenomenex Luna C18(2) column using a linear gradient of acetonitrile with absorbance monitoring at 360 nm. Gradient program: 10% B for 2 min, 10% to 90% B in 16 min, 90% B for 3 min, 90% B to 10% B in 1 min, 10% B for 2 min. (Solvent A=0.1% trifluoroacetic acid, Solvent B=acetonitrile). The fraction with retention time of 16 min contained the SPAE-tetraethylene glycol propionic acid (3.2 micromole based on UV-vis spectrum (30% yield). ESI mass spec, positive mode: m/z=777 (acridinium sulfonic acid carboxylic acid), m/z=799 (acridinium carboxylic acid sodium sulfonate). Negative mode: m/z=807 (methoxy adduct sulfonate anion), m/z=403 (methoxy adduct sulfonate carboxylate dianion). A mixture of SPAE-tetraethylene glycol propionic acid (0.77 micromole), 2.66 μl (15.5 micromole) of pentafluorophenyl trifluoroacetate and 1.3 μl (16 micromole) pyridine in 0.2 dry DMF was stirred in the dark at room temperature under argon for 1 hr. The reaction mixture was distributed into four vials and then the volatiles were removed in vacuum to produce SPAE-PEO4-PFP. ESI mass spec Positive mode: m/z=943 (acridinium PFP ester sulfonic acid), m/z=965 (acridinium PFP ester sodium sulfonate). Negative mode: m/z=973 (PFP ester methoxy adduct sulfonate anion). Example 8 SPAE-(Lys-HCA) 5 -PFP Signal amplification can be achieved by the use of a hydrophilic peptide linker that can carry several acridinium labels attached to pendant groups on the peptide backbone. This peptide amplifier can also carry several sulfonate groups at regular intervals for improved aqueous solubility and an amine-reactive functional group for covalent attachment to proteins. One advantage of such labeling strategy is that high specific chemiluminescence activity can be achieved while keeping most of the lysines intact to preserve immunoaffinity. An example of such amplifier is SPAE-(Lys-HCA) 5 -PFP. A synthesis for this exemplary molecule is provided schematically in FIG. 3 , and in additional detail below. The amplifier peptide SPAE-(Lys-HCA) 5 was prepared by the reaction between the synthetic peptide Lys-HCA-Lys-HCA-Lys-HCA-Lys-HCA-Lys-HCA (HCA=homocysteic acid) and excess SPAE (>10 moles SPAE per mole of peptide) in the presence of a base such as diisopropylethylamine. The resulting multi-acridinium peptide carboxylic acid was purified by gel filtration and then treated with excess pentafluorophenyl trifluoroacetate to produce the amine-reactive PFP ester. Example 9 Preparation of Acridinium-Protein Conjugates The chemiluminescent compounds of the present invention can be reacted with specific binding partner such as an antibody, antibody fragment, avidin or streptavidin, protein A or protein G, oligonucleotide, ligand, or hapten. A sulfonyl chloride group reacts readily with lysine or the terminal amino group of proteins in aqueous or mixed aqueous/organic buffered solution, typically at pH>9 to produce stable sulfonamide linkages as shown in the scheme in FIG. 4 . The following exemplary procedure used to label anti-TSH with SPAE is generally applicable for preparing the acridinium-antibody conjugates using sulfonyl chloride reagents/ In preparation for conjugation using SPAE, 1 mg (6.7 nanomole) of goat anti-TSH tag antibody was buffer-exchanged in an Amicon Centricon concentrator cartridge (MW cut-off=30,000) to produce a solution of 1 mg antibody in 400 μl of 100 mM carbonate pH 9.6. In a typical conjugation, the labeling reagent (7 μl of freshly prepared 22.8 mM SPAE (MW=547) in dry DMF, as determined by UV-vis absorbance at 368 nm, was added and then the mixture was shaken. The conjugation reaction was allowed to proceed for 30 minutes at room temperature with occasional shaking. The conjugate was purified by gel filtration though a 27 cm×1 cm column containing 2:1 bed volume of Sephadex G-75 and Sepharose 6B. The column was eluted with 100 mM phosphate pH 6.0 containing 150 mM NaCl with monitoring of UV absorbance at 280 nm. The fractions with elution times of 12 min, 18 min and 32 min contained the antibody aggregate, the antibody-SPAE conjugate and the hydrolyzed excess labeling reagent, respectively. The protein recovery based on Coomasie Blue colorimetric protein assay was 73%. The UV-vis spectrum of an aliquot of the conjugate fraction acidified to pH 2 was recorded to determine the number of acridinium labels per IgG molecule. Based on the acridinium and protein absorbances at 368 nm (ε=15,700 M −1 cm −1 ) and 280 nm (extinction coefficient=1.35 O.D. for a 1 mg/ml solution), respectively, the conjugate was estimated to contain 2.6 labels per IgG molecule. The specific chemiluminescence activity for this conjugate measured using the Berthold Chemiluminometer was 743 RLU/pg. The NHS ester activated acridinium compounds react with amino groups of proteins in aqueous solution in the pH range 7-9 to produce stable amide linkages as shown in the scheme in FIG. 5 a . In a similar manner, the pentafluorophenyl ester group reacts with amino groups of proteins in aqueous buffered solution typically at pH 7-8 to produce bioconjugates with the label attached via stable amide linkages as shown in the scheme in FIG. 5 b . The following procedure was used to prepare exemplary conjugates with the NHS or PFP activated acridinium derivatives: Example 10 Preparation of Conjugates Using Acridinium-NHS Reagents In a typical conjugation reaction, 1.5 mg of goat polyclonal ant-TSH antibody was buffer-exchanged twice on a 30,000 MW cutoff Amicon Centricon concentrator with 20 mM phosphate buffer pH 7.8 to produce 600 uL of 2.5 mg/ml antibody solution. MeAGly2-NHS (66 uL of 2.27 mM soln based on UV-vis absorbance) was added to produce a 15× reagent/antibody molar ratio. The conjugation was allowed to proceed for 1 hr at room temperature with occasional mixing. The conjugate was purified by gel filtration through a mixed bed column in the same manner as the SPAE conjugates. The recovery based on UV absorbance was 87%. The conjugate was found to contain 1.4 acridinium labels per antibody based on UV-vis absorbance. Example 11 Preparation of Conjugates Using Acridinium-PFP Reagents Goat polyclonal anti-TSH antibody (1.12 mg) was buffer-exchanged twice to produce 450 uL of 2.5 mg/mL antibody solution in 100 mM phosphate pH 7.4. Freshly prepared SPAE-PEO-PFP in dry acetonitrile (40 uL of 4.2 mM solution based on UV-vis absorbance) was added with mixing to produce a 22× reagent antibody molar ratio and then the conjugation was allowed to proceed for 1 hr at room temperature in the dark. The reaction was quenched by addition of 10 uL of 1 M glycine in water and then the mixture was chromatographed through the mixed bed gel filtration column in the same manner as the SPAE conjugates. The specific chemiluminescence activity was 332 RLU/pg. Example 12 Analysis of Conjugates The anti-TSH and anti-ACTH were labeled with the hydrophilic acridinium compounds at various molar ratios. The protein recovery was determined by Coomasie Blue colorimetric protein assay. The results are summarized below. Compared to the relatively hydrophobic MeAE compound, the hydrophilic labels gave much higher protein recovery. Very high levels of acridinium labeling were achieved with the hydrophilic labels. TABLE 1 TSH Goat Polyclonal Ab Conjugates Labeling Ratio % Recovery MeAE 26X 17 MeAE-Gly2-NHS 65X 41 MeAE-Gly3-NHS 46X 49 MeAE-Gly4-NHS 26X 72 MeAE-HCA-NHS 72X 108 SPAE 13X 104 SPAE 17X 91 SPAE 21X 82 SPAE 24X 73 SPAE 32X 53 SPAE 36X 55 SPAE 46X 34 TABLE 2 ACTH Monoclonal Ab Conjugates Labeling Ratio % Recovery MeAE 5X 58 SPAE 5X 72 SPAE 9X 78 SPAE 14X  86 Assay Results The assays were run on a Nichols Advantage Specialty System with Nichols Advantage assay wash and triggers. The assay results were generated using the magnetic particles, biotinylated antibodies, buffers and standards from commercially available Nichols Advantage Immunoassay kits. TSH Assay Protocol 1. Pipette 25 uL of a solution containing biotinylated monoclonal anti-TSH and acridinium labeled polyclonal goat anti-TSH. 2. Pipette 200 uL of patient sample. 3. Incubate for 20 minutes at 37° 4. Pipette 50 uL of assay buffer and 13 uL of streptavidin coated magnetic particles. 5. Incubate for 10 minutes at 37°. 6. Wash 3× with assay wash. 7. Trigger and count (2 sec.). ACTH Assay Protocol 1. Pipette 70 uL of biotinylated monoclonal anti-TSH. 2. Pipette 20 uL of acridinium labeled monoclonal anti-TSH. 3. Pipette 150 uL of patient sample or standard/ 4. Incubate for 20 minutes at 37° 5. Pipette 20 uL of streptavidin coated magnetic particles and 150 uL of buffer. 6. Incubate for 10 minutes at 37°. 7. Wash 3× with assay wash. 8. Trigger and count (2 sec.). Because the high acridinium labeling was achieved with the hydrophilic acridinium esters, less antibody was required in the assay. The amount of tracer antibody used was decreased by a factor of 2 for the TSH assay and a factor of 3 for the ACTH assay. Even with significantly less antibody, the hydrophilic acridinium ester labeled antibodies gave improved standard curves with higher signal to noise observed at all standard levels. The analytical sensitivity (limit of detection) was determined by reading the +2SD response from n=20 replicate measurements of the zero standard from the standard curve. The analytical sensitivity of the both the TSH and ACTH assays was significantly improved using the new hydrophilic acridinium labeled antibodies at a lower antibody concentration than the relatively hydrophobic acridinium (MeAE) labeled antibody. TABLE 3 TSH Assay Standard Curve and Analytical Sensitivity 0.4 ug/mL 0.8 ug/mL TSH Conc. 24X SPAE 24X MeAE STD uIU/mL RLU RLU 0 0 385 343 1 0.014 669 520 2 0.021 906 651 3 0.048 1632 1045 4 0.49 13111 7541 5 2.6 54164 30449 6 4.6 96720 56068 7 9.5 164203 93869 8 19 282692 166464 9 51 487052 310816 Analytical Sensitivity 0.0018 uIU/mL 0.0031 uIU/mL (uIU/mL) TABLE 4 ACTH Assay Standard Curve and Analytical Sensitivity 0.2 ug/mL 0.6 ug/mL ACTH Conc. 5X SPAE 5X MeAE STD pg/mL RLU RLU 0 0 507 436 1 3.4 928 624 2 10.3 1943 1035 3 36 5512 2438 4 110 15590 6441 5 355 55645 22393 6 1160 172923 73275 Analytical Sensitivity 0.29 pg/mL 0.73 pg/mL (uIU/mL) Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. While the invention has been described in detail with reference to certain preferred embodiments thereof, it will be understood that modifications and variations are within the spirit and scope of that which is described and claimed.
In accordance with the present invention, it has been discovered that introduction of hydrophilic sulfoalkyl substituents and/or hydrophilic linkers derived from homocysteic acid, cysteic acid, glycine peptides, tetraethylene oxide, and the like, offset the hydrophobicity of the acridinium ring system to produce a more soluble label which can be attached to an antibody at higher loading before precipitation and aggregation problems are encountered. Additional compounds described herein contain linkers derived from short peptides and tetraethylene oxide which increase aqueous solubility due to hydrogen bonding with water molecules. The present invention also embraces reagents for multiple acridinium labeling for signal amplification composed of a peptide bearing several acridinium esters with sulfonate groups at regularly spaced intervals for increased solubility. The invention also embraces assays employing the above-described compounds.
8
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a National Stage of International Application No. PCT/EP2006/009568, filed Oct. 4, 2006, which claims priority to German Patent Application No. 102005052394.3-23, filed Oct. 31, 2005. The disclosures of the above applications are incorporated herein by reference. FIELD [0002] The disclosure relates to a tine for an agricultural implement or a self-propelled working machine and, especially, to a tine attached on a support body of a reel. For example, it is used in connection with a harvesting machine. BACKGROUND [0003] The reel of a harvesting machine generally includes several support bodies that are radially distanced to and circumferentially distributed around a central tube. The support bodies can be formed as tubes or in any other profile. The support bodies are rotatably supported by corresponding support arms that are connected to the central tube. The reel is rotatable around the axis of the central tube. Commonly, at least 40 tines are attached on a reel for each support body to provide a working width of 6 metres. The design of the tine depends on the application of the harvesting machine. Tines made from spring steel wire are known. These tines are preferentially used with harvesting goods that are difficult to grip and to pull into the cutting trough, for example, cereals or grass, especially when they, because of the harvesting situation, rest on the ground. The tines generally have two or more spring windings between their attachment portion, with which they are attached on the support body, and the rod like gripping area. The tines contact the harvesting goods, via the windings, so that the gripping area can get out off the way, when it is heavily loaded. [0004] For other harvesting goods, especially leguminous plants, for example beans, tines made from a plastic material are preferably used. These harvesting goods have to be cut very close to the ground, to collect all the fruit. Here, very wide cutting tables are used on the harvesting machines, for example, a combine harvester, that has a flexible cutter bar. The cutter bar is guided with ground contact in front of the cutting table. When the ground is uneven, these flexible cutter bars carry out a vertical movement relative to the cutting table. Thus, the cutter bar is lifted off the ground and approaches the tine moving above the same. In this case interferences are produced so that the tines can get between the reciprocatingly moving knife blades. If tines made from steel are used, the blades rip off. In this case the cutter bar can break and the cutter drive can be overloaded. The resulting repair times are undesirable during the harvesting work which depends on the weather. [0005] Further, the loss of time has a larger effect than the cost for the repair. Because of this reason, tines are used in flexible cutter bars or for such application conditions that consist of an elastic material, for example, a nylon material, so that when such a tine gets into the cutting area of the knife, the tine is cut or shortened, respectively, by the knife blades. In this case, no damage is produced on the mower knife or on the knife drive. Such a tine can, for example, be exchanged during schedule maintenance. [0006] Several embodiments of reel tines that are made from a plastic material are described in EP 0 475 405 A2. The tine is formed with a slotted eye-let for attachment onto the support body. The slotted eye-let is elastically expanded so that the tine, with its attachment area, can spring back after being pushed on. In this condition, attachment of the tine can be achieved by attachment bolts, or if necessary, additionally in connection with clamps and pins, to achieve locking, as via the support body a torque is introduced into the tine. The danger exists that, when harvesting goods accumulate on or when the tine hits a rigid object, an overload is produced. Different from a tine made from spring steel wire, a tine made from a plastic material has to be sufficiently elastic. During larger loadings, excessive bending and a non-regular circumferential position relative to the support body may be produced. This can lead, in the final effect, to breaking of the tine. [0007] Tines are, however, also used in agricultural implements other than harvesting machines and reels, for example, in hay turning machines. [0008] DE 177 83 79 U1 discloses, for example, a spring tine for a grass tedder, that is attached to a support body, for example an arm. The tine is bent from an integral steel rod. It has a rod-like gripping portion that contacts the grass. Furthermore, it has an attachment portion, bent into an eye-let, that attaches it, by means of a screw, onto the support body. A spring portion, an extending coil, is provided between the gripping portion and the attachment portion. In the opening, formed by the coil-like path of the spring portion, a sleeve, also mounted on the support body, engages the spring. Therefore, the tine is secured on the support body in a double manner. The rod-like gripping portion can avoid an obstacle in a pivoting manner around the spring axes determined by the retainment of the spring portion. [0009] DE 178 20 043 U1 describes a tine for a spreading device, a tedder or rake, respectively. The rod-like tine includes a plastic material. Depending on the strength requirements, the rod-like tine can have reinforcement inserts. The required bending properties can, however, also be achieved by a corresponding design of the cross-sections. The tine is retained by screws on a carrying strap or similar support body. SUMMARY [0010] The present disclosure provides a tine that is made from a plastic material. Accordingly, damages to a mower blade can be prevented. The tine can be made from a relatively rigid plastic material and enables deflection during a corresponding loading without overloading occurring on the part made from the plastic material. [0011] According to an aspect of the disclosure, a tine for an agricultural implement or self-propelled working machine to be attached onto a support body comprises a separate gripping element made from a plastic material. A separate attachment element is connected to the gripping element. The attachment element is made of a spring steel. The attachment element has a connection portion that is connected to the gripping element. The attachment element has an attachment portion it onto the support body. The attachment element has an elastic deflectable spring portion arranged between the attachment portion and the connection portion. [0012] An advantage of the disclosure is that the common tine is made by combining a plastic material and a spring steel wire. This combination provides a rod-like gripping element made from a plastic material that can be used in the area where the danger exists that the tine may come into contact with other machine components, such as a mower sickle. Accordingly, no damages occur since cutting of the gripping element is possible without any adverse effect on the mower sickle. The plastic material can be cut through in an advantageous manner by the mower sickle. [0013] At the same time overloading is prevented. Here the attachment element provides an elastic area that, in the case of a large loading, ensures that the gripping element can deflect. Preferably the attachment element is formed from a wire. [0014] Advantageously, the spring portion of the attachment element, formed from a wire, is wound into the form of a coil. Wire portions projects from both ends of the coil. A first wire portion forms the attachment portion. The coil enables deflection. Also, since the coil is designed from a spring steel wire, it has a higher endurance. A second wire portion represents a connection portion to connect the gripping element. Alternatively, the second wire portion forms together with the spring portion to connect with the gripping element. [0015] The connection portion of the attachment element is embedded in the gripping element. Thus, it is non-detachably connected to the gripping element. The connection portion can be inserted into the injection mold when manufacturing the gripping element. Thus, the connection portion is molded into the gripping element. Thus, the connection portion automatically forms a recess in the gripping element, which accommodates the connection portion, and thus at this portion a close connection is achieved. [0016] The gripping element may be detachably connected to the connection portion of the attachment element. Thus, it is possible to exchange the plastic gripping element, without any problems, in the case that it is damaged. Accordingly, one can still use the attachment element that is made from spring steel. Such an exchange is possible in a simple manner. Furthermore, the plastic gripping element represents a cost-effective component. The costs for the exchange are correspondingly low. [0017] In the detachable embodiment, the gripping element has a recess at one end. The connection portion engages the recess and is detachably held by a fixation mechanism. [0018] The recess comprises a first recess portion that engages the wire portion. A second recess portion at least partially accommodates the coil that forms the spring portion. In this case it is possible for the second accommodation portion to hold the spring portion at its ends transversally to the axis generated by the coil via wall portions. If necessary, the wall portions have, respectively, a bore. A fixing bolt is guided through the bore and through the spring portion. The fixing bolt can be represented by a screw with or without a nut. [0019] Alternatively, the wall portions include elastic latch arms that have latch projections to engage within the spring portion to provide a fixing assembly. A further attachment possibility for the gripping element on the attachment element is a clamping body arrangement. Here, the second wire portion, forming the connection portion, extends in a straight line. The gripping element recess has a first recess portion, in the form of a bore, adapted to receive the second wire portion. A pocket-like second recess portion receives the clamping body arrangement to retain, by a screw or directly themselves, the connection portion. [0020] Spring steel wire can be used to form the attachment element. Here, the wire forming the connection portion is bent into a U. A screw or a pin is passed between the two legs forming the U and rests in bores of the gripping element crossing the recess. Thus, an advantageous attachment is achieved. Besides the fixation by a screw, also the possibility exists to form one of the legs in an elastic manner. The leg engages an indentation in the recess and thus provides fixation. If, then, for example, this indentation is accessible from outside, via a bore, a tool can be inserted from the outside into the bore and press one of the legs towards the other so that a pulling-off of the gripping element is possible. [0021] The fixation portion of the attachment element is bent into an eye-let. A screw or a pin or any other means can be passed through the eye-let to retain the reel tine on the support body of the reel. Additionally, two tines can be combined in such a manner with each other, that they have a joint attachment portion. [0022] Alternatively, it is possible, to manufacture the attachment element from a flat material, such as a flat spring elastic material. Thus, the spring portion is provided in the form of a leaf-spring. The attachment portion can, in this case, be bent relative to the spring portion and to the connection portion and have a hole. A screw or a different fixation mechanism can be passed through the hole to retain the attachment portion and, thus, the tine on the support body of a reel. [0023] In order to retain the plastic gripping element on the flat attachment element, the connection portion of the attachment element can have a through bore. A screw or a pin is passed to engage in the bores of the gripping element. Thus, the screw crosses the recess where the attachment element is accommodated with its connection portion. [0024] The gripping element may, depending on the application case, in the area that contacts the harvesting goods, extend straight with portions arranged under an angle relative to each other or be bent and have a convex and a concave side. Contours can be provided to achieve a stiffer construction of the plastic gripping element. As the spring properties are arranged to the attachment element, a stiffer construction is possible without the positive properties of the plastic gripping element being lost. However, any type of contour shape, leading to a stiff construction, can be selected. [0025] The recess for accommodating the connection portion of the attachment element is preferably arranged in a thickened portion of the gripping element. [0026] Depending on the application, the gripping element can be rod-like or flat according to a paddle-leaf type. Such leaf-like gripping elements are used with sensitive harvesting goods, for example sun flowers. [0027] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. DRAWINGS [0028] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way. [0029] FIG. 1 is a side elevation view of a first embodiment of a tine attached onto a support body. [0030] FIG. 2 is a rear elevation view of the tine according to FIG. 1 . [0031] FIG. 3 is a side elevation view of a second embodiment of a tine. [0032] FIG. 4 is an elevation view in the direction of the arrow A of FIG. 3 . [0033] FIG. 5 is a side elevation view of a third embodiment of a tine. [0034] FIG. 6 is an elevation view in the direction of the arrow B of FIG. 5 . [0035] FIG. 7 is a side elevation view of a fourth embodiment of a tine. [0036] FIG. 8 is a rear elevation view of FIG. 7 . [0037] FIG. 9 is a side elevation view of a fifth embodiment of a tine. [0038] FIG. 10 is a rear elevation view of FIG. 9 . [0039] FIG. 11 is plan view of a sixth embodiment with two tines combined to a double tine. [0040] FIG. 12 is a side elevation view of a seventh embodiment of a tine. [0041] FIG. 13 is a rear elevation view of FIG. 12 . [0042] FIG. 14 is a side elevation view of an eighth embodiment of a tine. [0043] FIG. 15 is a rear elevation view of FIG. 14 . [0044] FIG. 16 is a side elevation view of a ninth embodiment of a tine. [0045] FIG. 17 is a rear elevation view of FIG. 16 . [0046] FIG. 18 is a side elevation view of a tenth embodiment of a tine. [0047] FIG. 19 is a rear elevation view of FIG. 18 . [0048] FIG. 20 is a side elevation view of an eleventh embodiment. [0049] FIG. 21 is a rear elevation view of FIG. 20 . DETAILED DESCRIPTION [0050] The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. [0051] Following a first embodiment of a tine is described in detail using FIGS. 1 and 2 . [0052] In FIGS. 1 and 2 , a tine 1 is shown arranged onto a support body 2 . The support body 2 is a tube, which is, for example, rotatably mounted on the support element of a reel with a radial distance to the rotational axis of the reel. Due to the rotational movement of the support body 2 , the position of the tine 1 , in relation to the ground, can be changed along the rotational path of the reel. Also, the position can be changed with respect to the harvesting goods. The support body can also have a different shape for other applications of the tine. [0053] The tine 1 includes a gripping element 3 and attachment element 4 . In the present embodiment, according to FIGS. 1 and 2 , the two are non-detachably connected to each other. The gripping element 3 has a first end 5 facing the attachment element 4 and, thus the support body 2 forms a thickened portion. The gripping element 3 extends like an elongated rod from the first end 5 to the second end 8 . The gripping element 3 is, in this embodiment, slightly bent, so that it has a concave side 6 that contacts the harvesting goods. A convex side 7 faces away from the concave side 6 . Profiles 10 can be provided starting from the first end 5 in a direction towards the second end 8 . The profiles 10 end, however, in front of the second end 8 . For a stiffer design and also for saving material, the gripping element 3 can be formed T-like, U-like, H-like or have a similar profile. [0054] Towards the first end 5 , the gripping element 3 forms a recess 9 that engages a connection portion 11 of the spring steel wire attachment element 4 . The connection portion 11 and the gripping element 3 are, therefore, non-detachably connected to each other. In the manufacture of the gripping element 3 , plastic can be injection molded around the connection portion 11 of the attachment element 4 in the mold to embed it into the gripping element 3 . To improve the retainment of the connection portion 11 with the gripping element 3 , formations or projections, roughening the upper face of the connection portion 11 can be provided. A significant length portion of the plastic gripping element 3 extends from the attachment element 4 so that a sufficient length of the plastic gripping element projects from the connection portion 11 . Accordingly, in an application in a harvesting implement, if relative positional changes occur between the cutter bar and the reel, the gripping element 3 can be sheared off. [0055] Furthermore, the attachment element 4 has an attachment portion 12 , which forms, for example, an eye-let. A screw can pass through the eye-let to fix the tine 1 onto the support body 2 . In the area between the connection portion 11 and the attachment portion 12 , the attachment element includes a spring portion 13 . This spring portion 13 is represented by a helical spring, which generating axis is generally aligned parallel to the longitudinal axis of the support body 2 or extends at a right angle to the extension of the gripping element 3 . Thus, it is possible that excessive loading or impact loading that acts on the gripping element 3 can be elastically absorbed by the spring portion 13 . The gripping element 3 can deflect and it is thus protected against overstressing. Thus, it is also possible not to have to manufacture the gripping element 3 from a flexible plastic material but to manufacture it from a relative stiff plastic material and to design it in a stiffer manner. The elastic properties are provided by the attachment element 4 made from spring steel. [0056] A transition portion 14 is provided between the spring portion 13 and the eye-let-like formed attachment portion 12 . The transition portion 14 , in the shown embodiment, serves to provide the necessary distance between the spring portion 13 and the attachment portion 12 , to accommodate the support body 2 therebetween. The support body 2 may have any shape. It is not limited. A strip shape or any shape can also be used. In this case, the attachment portion 12 needs to be adapted to its shape, if necessary. In other connection types relative to the support body, such a transition portion can be eliminated. [0057] A second embodiment of a tine 101 according to the disclosure is described in detail with reference to FIGS. 3 and 4 . The essential difference between the embodiment of FIGS. 1 and 2 and the embodiment of FIGS. 3 and 4 is that the gripping element 103 of the tine 101 , made from a plastic material, is a separate component. The gripping element 103 is detachable from the attachment element 104 , which is made from spring steel. The tine 101 includes two elements formed separately from each other, namely the gripping element 103 and the attachment element 104 . The gripping element 103 is formed differently in the area of its first end 105 , formed as a thickened portion. In this area, a recess 109 is provided. The attachment element 104 is detachably accommodated by its connection portion 111 in the recess 109 . The attachment element 104 has a U formed in the area of the connection portion 111 . The spring steel wire that forms the attachment element 104 is bent into a U shape to form a first leg 111 a and a second leg 111 b . The legs 111 a , 111 b extends parallel to one another and are connected to each other by a web of the U. [0058] The intermediate space between the two legs 111 a , 111 b is used to receive a screw 15 when the connection portion 111 is inserted into the recess 109 . The gripping element 103 has a bore 16 intersecting the recess 109 . At both sides of the recess 109 , bore portions are formed like pockets so that the shaft of the screw 15 passes between the two legs 111 a and 111 b and is arranged close to the web of U. Thus, generally zero backlash is provided. Furthermore, the two legs 111 a and 111 b extend with respect to one another so that a biasing of the legs 111 a , 111 b acts on to the boundary of the recess 109 to hold the gripping element 103 essentially without play in the recess 109 . The screw 15 can be formed as a head screw with a self-cutting thread. The screw cuts its thread into the bores 16 at both sides of the recess 109 . Thus, it is possible, in the case, where a partial portion of the gripping element 103 is sheared off in the direction towards the second end 108 , to only exchange the gripping element 103 . This simply happens by detaching the screw 15 and fixing a new gripping element 103 onto the connecting portion 110 . [0059] Furthermore, the remaining components and portions of the gripping element 103 as well as of the attachment element 104 correspond to the embodiment of FIGS. 1 and 2 . Accordingly, comparable parts relative to FIGS. 3 and 4 have been given reference numerals corresponding to like parts of the embodiment of FIGS. 1 and 2 that are increased by the numerical value of 100. For their description, refer to the description of FIGS. 1 and 2 . [0060] Incidentally, for the attachment of the gripping element 103 designs other than a screw 15 are possible. Thus, it is possible to have the two legs 111 a and 111 b extend under an angle relative to each other and to provide an undercut in the recess 109 behind which the end of the leg 111 b is received so that a retainment against pulling-out is provided. Thus, a screw driver can be inserted into a notch in the gripping element 103 to deform the leg 111 b to move it in the direction towards the leg 111 a and thus out of engagement with the undercut. Accordingly, the gripping element 103 then can be pulled off the attachment element 104 . [0061] A third embodiment of a tine 201 is described according to FIGS. 5 and 6 . The gripping element 203 corresponds to the gripping element 103 according to FIGS. 3 and 4 . In FIGS. 5 and 6 , reference numerals are selected that are increased by a numerical value of 100 to those of the embodiment according to FIGS. 3 and 4 . Thus, for their description, refer to the description in connection with FIGS. 3 and 4 . [0062] In FIGS. 5 and 6 , the attachment element 204 of the tine 201 is formed differently from the embodiment according to FIGS. 3 and 4 . In this embodiment, the attachment element 204 is formed from spring steel as a leaf-type spring. It has a connection portion 211 with a through bore 17 . The connection portion 211 enters the recess 209 of the gripping element 203 . The fixation mechanism 215 , formed as a screw, enters the bore 216 and is passed through the bore 17 . Thus, the gripping element 203 is retained on the attachment element 204 . Starting from the connection portion 211 extending into the recess 209 , a leaf-spring-like acting spring portion 213 is provided in the direction towards the attachment portion 212 . The cross-section of the attachment element 204 in the area of the spring portion 213 is such, that, when loading the gripping element 203 in the area of the concave side 206 , an elastic bending of the spring portion 213 is achieved. The cross-section in the direction from the concave side 206 to the convex side 207 of the attachment element, has in the crosswise area of the spring portion 213 , a smaller material thickness. In the area between the spring portion 213 and the attachment portion 212 , a curved transition portion 214 is provided. The transition portion 214 is adapted to the support body formed correspondingly to FIG. 1 . Instead of the eye-let design of the attachment portion in the embodiment of FIGS. 1 to 4 , a hole 18 is provided in the embodiment according to FIGS. 5 and 6 . A fixation element is passed through the hole 18 to retain the reel tine 201 on a support body. In the embodiment according to FIGS. 1 to 4 , flexibility of the spring portion is provided when loading the concave side 206 , and transversally thereto. Thus, a lateral deflection of the gripping element 203 is possible. In the embodiment according to FIGS. 5 and 6 , a deflection is essentially only provided when loading the concave side 206 in the drawing plane of FIG. 5 . Thus, a deflection is only achieved in the lateral direction, to the left and right, using the spring properties of the spring portion 213 . [0063] In FIGS. 7 and 8 , a fourth embodiment of a tine 301 according to the disclosure is shown. Tine 301 differs from the embodiment according to FIGS. 1 and 2 only in the modified design of the gripping element 303 . Parts and portions of the components, which correspond to those of the embodiment according to FIGS. 1 and 2 , are identified with reference numerals that are increased by the numerical value 300 , compared to those according to FIGS. 1 and 2 . For their description, refer to the description of FIGS. 1 and 2 . [0064] The gripping element 303 is rod-like in FIGS. 7 and 8 . Profiles 310 , instead of the ribs, are arranged on the convex side as in FIGS. 1 and 2 . The profiles 310 , in cross-section, lead to an H-shape of the gripping element 303 . The profiles 310 also lead to a stiffened connection with the web arranged therebetween. In FIGS. 7 and 8 , the gripping element 303 is, as in FIGS. 1 and 2 , non-detachably connected to the attachment element 304 . [0065] FIGS. 9 and 10 show views of a fifth embodiment of a tine 401 . The parts and portions that correspond to those of the embodiment of FIGS. 5 and 6 include reference numerals increased by the numerical value 200 compared to those of FIGS. 5 and 6 . In the tine 401 according to FIGS. 9 and 10 , the construction of the attachment element 404 corresponds to that of FIGS. 5 and 6 . Also, it includes a hole 18 at the attachment portion 412 , as in FIGS. 5 and 6 , visible in FIG. 5 . Additionally, it includes the connection portion through bore 17 , according to FIG. 5 , to detachably connect the gripping element 403 to the attachment element 404 by the screw 415 , that serves as a fixation mechanism. The attachment element 404 is also leaf-spring-like, as in the embodiment according to FIGS. 5 and 6 . The design of the gripping element 403 differs from that according to FIGS. 5 and 6 . No ribs are provided on the gripping element 403 arranged on the convex side. Here, the gripping element 403 includes a profile 410 with an H-like cross-section. [0066] FIG. 11 illustrates a sixth embodiment. Here, two tines 501 are coupled to each other so that they can be mounted together on a support body 2 . The two gripping elements 503 correspond to the gripping elements of FIGS. 3 and 4 with the modifications described in connection with FIGS. 9 and 10 . In the embodiment according to FIG. 11 the construction of the attachment element 504 corresponds to that described in connection with FIGS. 3 and 4 for the attachment element 104 . The difference is that two attachment elements 504 are connected to each other by a bridging portion 19 . This bridging portion 19 also has the attachment portion 512 . The attachment portion 512 is formed like an eye-let. Thus retainment of the so-called double tine, which includes two reel tines 501 , can be achieved by a screw on the support body 2 . The bridging portion 19 is dimensioned so that the two reel tines 501 are held with necessary distance between them. [0067] The design of the two attachment elements 504 otherwise corresponds to the attachment element 104 according to FIGS. 3 and 4 . Thus, for its description, refer to the description of these Figures. This is also valid for the embodiment of the connection between the attachment element 504 and the respective gripping element 503 . [0068] FIGS. 12 and 13 illustrate a seventh embodiment of a tine 601 . The gripping element 603 in contrast to the gripping element, according to FIGS. 3 and 4 , is formed as a flat paddle leaf type. [0069] The connection between the attachment element 604 and the gripping element 603 corresponds to the embodiment described in connection with FIGS. 3 and 4 . Thus, concerning its description, refer to the description of FIGS. 3 and 4 . [0070] The attachment element 604 differs from that according to FIGS. 3 and 4 only in the design of the attachment portion 612 . In the embodiment according to FIGS. 12 and 13 , an eye-let is chosen for the attachment onto the support body 2 . The screw that fixes the attachment element 604 on the support body 2 is passed through the attachment portion 612 in form of an eye-let. The attachment portion 612 is arranged as the lengthening of the connection portion 611 . [0071] FIGS. 14 and 15 illustrate an eighth embodiment of a tine. The attachment element 704 differs from FIGS. 3 and 4 in that it has a straight extending connection portion 711 . In order to achieve a tight connection between the gripping element 703 and the attachment element 704 , a clamping member arrangement 20 is provided. The clamping member arrangement 20 is tightened by a screw 715 against the connection portion 711 . The gripping element 703 has a recess 709 with a first recess portion 709 a that accommodates an end portion of the connection portion 711 . A second recess portion 709 b accommodates the clamping member arrangement 20 . The clamping member arrangement 20 has a threaded bore 21 . In the second recess portion 709 b a bore 716 ends, through which the screw 715 can be inserted into the threaded bore 21 of the clamping body arrangement 20 . The connection portion 711 of the attachment element 704 is inserted into the first recess portion. It is held in a clamped manner between the clamping member arrangement 20 by tightening of the screw 715 . [0072] FIGS. 16 and 17 illustrate a ninth embodiment of a tine 801 . The tine 801 differs from to the tine in FIGS. 14 and 15 in that a deflector 22 is added. The deflector 22 is arranged in front of the coil-like spring portion 813 of the attachment element 804 . The deflector 22 should prevent the harvesting goods from entering between the windings of the spring portion 813 . Further, the essential portions and components are provided with reference numerals increased by a numerical value of 100 to 800 compared to those according to FIGS. 14 and 15 . For their description, refer to FIGS. 14 and 15 . [0073] FIGS. 18 and 19 illustrate a tenth embodiment of a tine 901 . The attachment element 904 corresponds to that of the eighth and ninth embodiment. However, the connection between the gripping element 903 and the attachment element 904 is different. The gripping element 903 has a recess 909 with a first recess portion 909 a and second recess portion 909 b . The first recess portion 909 a is represented by a bore to accommodate the connection portion 911 . The second recess portion 909 b is limited laterally by two wall portions, the first wall portion 23 and the second wall portion 24 . Each wall portion 23 , 24 has an elastic latch arm 25 with a latching projection 26 , projecting into the second recess portion 909 b . The attachment element 904 is accommodated with a part of the spring portion 913 between the two wall portions 23 , 24 . The latching projections 26 engage in the through opening 27 of the spring portion 913 . [0074] An eleventh embodiment of a tine 1001 is illustrated in FIGS. 20 and 21 . The embodiment differs from the tenth embodiment in that instead of the latch arms 25 and the latching projections 26 an attachment bolt 1015 , in the form of a socket pin or a screw is used. The bolt 1015 is retained in the bores 1016 in the two wall portions 1023 , 1024 of the gripping element 1003 . The bolt 1015 is passed through the through opening 1027 of the attachment element 1004 . [0075] The present disclosure has been described with reference to the preferred embodiments. Obviously, modifications and alternations will occur to those of ordinary skill in the art upon reading and understanding the preceding detailed description. It is intended that the present disclosure be construed to include all such alternations and modifications insofar as they come within the scope of the appended claims or their equivalents.
Tines ( 1 ) attached to a supporting body ( 2 ) have a gripping element ( 3 ) and a fastening element ( 4 ). The gripping element ( 3 ) has a bar-shape design and is made from plastic. The fastening element ( 4 ), made from spring steel, has a connecting section ( 11 ) connected to the gripping device ( 3 ). Also, the fastening element ( 4 ) has a fastening section ( 12 ) that fastens to the supporting body ( 2 ). An elastically resilient spring section ( 13 ) is arranged between the fastening section ( 12 ) and connecting section ( 11 ).
0
FIELD OF THE INVENTION [0001] The present invention pertains to the art of seismic surveying to monitor petroleum reservoirs, and more specifically to the joint use of linear sensors, rotational sensors, and pressure sensors in arrays of shallow monitoring wells to enhance the active seismic source and passive seismic monitoring of oil and gas field reservoirs, and the passive seismic monitoring of hydrofracturing of oil and gas wells. BACKGROUND OF THE INVENTION [0002] There is a long term trend of increasing interest in active and passive seismic monitoring in and around oil and gas fields. For a summary, see, for example, Weijers, L. Advanced Fracture Methods and Mapping , Soc. Petroleum Engineers training course (2005). The recording of seismic data on the surface of the earth, in arrays of shallow wells, and in deep boreholes has been utilized. The discrimination of compressional waves from shear waves is an integral part of applications to determine rock and fluid properties. In the monitoring of hydrofracturing of producing oil and gas wells, it can be useful to be able to discriminate between compressional and shear waves. [0003] Techniques such as described in U.S. Pat. No. 5,774,419 are used to detect seismic arrival events from background noise. Techniques such as described in U.S. Pat. No. 7,663,970 are utilized to locate seismic source events. Techniques such as described in U.S. Pat. No. 7,660,194 B2 are used to refine the seismic velocity field to enhance the location of seismic source events. Techniques such as described in U.S. Pat. No. 7,590,491 B2 are used to passively monitor production of fluids from reservoirs. [0004] Techniques for 3D and 4D seismic surveys of oil and gas fields using arrays of sensors and active seismic sources deployed on the surface are well established in commercial practice. Also, in recent practice, permanent deployments of 3C linear sensors and pressure sensors in arrays of shallow monitoring wells have become a common commercial practice over selected oil and gas fields. These deployments are used for active monitoring utilizing active seismic sources; and for passive monitoring to detect natural seismic events that may in turn be due to movement of fluids, hydrofracturing, or the like. [0005] Techniques have been devised to attempt to separate compressional and shear waves in the processing of multi-component linear motion data. These include many various well established seismic signal and image processing techniques, as well as wave propagation based processing, such as, for example that described in Sun, R. et. al., Separating P- and S-waves in prestack 3D elastic seismograms using divergence and curl, Geophysics, vol. 69, no. 1, pp. 286-297 (2004). [0006] It is well understood in many fields of physical science and engineering that a complete representation of mechanical motion requires the measurement of six degrees-of-freedom. Typically this is accomplished by measuring three orthogonal linear motions, and measuring rotations around three orthogonal axes. [0007] There is a well established technology for measurement of the linear particle motion of seismic wavefields in the earth. Many commercial sensors exist to measure particle velocity or particle acceleration along one, or up to three, linear axes, utilizing various physical concepts to accomplish the measurements. It is most common to utilize measurements of the vertical particle motion. [0008] There is an evolving commercial technology for measurement of the rotational particle motion of seismic wavefields in the earth. Early technology is represented by, for example, U.S. Pat. No. 3,407,305 and U.S. Pat. No. 4,603,407. Newer technology is represented by, for example, sensors such as those commercially offered by MetTech (model Metr-3), June, 2010, http://www.mettechnology.com/ and Eentec (models R-1 and R-2), June 2010, http://www.eentec.com/R-s_data_new.htm. U.S. Pat. No. 7,516,660 B2 describes MetTech sensor technology. U.S. Pat. No. 7,474,591 B2 describes technology to measure rotational data from differences of linear data. [0009] Seismic rotational motion is commonly understood to be the vector curl of the infinitesimal displacement field. The existing rotational sensors are understood to measure the components of this vector curl. [0010] The utility of rotational seismic measurements is appreciated in earthquake and regional crustal seismology, as discussed, for example, in Lee, W., et. al., Rotational Seismology and Engineering Applications, Bull. Seismological Society of America, vol. 99, no. 2B, supplement (May 2009). [0011] The free surface of the earth adds a significant complicating effect to the separation of compressional waves from shear waves. This is largely due to conversion between compressional and shear waves at the free surface. [0012] Elastic seismic wave theory is well understood, particularly for a linear homogeneous isotropic earth. The surface of the earth is approximately a stress free surface. The effect of the free surface on elastic waves is well understood, as described in technical references such as Aki, K. and Richards, P., Quantitative Seismology , University Science Books (2002) or Stein, S. & Wysession, M., An Introduction to Seismology, Earthquakes, and Earth Structures , Blackwell Publishing (2003). [0013] Prior art for separation of compressional and shear waves includes U.S. Pat. No. 2,657,373 which utilizes horizontal phase velocity as an input parameter. [0014] Prior art to determine the direction of propagation of compressional waves includes utilizing a pressure sensor and a vector component of linear motion in the direction of the propagation. This is commonly used, as for example, in the recording and processing of Ocean Bottom Seismic (OBS) data. [0015] Prior art to determine direction of propagation of known shear waves includes U.S. Pat. No. 4,446,541 which is applicable at a depth away from the free surface. This utilizes a combination of one linear motion vector component and one rotational vector component, both said vector components being orthogonal to the direction of propagation, and to each other. OBJECT OF THE INVENTION [0016] The object of the present invention is to improve the ability to separate compressional (P) and shear (S) seismic waves, and to enhance the determination of their propagation direction, by using a novel combination and deployment of rotational motion sensors, linear motion sensors, and pressure sensors, in an array of shallow monitoring wells, to yield a more complete description of seismic particle motion with minimal deleterious effects of the near surface. SUMMARY OF THE INVENTION [0017] The invention includes, in its many aspects and embodiments, a method to enhance the discrimination of compressional waves and shear waves in seismic data recorded by sensors located below the free surface of the earth in shallow monitoring wells. More particularly, the method comprises: recording the linear particle motion, preferably in three orthogonal directions at each sensor location; recording the rotational motion, preferably around three orthogonal axes at each sensor location; recording pressure at each sensor location; and utilizing the combination of the linear motion, rotational motion, and pressure to separate signals due to compressional and shear waves. BRIEF DESCRIPTION OF THE DRAWINGS [0018] FIG. 1 is a diagrammatic view of the linear motion and rotational motion of a representative elemental volume of the earth. [0019] FIG. 2 is a diagrammatic view of oil and gas production, or of a hydrofracturing project, for a reservoir at a particular depth, along with seismic monitoring in an array of shallow monitoring wells utilizing multi-component rotational sensors, multi-component linear sensors, and pressure sensors. [0020] FIG. 3 is a diagrammatic representation of the seismic signals for one conceptual seismic event, either reflected from the reservoir zone of interest, or seismically activated in and near the reservoir zone of interest, depicting the compressional and shear seismic waves on multi-component rotational sensors, multi-component linear sensors, and a pressure sensor, all of said sensors being co-located. DETAILED DESCRIPTION OF THE INVENTION [0021] The particle motion of a representative elemental volume 101 of the earth is as depicted in FIG. 1 . A Cartesian coordinate system is utilized, but those skilled in the art will recognize that various alternate equivalent coordinate systems and representations of particle motion may be utilized. The complete particle motion is comprised of three linear motions, 102 - 104 , and three rotational motions, 105 - 107 . A right-hand rule for axes and rotation sign conventions is arbitrarily chosen for use throughout the description of the present invention. [0022] Rotational seismic data measured by rotational seismic motion sensors may be directly related to the vector curl of the displacement wavefield, u , often with a factor of ½. Alternatively, measurements may be made of the time derivative of this rotational displacement which is angular velocity, also known as the angular rate, as is done in some commercially available rotational seismic sensors; or of the second time derivative of this rotational displacement which is angular acceleration. It will be understood by those skilled in the art that the use of various time derivatives does not affect the present invention so long as the same time derivative is consistently utilized for both the linear and rotational motion measurements. [0023] FIG. 2 diagrammatically shows a configuration in the field for recording data. Typically there will be one or more oil and/or gas wells 201 penetrating a target reservoir or zone of interest 202 . Compressional 203 and shear 204 seismic waves will be transmitted upwards. Said seismic waves may conceptually be due to one or more causes. These waves may include reflections of energy emitted by an active source; or may be emitted due to induced hydrofracturing around the well 201 ; or may be due to fluid flow during production of the reservoir 202 . [0024] Those skilled in the art will appreciate that the compressional 203 and shear 204 waves depicted in FIG. 2 may possibly include some or all of the various forms of elastic seismic energy that are possible in the earth, including body waves, converted waves, various up and/or down going waves, multiply reflected waves, waves in wave guides, surface attached modes of propagation, and dispersed waves. [0025] There typically will be an array of shallow monitoring wells 205 located in a region around the well 201 and geologic target of interest 202 . There typically will be one or more sensor deployment locations 206 at one or more depths in the shallow monitoring wells. [0026] Each sensor deployment location 206 will typically include up to three Cartesian linear motion sensors, up to three Cartesian rotational motion sensors; and a pressure measurement sensor. This sensor configuration at a sensor deployment location may be referred to as a seven-component sensor. [0027] The use of the present novel combination and deployment of rotational, linear, and pressure sensors allows for the separation of compressional (P) waves from shear (S) waves, as well as for the determination of direction for each wave. [0028] Consider the homogeneous isotropic equation of motion for a linear elastic continuum away from any boundaries such as the free surface (e.g., Aki & Richards, p. 35; or Stein & Wysessions, 2003, eq. (10), p. 53): [0000] ρ ü =(λ+μ)∇(∇• u )+μ∇ 2 μ   (1) [0000] where: ρ is the density u is the particle displacement vector; and double dots represent second time derivative λ is the first Lame constant μ is the second Lame constant, or shear modulus ∇ is the vector Del operator [0029] Those skilled in the art will recognize that we may now successively take the vector divergence and vector curl of this equation (1) to separate the infinitesimal displacement, u , into compressional waves at compressional wave velocity, and into shear waves at shear wave velocity. [0030] First, take the divergence of equation (1) and interchange the order of some operations to see that: [0000] ρ(∇•μ)=(λ+μ)∇•∇(∇• u )+μ∇ 2 (∇• u )  (2) [0000] Note that the dilation, θ, is defined as: [0000] θ ≡ ∇ · u _ ≡ e xx + e yy + e zz ≡ ∂ u ∂ x + ∂ v ∂ y + ∂ w ∂ x ( 3 ) [0000] where e's are components of the linear strain tensor, and u, v, w are the vector components of the displacement vector. Utilizing equation (3) in equation (2) it is seen that: [0000] ρ{umlaut over (θ)}=(λ+2μ)∇ 2 θ  (4) [0000] which is recognized as a scalar wave equation for dilation, θ, traveling with compressional wave velocity, v p , given as: [0000] v p = λ + 2   μ ρ ( 5 ) [0031] Thus a sensor that detects dilation will selectively detect waves traveling at the compressional wave velocity. This is as described by equations (3), (4), and (5). [0032] Second, take the curl of equation (1), interchange the order of some operations, and note that the curl of a grad vanishes to see that: [0000] ρ∂ n (∇× u )=μ∇ 2 (∇× u )  (6) [0000] which is recognized as a vector wave equation for the rotational seismic signal which is the vector curl of displacement, [0000] ( ∇ × u _ ) ≡ [ 0 - ∂ z ∂ y ∂ z 0 - ∂ x - ∂ y ∂ x 0 ]  [ u v w ] ( 7 ) [0000] traveling with shear wave velocity, v s , given as: [0000] v s = μ ρ ( 8 ) [0033] Thus a sensor that detects rotation, which is related to curl of displacement, will selectively detect waves traveling at the shear wave velocity. This is as described by equations (6), (7), and (8). [0034] In general, the pressure signal will be non-zero for compressional waves; and zero for shear waves. [0035] In general, the rotational signals will be zero for compressional waves; and non-zero for shear waves. [0036] In general, the components, u, v, w of the linear displacement vector will be non-zero for both compressional and shear waves. [0037] Those skilled in the art will recognize that there may be many complications in the seismic signals measured within any particular shallow monitoring well. These complications can depend on many factors, including but not limited to variations in elastic parameters and density around the shallow monitoring well; whether the shallow monitoring well is cased; whether it is cemented; how the sensors are coupled to the wall of the shallow monitoring well; whether the shallow monitoring well is filled with air, brine, sand, gravel, cement, or other material. Additionally there may be other modes of seismic wave propagation detected, including but not limited to tube waves, Rayleigh waves detected at depth, and potentially other waves. [0038] FIG. 3 shows typical expected signals from the several sensors at one sensor deployment location 206 for a compressional 308 wave and a shear 309 wave. Linear motion is typically sensed by particle velocity or particle acceleration sensors. Up to three Cartesian linear motion components are typically recorded as depicted by traces 301 - 303 . Rotational motion is typically sensed as angular velocity or angular acceleration. Up to three Cartesian rotational motion components are typically recorded as depicted by traces 304 - 306 . Pressure is typically recorded from a hydrophone as depicted by trace 307 . It is noted that there are characteristic variations in each of these seven-components that characterize compressional 308 vs. shear 309 wave arrivals. All prior art in signal processing and wavefield processing of seismic data may be utilized as necessary to enhanced desired signals. Those skilled in the art will appreciate that wavelet shapes and phases shown in FIG. 3 are diagrammatic only and will vary depending on many factors. [0039] The effect of the free surface is such as to typically cause the conversion between compressional waves and shear waves. This conversion effect complicates the ability to separate compressional waves and shear waves. Corrections for these effects can be utilized in data processing as described, for example, in Aki & Richards (2002), particularly pp. 184-185. However, these free surface corrections are dependent upon knowledge of near surface velocities and upon a relatively homogeneous nature for the near surface. This may not be a typical situation because it is commonly understood that near surface geology can be particularly variable. Deployment of sensors in shallow monitoring wells offers a direct mechanism to avoid the deleterious effects of the free surface and variable near surface geology. [0040] Those skilled in the art will recognize the novelty of the concepts engendered in recording the combination of rotational, linear, and pressure data in a deployment away from the free surface of the earth in an array of shallow monitoring wells. Dilational energy described in equation (3) propagates as governed by equation (4) at a compressional velocity given by equation (5). It is preferentially detected by pressure and linear motion sensors. The curl wavefield described in equation (7) propagates as governed by equation (6) at a shear velocity given by equation (8). It is preferentially detected by rotational and linear motion sensors. [0041] The deployment of the rotational, linear, and pressure sensors in an array of shallow monitoring wells also often has additional advantages which are not part of the present invention. Deployment in a shallow monitoring well can lower the seismic noise levels below those experienced at the free surface. Also, deployment in shallow monitoring wells below the water table allows for the more effective use of pressure sensors. [0042] Deployment of rotational, linear, and pressure sensors in shallow monitoring wells may often be advantageously done with sensors at several depth levels. Deployment of sensors at multiple levels allows for additional processing of the data. For example, compressional vs. shear waves may be separated; and upgoing vs. downgoing waves may be separated by well known techniques such as those commonly commercially used in Vertical Seismic Profiles, or as described, for example, in U.S. Pat. No. 4,446,541. [0043] In a preferred embodiment, there typically may be an array of shallow monitoring wells spaced more or less regularly at intervals on the order of several hundred meters horizontally apart, covering an area that extends horizontally a distance that is the same order of magnitude as the depths of interest for the reservoir or geologic target to be monitored. The shallow monitoring wells may typically be of a depth of at least a few meters, up to a depth of a few hundred meters. The preferred embodiment may utilize an array of wells on the order of 100 meters deep, with sensor deployment locations 206 typically at depths of 25 m, 50, 75 m, and 100 m. Each sensor deployment location 206 typically will sense three components of linear motion, three components of rotational motion, and pressure. The shallow monitoring wells may typically be filled with sand, drilling cuttings, and/or small gravel; and be saturated with brine or water. Said deployment is considered permanent. Said deployment may be used for multiple purposes, including 3D and 4D seismic with active seismic sources; passive monitoring of hydrofracturing of oil and gas wells; and/or passive monitoring of fluid flow in reservoirs. [0044] In another embodiment, the seven component sensors may be deployed in brine or water filled shallow monitoring wells, and coupled to the wall of these shallow wells with temporarily deployable locking arms. Said deployment is intended to be retrievable and is considered non-permanent. [0045] In another embodiment the deployment of the array of shallow monitoring wells will utilize a geometry suitable for location of fractures induced by hydrofracturing. Said geometry shall include shallow monitoring wells at various azimuths and various distances from the deep oil and gas well being hydrofractured. This embodiment may utilize the detection of both compressional and shear waves, and may possibly utilize t-s and t-p arrival times to solve for the distance from the sensor to the fractures of the seismic source. T-s and t-p are understood to be the arrival times for compressional (P) and shear (S) waves, both emanating from the same seismic event or source. [0046] In another embodiment the deployment of the shallow monitoring wells will utilize a geometry suitable for determination of double couple shear seismic source mechanism as is commonly understood in earthquake seismology. Said geometry shall include shallow monitoring wells at various azimuths, and may include relatively longer horizontal distances from the reservoir zone of interest. This embodiment may ideally benefit from detection and separation of both compressional and shear waves at all azimuths horizontally from the geologic target of interest, such as to enhance the determination of any radiation patterns. [0047] In another embodiment the deployment of the shallow monitoring wells will utilize a geometry suitable to analyze the polarization of three-component linear motion measurements, using techniques that are well known. These techniques may be used, for example, to determine the direction of arrival of compressional seismic waves, and thus to determine to location of the seismic event by utilizing sensor deployments at multiple locations. [0048] The above three embodiments: utilizing t-p and t-s arrival times to determine distances to seismic source events; utilizing the analysis of shear double couple source mechanisms; and utilizing the determination of compressional wave arrival direction; all require, or benefit from, the use of three or more shallow monitoring wells. The locations of the three or more shallow monitoring wells may be optimized based on various attributes such as azimuth and horizontal distance from subsurface areas of interest. [0049] A limited number of embodiments have been described herein. Those skilled in the art will recognize other embodiments within the scope of the claims of the present invention.
The present invention provides a technique to separate compressional seismic waves from shear seismic waves and to determine their direction of propagation to enhance the seismic monitoring oil and gas reservoirs and the seismic monitoring of hydrofracturing in oil and gas wells. The invention utilizes various combinations of multi-component linear seismic sensors, multi-component rotational seismic sensors, and pressure sensors. Sensors are jointly deployed in arrays of shallow monitoring wells to avoid the complicating effects of the free surface of the earth. The emplacement of sensors in the shallow monitoring wells may be permanent. The method has a wide range of application in oil and gas exploration and production. This abstract is not intended to be used to interpret or limit the claims of this invention.
4
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a Division of copending application Ser. No. 10/946,948 filed Sep. 22, 2004, the contents of which are hereby incorporated by reference in its entirety. FIELD OF THE INVENTION [0002] This invention relates to catalytic hydrocarbon conversion, and more specifically to the use of an activated alumina guard bed for extending the life of a transalkylation catalyst used in reacting aromatic C 9 + compounds with toluene to produce xylenes. By decomposing contaminant species present in transalkylation feed aromatics, such as chlorides, the guard bed reduces coke formation on the transalkylation catalyst. BACKGROUND OF THE INVENTION [0003] Xylene isomers, para-xylene, meta-xylene and ortho-xylene, are important intermediates which find wide and varied application in chemical syntheses. Para-xylene upon oxidation yields terephthalic acid, which is used in the manufacture of synthetic textile fibers and resins. Meta-xylene is used in the manufacture of plasticizers, azo dyes, wood preservers, etc. Ortho-xylene is feedstock for phthalic anhydride production. [0004] Xylene isomers from catalytic reforming or other sources generally do not match demand proportions as chemical intermediates, and further comprise ethylbenzene, which is difficult to separate or to convert. Para-xylene in particular is a major chemical intermediate with rapidly growing demand, but amounts to only 20 to 25% of a typical C 8 aromatics stream. Among the aromatic hydrocarbons, the overall importance of the xylenes rivals that of benzene as a feedstock for industrial chemicals. Neither the xylenes nor benzene are produced from petroleum by the reforming of naphtha in sufficient volume to meet demand, and conversion of other hydrocarbons is necessary to increase the yield of xylenes and benzene. Often toluene (C 7 ) is dealkylated to produce benzene (C 6 ) or selectively disproportionated to yield benzene and C 8 aromatics from which the individual xylene isomers are recovered. [0005] A current objective of many aromatics complexes is to increase the yield of xylenes and to de-emphasize benzene production. Demand is growing faster for xylene derivatives than for benzene derivatives. Refinery modifications are being effected to reduce the benzene content of gasoline in industrialized countries, which will increase the supply of benzene available to meet demand. A higher yield of xylenes at the expense of benzene thus is a favorable objective, and processes to transalkylate C 9 and heavier aromatics with benzene and toluene have been commercialized to obtain high xylene yields. [0006] U.S. Pat. No. 4,857,666 discloses a transalkylation process over mordenite and incorporating a metal modifier into the catalyst. [0007] U.S. Pat. No. 5,763,720 discloses a transalkylation process for conversion of C 9 + into mixed xylenes and C 10 + aromatics over a catalyst containing zeolites including amorphous silica-alumina, MCM-22, ZSM-12, and zeolite beta, where the catalyst further contains a Group VIII metal such as platinum. [0008] U.S. Pat. No. 6,060,417 discloses a transalkylation process using a catalyst based on mordenite with a particular zeolitic particle diameter and having a feed stream limited to a specific amount of ethyl containing heavy aromatics. The catalyst contains nickel or rhenium metal. [0009] U.S. Pat. No. 6,486,372 B1 discloses a transalkylation process using a catalyst based on dealuminated mordenite with a high silica to alumina ratio that also contains at least one metal component. [0010] U.S. Pat. No. 6,613,709 B1 discloses a catalyst for transalkylation comprising zeolite structure type NES and metals such as rhenium, indium, or tin. [0011] U.S. Pat. No. 6,740,788 B1 discloses an integrated process for aromatics production enabled by a stabilized transalkylation catalyst having a metal function. [0012] Many types of supports and elements have been disclosed for use as catalysts in processes to transalkylate various types of aromatics into xylenes, but there exists a problem presented by transalkylation aromatics feed stream contaminants, whereby such contaminants reduce the useful catalyst cycle life. Applicants have found a solution with the application of a contaminant removal guard bed that extends catalyst life, resulting in a more stable aromatics transalkylation process that will be more profitable over the catalyst life cycle by requiring less frequent down time for regeneration to remove deactivating coke deposits. SUMMARY OF THE INVENTION [0013] A principal object of the present invention is to provide a process of using a guard bed in front of a transalkylation catalyst, the guard bed catalyst system itself, and a reactor configuration for the transalkylation of alkylaromatic hydrocarbons into xylenes. More specifically, the present invention is directed to improved conversion of aromatic hydrocarbons by removal of feed contaminants. This invention is based on the discovery that feed contaminants removed in a guard bed prior to contacting the feed with a transalkylation catalyst demonstrates a process showing increased stability of xylene production under transalkylation conditions. [0014] Accordingly, a broad embodiment of the present invention is a process for contacting an aromatics stream containing a contaminant material with a guard bed and then with a catalyst suitable for transalkylation of the aromatics into xylenes. In another embodiment, the present invention is a catalyst system combining guard bed material with catalyst material. In yet another embodiment, the present invention is a reactor configuration providing an apparatus for situating a guard bed before a catalyst bed. [0015] These, as well as other objects and embodiments will become evident from the following detailed description of the invention. BRIEF DESCRIPTION OF THE DRAWING [0016] The FIGURE shows the effect of guard bed addition upon catalyst activity for transalkylation of C 7 , C 9 , and C 10 aromatics at a level of about 50 wt-% conversion while producing C 8 aromatics. The slope of the weighted average catalyst bed temperature (WABT) is proportional to stability, with a flatter slope representing greater stability. DETAILED DESCRIPTION OF THE INVENTION [0017] The feed stream to the present process generally comprises alkylaromatic hydrocarbons of the general formula C 6 H (6-n) R n , where n is an integer from 0 to 6 and R is CH 3 , C 2 H 5 , C 3 H 7 , or C 4 H 9 , in any combination. Suitable alkylaromatic hydrocarbons include, for example but without so limiting the invention, benzene, toluene, ethylbenzene, ethyltoluenes, propylbenzenes, tetramethylbenzenes, ethyl-dimethylbenzenes, diethylbenzenes, methylpropylbenzenes, ethylpropylbenzenes, triethylbenzenes, di-isopropylbenzenes, and mixtures thereof. The feed stream may comprise lower levels of ortho-xylene, meta-xylene, and para-xylene that are the desired products of the present process. [0018] The feed stream also may comprise naphthalene and other C 10 and C 11 aromatics and suitably is derived from one or a variety of sources. Polycyclic aromatics such as the bi-cyclic components including naphthalene, methylnaphthalene, are permitted in the feed stream of the present invention. Indane, which is also referred to as indan or indene, is meant to define a carbon number nine aromatic species with one carbon six ring and one carbon five ring wherein two carbon atoms are shared. Naphthalene is meant to define a carbon number ten aromatic species with two carbon six rings wherein two carbon atoms are shared. Polycyclic aromatics may also be present, even in substantial amounts such as greater than about 0.5 wt-% of the feed stream. [0019] Feed components may be produced synthetically, for example, from naphtha by catalytic reforming or by pyrolysis followed by hydrotreating to yield an aromatics-rich product. The feed stream may be derived from such product with suitable purity by extraction of aromatic hydrocarbons from a mixture of aromatic and nonaromatic hydrocarbons and fractionation of the extract. For instance, aromatics may be recovered from reformate. Reformate may be produced by any of the processes known in the art. The aromatics then may be recovered from reformate with the use of a selective solvent, such as one of the sulfolane type, in a liquid-liquid extraction zone. The recovered aromatics may then be separated into streams having the desired carbon number range by fractionation. When the severity of reforming or pyrolysis is sufficiently high, extraction may be unnecessary and fractionation may be sufficient to prepare the feed stream. Such fractionation typically includes at least one separation column to control feed end point. [0020] The feed heavy-aromatics stream, characterized by C 9 + aromatics (or A 9 +), permits effective transalkylation of light aromatics such as benzene and toluene with the heavier C 9 + aromatics to yield additional C 8 aromatics that are preferably xylenes. The heavy-aromatics stream preferably comprises at least about 90 wt-% total aromatics; and may be derived from the same or different known refinery and petrochemical processes as the benzene and toluene, and/or may be recycled from the separation of the product from transalkylation. When the feed is predominantly heavy-aromatics then de-alkylation or hydrocracking of the heavy aromatics to lighter aromatics may also occur and provide additional intermediate feed components that may further convert to benzene, toluene or xylene. [0021] Feed contaminants may be present in small amounts, such as amounts less than 100 wt-ppm, and more generally are present in amounts less than 10 wt-ppm. Feed contaminants include, but are not limited to, oxygen, chloride, sulfur, and nitrogen species. [0022] According to the process of the present invention, the feed mixture of heavy A 9 +, toluene, and feed contaminants is contacted with an alumina guard bed and then with a transalkylation catalyst of the type hereinafter described in a two zone system. The first zone is the guard bed zone, while the second zone is the transalkylation zone. The guard bed may be contained in a separate vessel from the transalkylation reactor of the types hereinafter described, or it may be contained within the same reactor vessel as the transalkylation catalyst. Better flow distribution is achieved when catalyst support materials, for example inert ceramic objects, are placed in upstream and downstream positions from the alumina guard bed material. Therefore, when the two zones are placed in separate vessels appropriate piping is used to serially connect them together. When the two zones are in the same vessel, then the zones are generally layered on top or next to each other such that contacting with hydrocarbons occurs sequentially and under the same conditions. Alternatively, the zones may be intermixed, such that physical mixtures of guard bed and transalkylation particles are combined together on a bulk basis where separate particles are intermingled, or on a particulate basis where effective guard bed material is directly composited alongside catalyst material. Finally, such zones are herein described as in fluid communication with each other by being present in the same vessel, or connected in series with separate vessels and piping there between for transference of the alumina guard bed product to the transalkylation reactor. [0023] The hydrocarbon feed is passed through an alumina guard bed and produces an alumina guard bed product stream. The alumina guard bed product stream is then preferably transalkylated in the vapor phase and in the presence of hydrogen. If transalkylated in the liquid phase, then the presence of hydrogen is optional. If present, free hydrogen is associated with the feed stream and recycled hydrocarbons in an amount of from about 0.1 moles per mole of alkylaromatics up to 10 moles per mole of alkylaromatic. This ratio of hydrogen to alkylaromatic is also referred to as hydrogen to hydrocarbon ratio. The transalkylation reaction preferably yields a product having increased xylene content. [0024] The feed to alumina guard bed zone usually first is heated by indirect heat exchange against the effluent of the transalkylation reaction zone and then is heated to reaction temperature by exchange with a warmer stream, steam or a furnace. The feed then is passed through the guard bed zone and then through a reaction zone, which may comprise one or more individual reactors. The use of a single transalkylation reaction vessel having a fixed cylindrical bed of catalyst is preferred, but other reaction configurations utilizing moving beds of catalyst or radial-flow reactors may be employed if desired. Passage of the combined feed through the reaction zone effects the production of an effluent stream comprising unconverted feed and product hydrocarbons including C 8 aromatic compounds. This effluent is normally cooled by indirect heat exchange against the stream entering the reaction zone and then further cooled through the use of air or cooling water. The effluent may be passed into a stripping column in which substantially all C 5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process. An aromatics-rich stream is recovered as net stripper bottoms, which is referred to herein as the transalkylation effluent. [0025] To effect a transalkylation reaction, the present invention incorporates a transalkylation catalyst in at least one zone, but no limitation is intended in regard to a specific catalyst other than such catalyst must possess a solid-acid component and a metal component. Conditions employed in the transalkylation zone normally include a temperature of from about 200° to about 540° C. The transalkylation zone is operated at moderately elevated pressures broadly ranging from about 100 kPa to about 6 MPa absolute. The transalkylation reaction can be effected over a wide range of space velocities. Weight hourly space velocity (WHSV) generally is in the range of from about 0.1 to about 20 hr −1 . Such transalkylation conditions are similar to the alumina guard bed conditions. [0026] The transalkylation effluent is separated into a light recycle stream, a mixed C 8 aromatics product and a heavy recycle stream. The mixed C 8 aromatics product can be sent for recovery of para-xylene and other valuable isomers. The light recycle stream may be diverted to other uses such as to benzene and toluene recovery, but alternatively is recycled partially to the transalkylation zone or the alumina guard bed zone. The heavy recycle stream contains substantially all of the C 9 and heavier aromatics and may be partially or totally recycled to the transalkylation reaction zone or the alumina guard bed zone as well. [0027] Several types of alumina guard bed materials may be used in the present invention including gamma alumina, theta alumina, and other alumina phase materials having high surface areas generally greater than about 25 m 2 /g, with gamma phase alumina being preferred. Alpha phase alumina generally has a low surface area is not generally suitable for the present invention. Gamma phase alumina is obtained by aging and calcining aluminum trihydroxides [Al(OH) 3 ], aluminum oxyhydroxides [AlOOH], transition aluminas derived from Al(OH) 3 and AlOOH, and, optionally metal promoters with any combination thereof. Generally, alumina will be precipitated from an aqueous solution containing Al+3 ions. Such precipitate is aged, filtered, washed and dried. During these operations alumina passes through various phases. Typically, the initial precipitation leads to a gel with minute crystals of boehmite. The gel can be aged at a temperature of about 80° C. into crystalline boehmite that forms gamma-phase alumina upon a calcination temperature of about 600° C. Gamma phase alumina has a high surface area, generally between 100 and 300 m 2 /g. Upon heating to higher temperatures of about 1100° C. or more, the alumina moves through theta or delta phases to becomes alpha phase and has a low surface area less than 25 m 2 /g and commonly less than 1 m 2 /g. [0028] Several types of transalkylation catalysts that may be used in the present invention are based on a solid-acid material combined with an optional metal component. Suitable solid-acid materials include all forms and types of mordenite, mazzite (omega zeolite), beta zeolite, ZSM-11, ZSM-12, ZSM-22, ZSM-23, MFI type zeolite, NES type zeolite, EU-1, MAPO-36, MAPSO-31, SAPO-5, SAPO-11, SAPO-41, and silica-alumina or ion exchanged versions of such solid-acids. For example, in U.S. Pat. No. 3,849,340 a catalytic composite is described comprising a mordenite component having a SiO 2 /Al 2 O 3 mole ratio of at least 40:1 prepared by acid extracting Al 2 O 3 from mordenite prepared with an initial SiO 2 /Al 2 O 3 mole ratio of less than 30:1 and a metal component selected from copper, silver and zirconium. Refractory inorganic oxides, combined with the above-mentioned and other known catalytic materials, have been found useful in transalkylation operations. For instance, silica-alumina is described in U.S. Pat. No. 5,763,720. Crystalline aluminosilicates have also been employed in the art as transalkylation catalysts. ZSM-12 is more particularly described in U.S. Pat. No. 3,832,449. Zeolite beta is more particularly described in Re. 28,341 (of original U.S. Pat. No. 3,308,069). A favored form of zeolite beta is described in U.S. Pat. No. 5,723,710, which is incorporated herein by reference. The preparation of MFI topology zeolite is also well known in the art. In one method, the zeolite is prepared by crystallizing a mixture containing an alumina source, a silica source, an alkali metal source, water and an alkyl ammonium compound or its precursor. Further descriptions are in U.S. Pat. No. 4,159,282, U.S. Pat. No. 4,163,018, and U.S. Pat. No. 4,278,565. The synthesis of the Zeolite Omega is described in U.S. Pat. No. 4,241,036. ZSM intermediate pore size zeolites useful in this invention include ZSM-5 (U.S. Pat. No. 3,702,886); ZSM-11 (U.S. Pat. No. 3,709,979); ZSM-12 (U.S. Pat. No. 3,832,449); ZSM-22 (U.S. Pat. No. 4,556,477); ZSM-23 (U.S. Pat. No. 4,076,842). European Patent EP 0378916 B1 describes NES type zeolite and a method for preparing NU-87. The EUO structural-type EU-1 zeolite is described in U.S. Pat. No. 4,537,754. MAPO-36 is described in U.S. Pat. No. 4,567,029. [0029] MAPSO-31 is described in U.S. Pat. No. 5,296,208 and typical SAPO compositions are described in U.S. Pat. No. 4,440,871 including SAPO-5, SAPO-11 and SAPO-41. Typically, the solid-acid component will be present in the catalyst in an amount from about 1 to about 99 wt-%. [0030] A refractory binder or matrix is optionally utilized to facilitate fabrication of the catalyst, provide strength and reduce fabrication costs. The binder should be uniform in composition and relatively refractory to the conditions used in the process. Suitable binders include inorganic oxides such as one or more of alumina, magnesia, zirconia, chromia, titania, boria, thoria, phosphate, zinc oxide and silica. Alumina is a preferred binder. Typically the binder may be present in about 5 to about 95 wt-% of the catalyst when it is used. [0031] The catalyst also may contain a metal component. One preferred metal component is a Group VIII (IUPAC 8-10) metal that includes nickel, iron, cobalt, and platinum-group metal. Of the platinum group, i.e., platinum, palladium, rhodium, ruthenium, osmium and iridium, platinum is especially preferred. Another preferred metal component is rhenium and it will be used for the general description that follows. This metal component may exist within the final catalytic composite as a compound such as an oxide, sulfide, halide, or oxyhalide, in chemical combination with one or more of the other ingredients of the composite. The rhenium metal component may be incorporated in the catalyst in any suitable manner, such as coprecipitation, ion-exchange, co-mulling or impregnation. The preferred method of preparing the catalyst involves the utilization of a soluble, decomposable compound of rhenium metal to impregnate the carrier material in a relatively uniform manner. Typical rhenium compounds which may be employed include ammonium perrhenate, sodium perrhenate, potassium perrhenate, potassium rhenium oxychloride, potassium hexachlororhenate (IV), rhenium chloride, rhenium heptoxide, perrhenic acid, and the like compounds. Preferably, the compound is ammonium perrhenate or perrhenic acid because no extra steps may be needed to remove any co-contaminant species. This component may be present in the final catalyst composite in any amount which is catalytically effective, generally comprising about 0.01 to about 2 wt-% of the final catalyst calculated on an elemental basis. [0032] The catalyst may optionally contain additional metal components along with those metal components discussed above or include additional metal components instead of those metal components in their entirety. Additional metal components of the catalyst include, for example, tin, germanium, lead, and indium and mixtures thereof. Catalytically effective amounts of such additional metal components may be incorporated into the catalyst by any means known in the art. A preferred amount is a range of about 0.01 to about 2.0 wt-% on an elemental basis. [0033] One shape of the catalyst of the present invention is a cylinder. Such cylinders can be formed using extrusion methods known to the art. Another shape of the catalyst is one having a trilobal or three-leaf clover type of cross section that can be formed by extrusion. Another shape is a sphere that can be formed using oil-dropping methods or other forming methods known to the art. [0034] At least one oxidation step may be used in the preparation of the catalyst. The conditions employed to effect the oxidation step are selected to convert substantially all of the metallic components within the catalytic composite to their corresponding oxide form. The oxidation step typically takes place at a temperature of from about 370° to about 650° C. An oxygen atmosphere is employed typically comprising air. Generally, the oxidation step will be carried out for a period of from about 0.5 to about 10 hours or more, the exact period of time being that which is required to convert substantially all of the metallic components to their corresponding oxide form. This time will, of course, vary with the oxidation temperature employed and the oxygen content of the atmosphere employed. [0035] In preparing the catalyst, a reduction step may be employed. The reduction step is designed to reduce substantially all of the metal components to the corresponding elemental metallic state and to ensure a relatively uniform and finely divided dispersion of this component throughout the catalyst. [0036] Finally, the catalytic composite is subjected to an optional sulfur treatment or pre-sulfiding step. The sulfur component may be incorporated into the catalyst by any known technique. Any one or a combination of in situ and/or ex situ sulfur treatment methods is preferred. The resulting catalyst mole ratio of sulfur to rhenium is preferably from about 0.1 to less than about 1.5. EXAMPLES [0037] The following examples are presented only to illustrate certain specific embodiments of the invention, and should not be construed to limit the scope of the invention as set forth in the claims. There are many possible other variations, as those of ordinary skill in the art will recognize, within the scope of the invention. Example 1 [0038] A transalkylation catalyst comprising mordenite was prepared for comparative pilot-plant testing by the forming process called extrusion. Typically, 2500 g of a powder blend of 25 wt-% alumina (commercially available under the trade names CATAPAL B and/or VERSAL 250) and 75 wt-% mordenite (commercially available under the trade name ZEOLYST CBV-21A) was added to a mixer. A solution was prepared using 10 g nitric acid (67.5 wt-% HNO 3 ) with 220 g deionized water and the solution was stirred. The solution was added to the powder blend in the mixer, and mulled to make dough suitable for extrusion. The dough was extruded through a die plate to form cylindrically shaped (0.08 cm diameter) extrudate particles. The extrudate particles were calcined at about 565° C. with 15 wt-% steam for 2 hours. [0039] The catalyst was finished using the extrudate particles and an evaporative impregnation with rhenium metal by using an aqueous solution of ammonium perrhenate (NH 4 ReO 4 ). The impregnated base was calcined in air at 540° C. for 2 hours and resulted in a metal level of 0.15 wt-% rhenium. Next the catalyst was reduced for 12 hours in substantially dry hydrogen at 500° C. Example 2 [0040] The catalyst was tested for aromatics transalkylation ability in a pilot plant using an aromatics feed blend of C 7 , C 9 , and C 10 aromatics to demonstrate effectiveness of using an alumina guard bed to remove contaminant chlorides when producing C 8 aromatics. The feed properties are listed in the table below. Feed Wt-% Non Aromatics 0.11 Benzene 0.00 Toluene 44.33 Ethylbenzene 0.01 Mixed Xylenes 0.37 Propylbenzene 3.98 Ethyltoluene 20.64 Trimethylbenzene 17.90 DEB + C10A 3.74 Ethyl Xylenes 5.21 Tetramethylbenzene 1.41 Butylbenzene 0.40 Indane 1.22 C11+ 0.67 Total 100.0 [0041] Methylene chloride was also present in the feed at an amount of 3.0 wt-ppm. [0042] The test consisted of loading a vertical down-flow reactor with 60 cc catalyst located below 240 cc alumina particles. Two types of alumina particles were loaded in two different tests. First, a gamma-phase alumina oxide (obtained by calcining crystalline boehmite at approximately 600° C.) having 185 m 2 /g surface area was loaded in Run A. Second, commercially available corundum, alpha-phase aluminum oxide with 0.83 m 2 /g surface area was loaded in Run B. [0043] The loaded reactors were contacted with the feed at 2860 kPa abs (400 psig) under a space velocity (WHSV) of 4 hr −1 and hydrogen to hydrocarbon ratio (H 2 /HC) of 2. A conversion level of about 50 wt-% of feed aromatics was achieved during the initial part of testing. The Figure shows the effect of guard bed addition upon catalyst activity for transalkylation of C 7 , C 9 , and C 10 aromatics at a level of about 50 wt-% conversion while producing C 8 aromatics. The slope of the weighted average catalyst bed temperature (WABT) is related to stability where the flatter slope represents more stable operation and where higher slope represents less stability and increased catalyst deactivation. Run B, with the alpha alumina guard bed, also indicates a time period wherein the hydrogen to hydrocarbon ratio was increased from 2:1 to 3:1, without approaching the stability of Run A, with the gamma alumina guard bed. [0044] The data showed that the addition of a high surface area gamma phase alumina guard bed improved the stability over a comparable low surface area alumina phase guard bed. Even under conditions of increased hydrogen to hydrocarbon ratio, the stability difference persisted. After testing, the alumina and catalyst chloride contents were analyzed for each run. Alpha alumina showed about 0.01 wt-% chloride in front of a catalyst that showed about 0.25 wt-% chloride. In contrast, gamma alumina showed approximately 1.2 wt-% chloride in front of a catalyst that showed about 0.01 wt-% chloride. Accordingly, the gamma alumina guard bed permitted extended operation of an effective transalkylation catalyst by removing contaminant feed species.
A transalkylation process for reacting carbon number nine aromatics with toluene to form carbon number eight aromatics such as para-xylene is herein disclosed. The process is based on the discovery that deactivating contaminants present in typical hydrocarbon feeds, such as chlorides, can be removed with an alumina guard bed prior to contacting with a transalkylation catalyst. Effective transalkylation catalysts have a solid-acid component such as mordenite, and a metal component such as rhenium. The invention is embodied in a process, a catalyst system, and an apparatus. The invention provides for longer catalyst cycle life when processing aromatics under commercial transalkylation conditions.
2
TECHNICAL FIELD Fabrication of Large Scale Integrated circuits and other devices having submicron features entailing projection lithography by use of extreme ultraviolet delineating radiation. TERMINOLOGY EUV--"Extreme Ultraviolet" electromagnetic radiation--radiation within the wavelength range of from 3 nm to 50 nm. This wavelength range is sometimes described as "soft x-ray". Vacuum Ultraviolet--Electromagnetic radiation in the wavelength range of from 50 nm to 150 nm. Sometimes known as "Deep UV", such radiation is highly absorbed in usual optical materials which are transmissive at longer wavelengths--an absorption, which like that of the EUV, suggests use of reflecting, rather than transmitting, optics. Proximity X-ray--A lensless, one-to-one (mask-to-image), lithography system in which the information-containing mask is in near-contact with the image plane. Image--Replicated mask pattern as produced: on the focal plane ("aerial image"); upon exposure in the resist ("exposed image"); upon development of the exposed image ("developed image"); as used for masking device-functional material ("masking image"). Exposed Image--Constituting the latent image produced upon exposure to patterning radiation. Developed Image--Images produced upon development of the exposed image. Depending upon resist tone, retained resist material constituting these images may correspond with light or dark regions of the aerial images. Wavelength--Unless otherwise noted or implicit, reference to wavelength of delineating radiation is as measured in vacuum. Leaky Phase Mask--A phase mask in which deliberate passage of illuminating radiation through blocking regions destructively interferes with edge-scattered radiation to lessen scatter-blurring of feature edges. The structure is sometimes referred to as an "attenuated phase mask". Radiation Coherence--Reference is made to spatial coherence of delineating radiation in terms of Filling Factor, σ--i.e. by reference to the degree of coherence yielded by a system satisfying the relationship: ##EQU1## In accordance with the relationship, a σ value of zero indicates 100% coherence. Transmission (followed by a parameter such as absorption value)--The description contemplates reflective optics and masks. In conventional usage, the round-trip experience of the radiation is described as though it had undergone one-way passage through an analogous transmission element. DESCRIPTION OF RELATED ART It is generally agreed that "next generation LSI" --LSI built to design rules of 0.25 μm or smaller, will require delineating radiation of shorter wavelength than that in the presently-used "near ultraviolet" spectrum. Shorter wavelengths in the deep ultraviolet spectrum (DUV), e.g., at wavelength values of 248 nm initially, and eventually of 193 nm, should be satisfactory for design rules of 0.25 μm and, approaching 0.18 μm. Two candidates are being pursued for use with still smaller design rules. The first uses accelerated charged particles--electrons or ions. The second uses electromagnetic radiation beyond the DUV. Radiation in the EUV spectrum (λ=3 nm-50 nm) is under study for fabrication of 0.18 μm devices, and is prospectively useful for smaller design rules, e.g., 0.10 μm and smaller. Proximity x-ray is, at this time, the most advanced short wavelength delineation technique. A typical system operates at a wavelength in the range of from 0.6 to 1.8 nm. Thin gold or tungsten membrane masks spaced 5 to 10 μm from the wafer to avoid mask damage, have yielded pattern images of 0.1 μm and smaller feature size. Diffraction and penumbra blurring at feature boundaries have been successfully addressed. Diffraction effects are inherently minimized by the short wavelength radiation. Resolution, for already-excellent resist materials, may be further improved by use of phase masks. See, Y.-C. Ku, et at., J. Vac. Sci. Technol. B 6, 150 (1988). Penumbra blurring is not a problem for synchrotron and small size plasma sources. The proximity system, still widely pursued, has a significant drawback. Masks, necessarily made to the same design rules as the image, ("1:1 masks") are expensive to fabricate and difficult to repair. Projection systems providing for image reduction permit use of less expensive, larger-featured masks--features perhaps 5 or more times larger than that of the desired image. Unfortunately, proximity x-ray technology is not transferable to projection. The 1.2 nm radiation, desirable for its lowered diffraction, commensurate with acceptable transmissivity in the membrane mask, is unsuited for transmission optics. Required values of refractive index and transmissivity are not available in otherwise suitable materials. As a consequence, x-ray projection systems use reflective, rather than transmission optics. Since conventional single-surface mirrors have inadequate reflectivity, distributed mirrors--"Distributed Bragg Reflectors" (DBRs)--are used. (These are often called "multilayer mirrors" in the EUV literature.) Again, the 1.2 nm proximity printing wavelength range is unacceptable. Required index differences for suitable DBR structures are unavailable at this wavelength. Substrate-supported DBRs and patterned metal layers, serve as reflecting masks. (Chromium layers, commonly used at longer wavelengths in the ultraviolet spectrum, are replaced by gold or germanium layers in the EUV spectrum.) Features as small as 0.05 μm have been printed in PMMA resist layers using delineating radiation of 13.9 nm wavelength. See, J. E. Bjorkholm, et al., J. Vac. Sci. Technol. B 8, 1509 (1990). Another problem arises. While the gap-induced limitation of proximity printing is avoided--while the projection process offers a high resolution aerial image--appropriate resist materials--have not been found. Delineating EUV radiation is absorbed within a very thin surface layer--far too thin a layer to use as a stand-alone etch-barrier. In thicker, single material, resist layers, the underlying major portion is effectively unexposed, resulting in poorly defined profiles, and in unsatisfactory resolution. The problem is under study. One approach is described in "Use of Trilevel Resist for High Resolution Soft X-ray Projection Lithography", D. W. Berreman, et al., Appl. phys. Lett., vol. 56(22), 28 (1990). The reference describes a tri-level system constituted of a thin layer of photosensitive material, an underlying thin layer of germanium, and, finally, a thick layer of organic material. After developing the surface image, it is transferred to the silicon substrate in an etch step (in which the two underlying layers serve in succession as etch-barriers). A promising approach uses a different form of "surface activated" resist, and a two-part process providing for transfer of a developed surface image into the underlying part of the resist. The problem is most severe in the EUV spectrum for wavelengths greater than 10 nm, although it is still a concern at longer wavelengths (e.g. at 193 nm). SUMMARY OF THE INVENTION The invention is concerned with the fabrication of devices built to design rules of 0.18 μm or smaller. Patterning is by projection-reduction using radiation in the EUV spectrum. The high absorptivity for this radiation changes the role of the resist which now becomes a controlling factor in process design. The inventive processes use state-of-the-art technology to relax resist constraints. In particular, improved edge definition, due to phase masking, offers processing advantages including a thicker exposed image and increased freedom in processing conditions; in exposure; in development; and in depth-of-field. A common aspect of all included processes provides for a thickened "exposed image"--resulting from initial exposure to patterning radiation. Upon development, the mask pattern is of thickness greater than in conventional processing. This developed pattern may then serve to mask device-functional material, or it may be transferred into underlying masking material to yield a sail more robust mask pattern. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a schematic cross-sectional view of apparatus suitable for inventive use. This apparatus includes a phase mask operating in transmission. FIG. 2 shows analogous apparatus, using a reflective phase mask. FIG. 3 is a schematic view of a transmission phase mask. FIG. 4 is a schematic view of a reflecting phase mask. FIG. 5, on coordinates of image intensity and position, relates these characteristics for aerial images produced by mask structures of varying attenuation. FIG. 6, in the same units of position, shows resist image characteristics resulting from aerial images of FIG. 5 for a normal (non-phase-shifting) mask. FIG. 7 shows the corresponding resist image characteristics when using an attenuated phase-shifting mask. DETAILED DESCRIPTION I. General--A consensus on the likely commercial form of EUV pattern delineation has been reached. Projection apparatus is likely to be all-reflecting and to use aspherical elements. Radially-dependent aberrations lead at least to preference for scanning, with use of an arc-shaped scanning region at constant radius from the optical axis. The all-pervasive problem of short absorption distance for the EUV radiation leads to a variety of resist materials of sophisticated design. These are described with reference to the literature. All included processes use phase masking. A particularly suitable "leaky" phase mask is described in companion U.S. patent application Ser. No. 08/326,449. II. Apparatus--Two forms of apparatus appropriate for inventive use are shown. That of FIG. 1 is ganged for use with a transmission mask--it is a Schwarzschild projector using two-element reflecting optics. That of FIG. 2 is an Offner ring field projector again, with two-element reflecting optics (but three reflections), suitably used with a reflection phase mask. Commercial apparatus is likely somewhat more complex--perhaps of the form shown in U.S. Pat. No. 5,315,629, issued May 24, 1994. The patented apparatus is all-reflective, 4 element, with aspherical correction. Both figures show "normal incidence" reflection. (The terminology is to include usual deviation from normal incidence, required to avoid blocking when using reflective optics. Deviation of from a few degrees to about 25° from normal incidence is common practice.) State-of-the-art grazing-incidence optics introduce resolution-limiting aberrations and are generally non-preferred. As used in Example 1, radiation 10 is 13.9 nm synchrotron wavelength (the 3rd harmonic of the VUV ring of the U13 Brookhaven undulator). Mask 11 consists of a patterned layer of germanium supported by a silicon membrane. (The mask used is shown in FIG. 3.) Both focusing elements use multilayer reflectors of appropriate material pairs. Individual pairs are graded in thickness in the radial direction to assure constant 180° phase delay for varying angle of incidence. In Example 1, the resist layer 15 is a 60 nm thick film of PMMA on silicon wafer 24. For the 13.9 nm radiation, a molybdenum/silicon multilayer is used. FIG. 2 shows the equivalent system substituting a reflection mask. Incoming radiation 20 illuminates mask 21, and as modulated, is focused and directed by lens elements 22 and 23. The image is projected on layer 25 which is supported by wafer 24. Proper design of EUV sources, whether synchrotron or plasma, is critical. Collection efficiency is a different problem for the two. Synchrotron emission is of changing angle--is tangential to the circular path of the accelerated particles. Emission forms an arc which is thin in the normal dimension. The emission pattern should be reshaped. Synchrotron radiation is likely to be excessively coherent; plasma radiation, incoherent. Effective use requires modifying both. Collection systems have been described. See U.S. patent application Ser. No. 08/059,924, filed May 10, 1993, for synchrotron collection, and U.S. Pat. No. 5,339,346, Aug. 16, 1994 for plasma collection. III. Mask--Processes herein preferably use "leaky" phase masks (attenuated phase masks) operating on the principle of U.S. Pat. No. 4,890,309, issued 1989. Masks may operate in transmission (Example 1) or, in reflection, (Example 2)--reflection masks are preferred for the inventive purposes, since less lossy and more robust. Co-filed U.S. Pat. application Ser. No. 08/326,449 describes and claims a leaky mask structure, operating in reflection. Operating levels of attenuation and phase delay are the same, whether for one-way passage in transmission or for round-trip in reflection. Transmission in the range of from 5% to 15% has been found effective for cancellation of scattered radiation from clear regions. Greater transmission, to 25% may be tolerable, but is considered an upper limit. Depending on resist characteristics, resist removal in masked regions may become a problem. (Discussion is for simple structures in which there is no phase delay introduced in the clear regions. If, for some reason, this is not true, the phase delay of the blocking regions is adjusted to maintain a "differential" π shift, relative to the clear regions. This meaning is intended in this description.) FIG. 3 shows an attenuated phase mask for operation in transmission. As used in Example 1, it consists of a 0.6 μm thick membrane 30, supporting a patterned bilayer 31 constituted of a 262 nm thick PMMA phase-shift layer 32, and a 27 nm thick germanium attenuation layer 33. The bilayer delivers the differential π phase shift with 25% transmission. The two functions may be served by a mixed, or "alloy" layer, or in the future may be met by an as-yet unidentified single-component material. The π phase difference is illustrated by "attenuated" rays and "clear" rays 34 and 35, with respective delays of 181° and 1°. The reflection structure of FIG. 4 shows a substrate 40, supporting a multilayer reflector 41 made of alternating high and low index materials 42 and 43. The patterned bilayer 44 is constituted of phase-shifter 45 and absorber 46. Radiation 47 is patterned by the mask to yield "attenuated" rays 48 and "clear" rays 49. These emitting rays have the same phase relationship as rays 34 and 35 of FIG. 3. The studied structure introduces 10% attenuation (in this instance, for round-trip passage). Radiation 47 is illustratively shown at an angle of incidence of approximately 65° (relative to the surface). Greater deviation from normal incidence, generally not required, may be used. The leaky phase mask, while something of a compromise in reducing contrast--is simpler to construct and places no restriction on pattern design. For temperature stability the mask substrate (substrate 40 of FIG. 4) is either a low expansion material or a high thermal-conductivity material. A mixed glass composition, of 92.6 wt % SiO 2 7.4 wt % TiO 2 , is a suitable low-expansion material. Elemental silicon is a suitable thermally-conductive material. Layer pairs of the multilayer reflector each introduce a phase delay of one or more half wavelengths so that the composite reflection is in phase. Alternating layers of silicon and molybdenum are suitable in the 13 nm-15 nm wavelength range (40 layer pairs give 60%-63% reflectivity in this range). Molybdenum/beryllium pairs have been used with radiation at λ=11.4 nm. Resist absorption is somewhat less at this wavelength, and reflectivities as high as 68.7% have been reported. (Theoretical reflectivity for Mo/Be DBRs is 80%.) Ruthenium and boron carbide multilayer mirrors have been used with 6.8 nm radiation. Thickness dimensions are here discussed for waves of normal incidence. Precise ML reflector design provides for one or multiple π delay/pair adjusted for deviation from normalcy. As noted, bilayer 44 may be replaced by a single layer masking region, serving both for attenuation and phase shifting. The single layer may be composed of a single component, or two or more components forming a solid solution or fine mixture. An illustrative mixed layer is composed of an organo-silane serving for phase-shifting, and an iodine- or bromine-containing molecule for absorbing. The layer may use a heavy metal for absorption together with a lighter metal for phase shifting. While the larger mask size, permitted by projection, reduces mask cost, repair continues to be a factor. Pin-hole repair is particularly problematic for binary layers. Repair of homogeneous layers--alloy or single material layers--serving both for shifting and attenuation--is simpler than for bilayers. Pin-holes may be plugged, using material deposited by the method used for the initial layer. Excess material may be removed by planarization--e.g., by use of an overlying organic layer selected to be etch-eroded at the same rate as that of the masking material. FIG. 5 shows a 0.50 μm wide part of an image using 0.50 μm lines and spaces. It shows a single feature edge (in the center of the span), bounded by a half line (left-hand portion) and a half space (right-hand portion). Ordinate units are image intensity. Aerial images for four values of mask attenuation are plotted. Curve 50 is a normal mask using blocking regions of 100% nominal opacity. Curves 51, 52 and 53 are for phase masks with varying transmission--curve 51 for 10%, curve 52 for 20%, and curve 53 for 30%. The feature edge is considered to lie at 0.25 μm on the abscissa. Improvement in edge definition is substantial to a transmission value of about 10% and improves only slightly for values greater than about 15%. The preferred range of transmission values is 5%-15% (2.5%-7.5% for one-way passage in a reflecting mask). Mask patterning was by e-beam writing using Electron Beam Lithography, followed by reactive ion etching. Mask fabrication is described in D. M. Tennant, etal., J. Vac. Sci. Technol. B, vol. 10(6), 3134 (1992). IV. Imaging Resist--The primary objective is to relieve processing limitations due to the high resist absorption. A 1/e attenuation thickness of 0.10-0.15 μm, in practice, leads to a resist thickness of 60-70 nm. This is too thin a layer to serve as stand-alone protection during etching. A number of innovative resist structures have been designed to solve the problem. Most provide for transfer of a thin surface image into underlying material in a separate step. The "bilayer" approach uses a discrete surface layer, e.g. of an organo-metallic, light-sensitive material, and an underlying layer of organic material. A liquid developer has been used to generate an aperture-image in the surface layer. Transfer is by plasma etching. See, A. E. Novembre, et al. "A Sub-0.5 μm Bilevel Lithographic Process Using the Deep-UV Electron-Beam Resist P(SI-CMS)", Polymer Engineering and Science vol. 29, no. 14, p. 920 (1989). In "near-surface" imaging, the thin surface image is developed by chemical crosslinking of the exposed regions, after which uncrosslinked regions are made resistant to plasma transfer, by use of an agent which selectively reacts in these regions. A form of the process uses silylation. See, G. N. Taylor, etal. "Silylated positive tone resists for EUV lithography at 14 nm ", Microelectronic Engineering, vol. 23, p. 279 (1994). In "at-the-surface-imaging", refractory films, chemically bonded to organic resist surfaces, provide a plasma resistant etching mask during image transfer. See, G. N. Taylor, etal. "Self-assembly; its use in at-the-surface imaging schemes for microstructure fabrication in resist films", Microelectronic Engineering, vol. 23, p. 259 (1994). V. Processing Conditions--It is convenient to consider invention-specified processing conditions in terms of a unifying characteristic--of now-permitted increased thickness of the resist layer. In conventional lithographic fabrication, resist thicknesses was not a problem. Resist characteristics (sensitivity, response linearity, development, etc.) were accompanied by inherent absorption characteristics which permitted their use in convenient thicknesses. Occasionally, their transparency was too large, and absorbing material was added. Resist characteristics in the EUV spectrum are quite different. High absorption requires very thin layers. An objective is to overcome disadvantages--pinholes, poor etch resistance--while retaining good dimensional control. Phase masking offers a solution. Phase masking is valuable, not so much for finer features, but for steepened resist profile. This permits a thickened resist image. A note in passing--the term, "initial resist image", describes the image produced by the patterning EUV radiation, which is then developed. This "initial developed image" may then serve in usual fashion to mask underlying device-functional material. Alternatively, it may be transferred into underlying masking material. This is done with the multi-layer resist approach as well as in other structures described in the preceding section. 1. Coherence--It has been conventional to operate at a coherence level of σ≧50%. Required coherence is greater in the present work. The needed range is σ=0.5-0.2 with a preference for the narrower range σ=0.45-0.25. This is a balance between the coherence required for the destructive interference fundamental to phase masking, and spurious structure due to constructive interference. 2. Exposure--Increased image thickness requires increased exposure. An alternative way of viewing the invention is as permitting the necessary exposure. Exposure magnitude, "overexposure" in usual processing, is now permitted for a variety of reasons. For greater exposure, corresponding with increased resist penetration, produces lessened dimensional change, due to steeper profile. The required exposure is that for imaging through the thickest resist layer. 3. Development--This requirement, inter-related with exposure, is relaxed. Developer and development conditions need not be optimized solely for near-surface contrast. Higher edge definition permits use of a lower contrast, but more sensitive resist. 4. Design Rules--With permitted increased resist thickness, facility for small feature size improves. This is not due to "relaxation" in wavelength limitation, but to relative freedom from pinholes and thickness-dependent dimensional changes. 5. Radiation Wavelengths--Processing advantage permits some freedom in wavelength choice. Increased radiation wavelength, while of increased absorptivity, may offer advantage, in resist chemistry. 6. Optics--Experimental results reported in the literature have sometimes depended upon use of optical elements of near-hypothetical perfection. Cost of such elements may be prohibitive. The invention, in increasing edge definition, shows increased tolerance for the faulty image produced by imperfect optics. 7. Critical Dimension--"CD" is viewed as an important process qualifier. Steepened profile improves resolution, and accordingly, dimensional reliability. 8. Biasing--It is usual to specify processing conditions permitting use of unbiased masks. Improved profile steepness lessens need for distortion of mask features to compensate for dimensional variations due to increasing exposure. Changed values of equivalent parameters: development; choice of resist; etc., are relatively free of this consideration. Since the invention invariably yields a thicker resist pattern for any selected resist composition, it is appropriate to view resist layer thickness as the one pervasive advantage. It has been conventional practice to design processing conditions, for a thickness no greater than about 1/3 of the absorption depth (0.33 1/e)--a thickness resulting in a penetration intensity at least 70% of that of the surface intensity. A requirement of all processes of the invention is increased thickness--a thickness of at least 70% of the absorption depth, yielding a penetration intensity of no more than 50% of the surface intensity. Specific values are for PMMA. For higher contrast resists, it is possible to increase thickness beyond the 70% figure. Experimental work has yielded acceptable resolution for thicknesses of a full absorption depth. Such thicknesses approach the minimum requirement for reliability in a stand-alone resist layer. An essential element of the invention is production of a latent image by mask-patterned exposure, followed by development, to produce an "initial image" of the required thickness--of a thickness greater than that of a penetration depth equal to 70% of the absorption distance. In single-layer resists, and in multi-layer resists, this initial pattern thickness corresponds with the thickness of the initial top-most or "resist layer". Under other circumstances, the thickness of the resist layer may exceed the thickness of the initial image, with subsequent transfer into underlying material, which, itself, part of the initial homogeneous resist layer. There may be chemical conversion following development or exposure. The silylated positive-tone resist is an example in which the developed pattern is altered to resist pattern transfer. Reference to "image thickness" is intended to be descriptive both of arrangements in which it corresponds with thickness of an initial discrete resist layer (whether or not transfer into underlying protective material is contemplated), and in which it results from patterning exposure which penetrates only part way through the layer. Proper choice of resist takes nonlinearity into account. Resists are characteristically exponentially dependent on radiation intensity below some saturation value. Accordingly, there may be further improvement in contrast where threshold conditions are exceeded (so that some resist is removed from regions of peak constructive interference). Meaningful resist removal data, such as that of FIG. 7, should reflect differential removal. Unwanted resist removal should not exceed some maximum. Residual material must be sufficient for error-free masking. This consideration is generally avoided for multi-layer resist structures, in which masking is largely due to material underlying the resist layer. However described, the inventive processes give increased yield. This is true for less-than-perfect optics, surface smoothness, and layer thickness. They are sometimes used for processing freedom--may permit substitution of dry-developed, relatively insensitive resists. The improved aerial image is accompanied by greater depth of focus--again contributing process flexibility. FIGS. 6 and 7 plot computer simulations for apparatus and process conditions used in the development of the data of FIG. 5. Abscissa units for the three figures correspond. All are based on: (a) 0.50 μm lines and spaces as viewed in the image plane; (b) a numerical aperture (NA) of 0.0835, for the camera; (c) a wavelength of 13.9 nm; (d) 100% coherence; (e) constant optimal phase shift of 180°. The information represents a "worst case" in low resist threshold and high coherence. It was used in designing processing conditions for the examples and is included for this purpose. Ordinate units for FIGS. 6 and 7 are depth of resist removed during development of a surface image of 0.6 μm thickness. The curves show the improvement in the resist image produced by the improved aerial image. Values presented are for PMMA--a positive tone resist, so that removed areas correspond with bright areas of the aerial image. Negative tone resist data is similar, but with removal corresponding with dark areas of the aerial image. The ordinate scale for FIGS. 6 and 7 extends from 0.00 μm (unexposed resist) to a maximum of -0.06 μm ("total" removal). FIG. 6 is a plot of dose-dependent data describing a resist image produced by the aerial image using the normal mask of curve 50. Curves 60-65 are plotted for doses of 20, 30, 40, 50, 70 and 95 mJ/cm 2 , respectively. Since there is no transmission through the masked region (that from 0.00 μm to 0.25 μm on the abscissa), no resist is removed in this region. For the dose range shown, sidewall angle (resist slope at the feature edge) increases with dose, reaching a maximum value of 71° for the 95 mJ/cm 2 dose of curve 65. A dose of 50 mJ/cm 2 was required for development of the full 0.06 μm thick image. FIG. 7 presents the same data, but substituting a 10% transmission phase mask for the normal mask of FIG. 6. Curves 70, 71, 72, 73, 74, 75 and 76 represent dose values of 20, 30, 40, 50, 70, 95, and 144 mJ/cm 2 , respectively. Sidewall slope has been increased substantially, attaining a value of 81° for a dose of 144 mJ/cm 2 . Interference structure in the masked region becomes more pronounced with increasing dose--corresponding with increasing intensity for the corresponding region of the aerial image in FIG. 5. Plotted data is for faithful replication of lines and spaces--generally preferred. Biased masks may serve the same purpose as for usual processing. There may be circumstances where the added expense and convenience are justified. VI. Examples--A number of experiments were conducted. They vary in radiation wavelength, in degree of coherence, in radiation dose, etc. Much of the data presented is taken from experimental results. Example 1--The apparatus as shown in FIG. 1--a 20:1 reduction, 0.0835 NA Schwarzschild projector, with a transmission phase mask, is used with 13.9 nm radiation to image 0.1 μm lines and spaces in a 0.07 μm thick "PMMA film". The mask, described as a FIG. 3 example, uses a bilayer of germanium and PMMA for phase shifting. Transmission is 25%. (While serving for experimental purposes, the transmission value exceeds the ˜10% found adequate in other work.) Reflectivity of 60%-63% results from a 40-layer pair Mo/Si multilayer reflector. Radiation, collected from a synchrotron and unprocessed, is near 100% coherent. A dose of 144 mJ/cm 2 yields sidewall characteristic of curve 76 of FIG. 7 (˜81°). Example 2--Example 1 is repeated, substantially unchanged, but using radiation of λ=11.4 nm. Choice of this wavelength is based on experimentally-shown increased absorption distance. While not experimentally verified in this work, it is reported that observed absorption distance in PMMA is 0.27 μm compared with 0.16 μm for 13.9 nm radiation. Multilayer mirrors using 50 molybdenum/beryllium pairs are 68.7% reflective. Example 3--Example 1 is repeated with a 1:1 Offner projector, as shown in FIG. 2. The mask structure is shown in FIG. 4. 0.1 μm equal dimensioned lines and spaces are faithfully replicated.
The fabrication of integrated circuit devices built to design rules of 0.18 μm and below uses patterning radiation in the EUV spectrum. Optimized processing conditions take advantage of independently developed EUV characteristics such as short resist absorption lengths.
6
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the field of apparatus for hydrogen generation, more particularly to a novel simplified shift reactor for use with an underoxidized burner which substantially increases the concentration of hydrogen by reacting carbon monoxide and water to form hydrogen. The apparatus has widely diversified uses in providing hydrogen generation, in general, including fuel for fuel cells and on-site hydrogen production, and for injection into combustors of internal combustion and turbine engines to reduce nitrogen oxide emissions. 2. Brief Description of the Prior Art Underoxidized burners having a single or double stage internal combustion chamber for receiving gaseous or liquid fuel for combining with air or oxygen and subsequent ignition by a spark plug are disclosed in prior U.S. Pat. Nos. 5,207,185 and 5,299,536 as well as in co-pending U.S. application Ser. No. 08/148,472. Additionally, U.S. application Ser. No. 08/309,041 discloses improvements in injectors for such burners. These devices have been successful in producing hydrogen from fuels. However, they also produce carbon monoxide, CO, which can be minimized and the concentration of hydrogen increased by the shift reaction between CO and water, as CO+H 2 O=CO 2 =H 2 . Conventionally, this reaction involves passage of gaseous water (steam) and CO through a catalyst bed. Calculations and tests have shown various advantages can accrue to the shift reaction and the overall system by including a liquid water bath before the catalyst chamber wherein the products of the underoxidized burner are passed. Therefore, a long-standing need has existed to provide a simple shift reactor for use with an underoxidized burner which will readily increase the concentration of hydrogen, and with other advantages as heated water for various heating purposes, simplified means to add water vapor without likelihood of detrimental water condensation in the shift catalyst, means to increase the extent of the shift reaction, means to eliminate certain undesirable side reaction products of the burner, and the like. SUMMARY OF THE INVENTION Accordingly, the present invention involves improvements derived from a novel shift reactor coupled with an underoxidized burner so that its exhaust products are introduced into a compartment partially occupied by liquid water, which is of a cooler temperature than the exhaust products. The compartment includes gas diffuser(s) for distributing the exhaust gases into the surrounding water bath whereby the product is cleansed and filtered into a more purified state, and the product gases are saturated with water. Additional conduit means communicates with the water bath so that heated liquid water from the process may be conducted from the compartment for other heating purposes. An excess drain may be connected to the conduit for draining off a quantity of liquid water from the bath and regulating the water temperature, when desired, and/or for removing water soluble and/or water dispersible impurities. The hydrogen-containing gas product from the water containing compartment is passed into a catalytic reactor section. The latter includes an internal eductor that automatically educts a portion of the gases that have passed through the catalyst and cause it to pass back through the catalyst to effect a degree of recirculation. Subsequently, the purified product with increased hydrogen concentration is passed to a use function. Therefore, it is among the primary objects of the present invention to provide a novel shift for use with an underoxidized burner which accepts the exhaust mixture of hydrogen and carbon monoxide for filtering, cleansing and hydrating in a bath of a temperature lower than the temperature of the mixture and also includes a shift reactor with a degree of recirculation so that the concentration of hydrogen is increased. Another object of the present invention is to provide a novel shift reactor which provides a low cost and practical method and apparatus for collecting useful thermal energy normally provided by an underoxidized burner by circulating heated water through a downstream system. Yet another object of the present invention is to provide a novel shift reactor for use with an underoxidized burner which produces soot whereby the soot spontaneously forms a dispersion in the water from which it can be readily filtered. Yet another object of the present invention is to provide a novel shift reactor for use with an underoxidized burner whose products include sulfur in the form of gaseous hydrogen sulfide, H 2 S, and carbon in the form of CO 2 , both of which spontaneously dissolve in the water which afford means for their removal. A further object resides in placing a catalyzed shift reaction after the burner in such a manner that the shift can be repetitively reactivated without complex intervening hardware and valves. Also, an object resides in inserting or placing a catalyst chamber after the burner and the water-cooling chamber utilizing simple flow controls and including simple means for recirculating. Finally, an object is to enable the catalyst to be activated or reactivated in situ with the underoxidized burner and shift catalyst chamber attached in a unitary construction in a single overall container which simplifies the activation process. BRIEF DESCRIPTION OF THE DRAWINGS The features of the present invention which are believed to be novel are set forth with particularity in the appended claims. The present invention, both as to its organization and manner of operation, together with further objects and advantages thereof, may best be understood with reference to the following description, taken in connection with FIG. 1 which is a diagrammatic view of the inventive shift reactor used in connection with an underoxidized burner. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, an underoxidized burner is illustrated in the general direction of arrow 20 which has been previously disclosed in prior U.S. Pat. No. 5,207,185 and 5,299,536. Additionally, U.S. application Ser. No. 08/309,041 discloses improvements in injectors for such burners. The burner may be referred to as a hydrogen generator. In the present instance, its exhaust products are supplied to a special shift reactor, as indicated by numeral 19, which increases the hydrogen output and produces other advantages, and its major purpose is to supply hydrogen for various purposes, as for a fuel cell system. Referring now in detail to FIG. 1, the hydrogen generator 20 is described with particular reference to U.S. Pat. No. 5,207,185 but applies to related patents and applications as above stated. It includes a housing 21 having an underoxidized combustion chamber 25 in which the hydrogen generating means are located. Fuel is introduced via a tube 36 leading to a heat exchanger 33 and subsequently to holes 38, in combination with air supplied via an inlet 26 so that the fuel/air is initially combined in a tube 27 within the combustion chamber 25. The fuel in heat exchanger 33 is preheated and liquid fuel vaporized by heat transfer with hot combustion gases in chamber 25. Tube 27 is open-ended so that the combined fuel/air is directed towards, and impinges on, a baffle 28 on the end of a cup 30. As indicated by the flow of arrows, the flow is reversed upon itself and exits through the open end of the cup 30, indicated by number 31. This process induces mixing of the air and fuel. The reversed flow exits the cup at the orifice or opening 31 and immediately impinges on the end of the burn wall, indicated by numeral 32, serving as a second baffle where the flow is again abruptly caused to move at successive right angles producing further mixing. The thoroughly mixed gas and air is now within the combustion chamber 25 wherein ignition of the mixed gases by gases already burning in the burner combustion chamber takes place. The initial ignition of the first entry of unignited gases occurs upon operation of a spark plug 34 having its electrodes within the combustion chamber 25. The flame continues through the burner and finally the exhaust or burner products exit at a discharge duct 35 from which they are introduced to the shift reactor assembly 19. The underoxidized burner products include hydrogen (H 2 ) and carbon monoxide (CO). The concentration of hydrogen is substantially increased by effecting the shift reaction between carbon monoxide and water, CO+H 2 O=CO 2 +H 2 . Conventionally, this reaction involves passage of water and carbon monoxide through a catalyst bed. Calculations and preliminary tests have shown that the shift reaction plus various improvements can be attained by use of the combined inventive burner 20 and shift reactor 19 of FIG. 1. A water bath section 41 of shift reactor 19 includes a plurality of diffuser apparatuses 57. In them, gaseous products from discharge duct 35 pass through a tube 58, are turned 180° on impinging onto the interior of a cup 42, and then enter cooler water bath 40 at opening 44. The gasses bubble through water 40, causing temperature and solution equilibration and dispersion of particulate matter, and then enter space 60 above the water from which they leave via opening 45 and pass into shift reactor section 61. One-way valve 43 on cup 42 closes when the pressure in cup 42 is greater than in space 60 and opens when the pressure in space 60 is lower than within cup 42, thus maintaining flow only in the desired direction. Inlet opening 47 is for introduction of water, which may derive from a downstream component, as a fuel cell effluent, and outlet opening 56 is for egress of excess water 40. Heat exchanger 59 may be used to heat water, which is then circulated elsewhere for heating purposes. It also may be connected to a downstream air-cooled exchanger for cooling water 40. Gases leaving at opening 45 pass through a tube 46 and are directed downward on passing into cup 62. Tube 48 is of larger diameter than tube 46 and surrounds tube 46, and its upper end is higher than a catalyst bed 49, and its lower end is below catalyst bed 49. The top of tubes 46 and 48, cup 62 and annulus opening 51 constitute an eductor. Bed 49 is held in place by a pair of spaced apart screens 50 at top and bottom. The diameter of the cylindrical opening of cup 62 is greater than tube 46 and less than tube 48, and fits into the annulus between tubes 46 and 48, forming an opening 51. Cup 62 causes circulation at 51 to be turned down, and the relatively high velocity at opening 51 results in educting gases from a space 53 above the catalyst bed, which mix with the main gas stream to effect recirculation. The original and recirculated gases move to space 54 below catalyst bed 49. The mixture then passes upward through bed 49 and into space 53, eventually leaving at an outlet opening 55, and are then directed to the use site, such as a fuel cell. In operation, gases from discharge duct 35 pass into water container 41. When the pressure at duct 35 is greater than that in space 60, one-way valve 43 prevents water from flowing into water bath section 41 and thence into duct 35, and vice versa. Other means of preventing reverse flow may be used without falling outside of the inventive concept. The gases passing orifice or opening 44 bubble through water 40. One consequence of this process is temperature equilibration between gas and water, which depends on the original water temperature and flow rates both into space 60, via inlet 47, and out of space 60, via outlet 56, and the temperature and flow rate of the gases. The so-heated water is plumbed via outlet 56 to locations downstream of the system where heat is needed, such as space heating and the like. Or, water circulated through a heat exchanger 59 may be used for this purpose. These represent low cost and practical methods for collecting useful thermal energy normally provided by the burner via circulating heated water for external use in a water or space heater. Heat exchanger 59 coupled with an external air cooled heat exchanger may also be used for adjusting the water temperature. The gases leaving space 60 at opening 45 spontaneously have become saturated with water vapor at the equilibrium temperature. Since this temperature is always lower than attained by the subsequent shift reactor (which develops heat), spontaneous condensation of water in the shift reactor, which may cause damage, is avoided. The water flow rate into space 60 via inlet 47 and out of outlet 56 are regulated to provide a temperature that produces the maximum acceptable water content for the shift. The process results in high hydrogen yield because the shift reaction is favored by the low temperature. On passing through the water bath, gaseous H 2 S, which is very soluble and is formed in the UOB when sulfur is present in the fuel, will dissolve in the water. This material is toxic and can poison the downstream shift reactor. It can be removed by directing the water to the sewer or passing the water through absorbents, such as calcium oxide or zinc oxide. The latter absorption process is more efficient from a water solution than from a gas mixture. CO 2 formed by the UOB will also dissolve in the water and can be removed in a similar fashion. While oxides of sulfur, as SO, SO 2 or SO 3 , are not likely to be present in the effluent of an underoxidized burner, any which may form in non-optimized operation will also dissolve and can be removed in similar fashion. Finally, particles of carbon which are produced by the UOB and can cause problems downstream of the system readily disburse in the water. They can then be removed by directing the water to a sewer or passage through a filter. The cleansed and filtered gas from the water bath enters the shift chamber 61 via opening 45. The stream undergoes recirculation via eduction from space 53 at opening 51. The degree of recirculation via eduction is relatively mild: sufficient to aid heat transfer, which is critical to catalytic efficiency, but not enough to notably dilute concentrations, which would harm efficiency. One consequence of increased efficiency is need for a lesser amount of catalyst. Additionally, recirculation in the catalyst bed holds overall temperatures in bed 49 more nearly constant which permits optimized operation for the shift equilibrium. The burner-shift and reactor design indicated in FIG. 1, locates the hydrogen producing process within a single overall container, which results in great overall simplifications. Yet, it remains highly versatile, as indicated, and leads to simple means to activate the catalyst, as next discussed. So-called low temperature catalyst is normally supplied with its major operative component, copper, Cu, in the oxidized, ineffective CuO state. So-called high temperature catalyst, as C12 obtained from United Catalyst, Inc. consists of coprecipitated iron and chromium oxides. Activation involves reduction of the oxide, as CuO, to the metal, as Cu. It is normally accomplished by passing warmed, commercial hydrogen-containing gases through the catalyst bed (CuO+0.5H 2 O=Cu+0.5H 2 O) with the bed removed from the system. With the new design, however, this activation may, instead, be performed in situ by passing the output of the underoxidized burner, which contains considerable H 2 , through the undisassembled system. In addition, underoxidized burner operations which can cause oxygen to pass through the catalyst, say during preheat with a burner with excess air, need not be avoided, and complex intervening hardware and valves to direct oxygen-containing gases around the catalyst chamber are not needed. Thus, FIG. 1 does not include complex plumbing to bypass the catalyst chamber during preheat. This is not needed in the inventive process because the catalyst is rapidly reactivated during later passage of hydrogen-containing gases from the burner. With catalyst, hydrogen yield is increased. However, similar results were obtained with porous rocks formed from cement, and comparable results are expected with pieces of copper. As a consequence, wherever this disclosure refers to catalysts, these may be replaced with materials with a large surface area. While the combination of water bath section 41 and shift section 61 of shift reactor 19 have considerable advantages, it is notable that shift section 61 includes several novel features. Thus, for circumstances where water bath section 41 is not needed, section 41 may be eliminated and shift section 61 instead attached directly onto burner 20. In this case, water (or steam) required for the shift is introduced at known flow rates into opening 35 (or 45) where it is vaporized by the hot gases from the burner and the steam-gas mixture passed into tube 45 with the consequences as indicated previously. While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of this invention.
A shift reactor is disclosed that is mounted on the exhaust end of an underoxidized burner so that the exhaust product is introduced to a cooler water bath in a compartment of the reactor. The exhaust product is passed through the water bath via submerged gas diffusers. The reactor compartment includes a collection chamber for receiving the bathed exhaust product containing hydrogen gas which is then exited to a shift catalyst chamber. The latter includes eductor for recirculation. A conduit may be coupled to the water bath for distributing heated water from the bath for exterior heating purposes or for purification means. A drain is operably connected to the conduit for permitting removal of excess water and a fill inlet is provided for adding water.
5
TECHNICAL FIELD The present invention relates in general to telecommunications networks, and in particular, to the maintenance of profile information for users in such networks. BACKGROUND In a cellular system, the geographic area which is serviced by the system is divided into cells. In each cell there is a base station possessing a number of transmitters and receivers, each of which is tuned to a different frequency or radio channel. A mobile subscriber within a cellular system has a transceiver which uses two radio channels to initiate a telephone call. Since government authorities allocate a fixed number of channels for mobile telephonic communications, subdividing the geographic area serviced by a system, or service area, into cells allows the same radio channel to be reused in more than one cell within the service area. Thus, the number of calls which the system can process at any given time is increased. A mobile switching center (MSC) within the service area determines the radio channels to which the mobile subscriber transceiver may tune to communicate with a base station. Furthermore, the MSC switches a base station transceiver to a switched telecommunications network, such as the public switched telephone network (PSTN) for transmission elsewhere. To obtain mobile telephone service, a mobile subscriber must first make arrangements with a provider of mobile telecommunications services. In most cases, the services offered by the provider will extend beyond the area covered by a single mobile telecommunications system. Typically, the service provider may do so by owning or controlling a network of such mobile telecommunications systems, making arrangements with systems owned by others in other territories, or both. The service provider assigns each mobile telephone subscriber to a home MSC. The home MSC maintains a register called a home location register (HLR) in which subscribers assigned to that MSC are recorded or stored. FIG. 1 illustrates an example of a network of cellular telecommunications systems. Mobile telecommunications network 100 includes a plurality of MSCs, such as MSC 101, MSC 103 and MSC 104. MSC 103 performs switching operations for base stations 108, 109 and 110 through communication links 113, 114 and 115, respectively. As defined herein, a communication link refers to any medium for transmitting a message. The message may be data, voice and/or video information, in an analog or a digital format. Communication links also include, without limitation, wireline media such as copper or fiberoptic cable, and wireless media such as radio frequency and microwave transmission systems. Similarly, MSC 104 performs the switching operations for base stations 111 and 112 through communication links 116 and 117, respectively. Although not illustrated in FIG. 1, MSC 101 is able to perform switching operations for a plurality of base stations. Each of the plurality of MSCs may be connected to PSTN 102. However, only the connection between MSC 101 and PSTN 102 has been illustrated in FIG. 1. A mobile subscriber 120, is assigned, or homed, to MSC 101. However, in the example illustrated in FIG. 1, mobile subscriber 120 is travelling between the service areas corresponding to MSC 103 and 104. MSCs 101, 103 and 104 are interconnected by a data network which is represented using communications links 105, 106 and 107. It should be noted that no particular type of network protocol or network topology is intended to be represented by communications links 105, 106 and 107. Communications links 105, 106, and 107 are provided to indicate that each MSC is able to communicate data to another MSC using some form of data communication. Additionally, it should be noted that communications links 105-107 may be included as a portion of the PSTN or as dedicated connections. Furthermore, communications links 105, 106 and 107 are not intended to represent a network for carrying calls, although data may be communicated over the same networks which service voice calls. During a communications operation, a service provider maintains a service profile for each of its mobile subscribers. A service profile includes information about the services to which a mobile user has subscribed, as well as other data necessary to provide a desired service. For example, a service profile may include information regarding one or more of the following: call forwarding, call waiting, three-way conferencing, calling features indicator, origination indicator, digits restriction, termination restriction code, digits carrier, routing digits, geographic authorization, authentication capability, DMH Account Code digits, DMH alternate billing digits, DMH billing digits, mobile directory number, message waiting notification count, message waiting notification type, origination triggers, PACA indicator, preferred language indicator, SMS origination restriction, SPNI PIN, SPNI Triggers, SMS termination restrictions, termination triggers, and the like. A service profile for a mobile subscriber is stored by the HLR of the mobile subscriber's home MSC. HLR 121 represents a HLR for mobile subscribers assigned, or homed, to MSC 101. A HLR is implemented by a data processing system associated with a corresponding MSC. Furthermore, it should be noted that while HLR 121 is illustrated separately from MSC 101, this separation does not imply HLR 121 is physically separate from MSC 101. Indeed, the functions of HLR 121 may be performed by a computer which also operates MSC 101. In any instance, an HLR maintains and, as will be subsequently described, distributes to other MSCs, service profiles for subscribers assigned to it and homed to its corresponding MSC. When a subscriber travels from an area serviced by its home MSC to another service area in the network of the service provider, the visited system will obtain the service profile of the mobile subscriber before providing service to the mobile subscriber. For example, when mobile subscriber 120 moves from a cell of MSC 103 to a cell of MSC 104, mobile subscriber 120 must register for service with MSC 104 before telephone service is available. Such a registration process begins when mobile subscriber 120 sends a standard message to a closest base station corresponding to MSC 104. FIGS. 2, 3 and 4 illustrate a prior art method for transferring service for a mobile subscriber from one visited system to another visited system within network 100. This prior art method is implemented in accordance with the IS41 North American Wireless Standard. FIG. 2 depicts a flow chart which illustrates the steps performed by HLR 121 of MSC 101 during such a service transfer from a visited MSC 103 to another MSC 104. In step 201, HLR 121 receives a registration notification message from MSC 104. In step 202, the HLR 121 responds to the registration notification message by transmitting a service profile associated with mobile subscriber 120 to MSC 104. MSC 104 stores the service profile within an associated visiting location register (VLR) 123. VLR 123 includes a list of all mobile subscribers visiting the area serviced by MSC 104 and currently registered with MSC 104 for service. VLR 123 of MSC 104, like HLR 121 of MSC 101, is maintained by a data processing system. This data processing system can be part of, or separate from, the MSCs, within a system and may perform additional functions not specifically set forth herein. In the description provided herein, both the register and the data processing system maintaining the register are referred to herein as the VLR. At step 203, HLR 121 of MSC 101 sends a registration cancel message to MSC 103 to cancel the registration of mobile subscriber 120 within VLR 125 of MSC 103. Thereafter, in step 204, HLR 121 of MSC 101 receives an acknowledgement of the registration cancel message from MSC 103. FIG. 3 depicts a flow chart illustrating steps performed by VLR 125 of MSC 103. MSC 103 receives the registration cancel message from HLR 121 of MSC 101 in a step 301. In step 302, MSC 103 transmits an acknowledgement of the registration cancel message to HLR 121 of MSC 101. MSC 103 then deletes the service profile associated with mobile subscriber 120 from VLR 125 in step 303. FIG. 4 illustrates a flow chart indicating a method performed using VLR 123 of MSC 104 to transfer the service of mobile subscriber 120 from MSC 103 to MSC 104. In step 401, MSC 104 (the visited MSC) receives the registration message from mobile subscriber 120. At step 402, MSC 104 transmits the registration notification message to HLR 121 of MSC 101. In step 403, MSC 104 receives the service profile associated with mobile subscriber 120 sent from HLR 121 of MSC 101. This step corresponds to step 202 of FIG. 2. The service profile is subsequently stored within VLR 123 of MSC 104. The communication of messages and service profiles between MSCs 101, 103 and 104 occur over a data network. represented by communications links 105, 106 and 107. The methods represented by FIG'S 2, 3 and 4 are partially accomplished through the use of a data processing system implemented at each MSC. An example of such a data processing system is data processing system 500 illustrated in FIG. 5. Data processing system 500 includes a central processing unit (CPU) 510, such as a conventional microprocessor, and a number of other elements interconnected via one or more system buses, which are collectively represented by bus 512. These elements include a random access memory (RAM) 514 for temporary storage of data and program instructions, read only memory (ROM) 516 for read only storage of data and program instructions, an input/output (I/O) adapter 518 for connecting peripheral devices such as disk units 520 and tape drives 540 to bus 512, a user interface adapter 522 for connecting keyboard 524 and mouse 526, a communications adapter 534 for connecting the data processing system to a data network, and a display adapter 536 for connecting bus 512 to display device 538. The data processing system 500 is provided as one embodiment of a data processing system. It should be noted that a data processing system used by a MSC need not include all of the elements illustrated in FIG. 2 and may perform other data processing functions associated with the MSC and not specifically described herein. SUMMARY OF THE INVENTION A limitation of the prior art methodologies outlined above is that, each time a mobile subscriber moves from one visited MSC to another visited MSC, the mobile subscriber's service profile must be transmitted, consuming bandwidth on a data network interconnecting the visited MSCs with a home MSC of the mobile subscriber. The tremendous growth in mobile communications traffic has necessitated the use of multiple MSCs in a metropolitan area. As the area served by a single MSC shrinks, there is a corresponding increase in a number of visiting subscribers within a network and in a number of new registrations to be performed by an MSC. This problem is heightened in a metropolitan area network. For example, when a delivery truck or cab traverses a metropolitan area, it is likely to visit several MSCs and may even register with the same MSC several times in one day. As previously described, each registration with a visited MSC involves a transfer of a service profile corresponding to the mobile user on the network interconnecting the MSCs and, therefore, a load on the visited MSC is increased. Furthermore, as more services, such as Wireless Intelligent Network ("WIN"), become available to a mobile subscriber, the service profiles associated with the mobile subscriber will grow larger. In accordance with one embodiment of the present invention, traffic on data networks interconnecting mobile switching centers in a communications system is reduced. Thus, the demand on bandwidth of the data network is alleviated by eliminating unnecessary transmission of service profile information. In particular, loads of mobile switching centers in the communications system are reduced when a home switching system or a centralized register serving several switching systems recognizes that service profiles for a subscriber do not need to be transmitted to a visited switching systems when the visited switching system was previously sent (within a predetermined time period) a most current service profile for the mobile subscriber. According to one aspect of the invention, a service profile maintenance system for subscribers of a mobile communication system or for a network of such systems maintains a list of last visited mobile telecommunications systems for each mobile subscriber. Upon receiving a registration notification from a visited system, the service profile maintenance system determines whether a visited system is on the list of last visited systems which has previously received the subscriber's current profile for that mobile subscriber. The service profile maintenance system will send the service profile in response to a registration message from the visited system only when the system is not on the list of last visited systems. According to another aspect of the invention, a mobile switching center stores a service profile of a visiting subscriber following receipt of a registration cancel message so that the service profile is not downloaded again if the visiting subscriber returns to that system. According to yet another aspect of the present invention, when a service profile associated with a particular subscriber is modified, the mobile switching center maintaining a subscriber's service profile will mark all entries in the list of last visited systems as changed or "dirty," or deletes the visited systems from the list with the exception of an entry associated with a mobile switching center in which the subscriber is then registered. When the subscriber revisits any of these mobile switching centers, the updated profile information will be sent to that mobile switching center. The forgoing summary is intended only to explain advantages of the invention in its various aspects and is not intended to limit the invention as defined in the appended claims in any manner. BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding of the present invention and the advantages thereof, following is a description of a preferred embodiment which is made in reference to the accompanying drawings, in which: FIG. 1 is a schematic illustration of a typical cellular communication network; FIG. 2 is a flow diagram of a prior art method of downloading service profile data in a cellular communications network; FIG. 3 is a flow diagram of a prior art method for cancelling a registration of a mobile subscriber at a visited MSC; FIG. 4 is a flow diagram of a prior art method for registering a mobile subscriber at a visited MSC; FIG. 5 is a block diagram of a data processing system used to implement the various systems and methods of the present invention within a cellular communications network; FIG. 6 is a flow diagram of a method for maintaining profile information for mobile users 2 in accordance with one embodiment of the present invention; FIG. 7 is a flow diagram of a method for maintaining a mobile subscriber's service profile data within a cellular communications network in accordance with one embodiment of the present invention; and FIG. 8 is a flow diagram of a method for updating a mobile subscriber's service profile data in accordance with the present invention. DETAILED DESCRIPTION Refer now to the drawings wherein depicted elements are not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views. FIG. 6 illustrates a methodology for maintaining profile information for mobile users in accordance with one embodiment of the present invention. Referring now to FIG. 6, together with FIG. 1, during operation of one embodiment of the present invention, a subscriber service profile maintenance system, such as home location register HLR 121, maintains service profiles for mobile subscribers assigned to home mobile switching center MSC 101. For each subscriber, or subscriber service profile, HLR 121 also maintains a last visited list of each mobile communications system, such as mobile switching centers MSCs 103 and 104, with which the subscriber has previously registered. It should be noted that the last visited list includes a number of MSCs which a mobile subscriber has previously visited, and is not limited to a single MSC which was immediately visited prior to being noted in the last visited list. Each entry on the last visited list is maintained indefinitely. In the alternative, each entry on the last visited list is maintained for at least a predetermined time period or until the last visited list has reached a preselected maximum length. When the last visited list reaches the maximum length, the last visited list may then be purged. For example, in step 601 of FIG. 6, when mobile subscriber 120 registers with a MSC other than home MSC 101, HLR 121 or MSCIO1 makes an entry into a last visited list for mobile subscriber 120. This last visited list is stored and maintained by data processing system 300 which provides control information for HLR 121. Subsequently, when mobile subscriber 120 registers with visited, MSC, such as MSC 104, the visited MSC sends a registration notification message via communications link 106 to HLR 121. When HLR 121 receives the registration notification message from a visited MSC 104 in step 602, the subscriber service profile maintenance system reviews the last visited list to determine whether visited MSC 104 is included on the last visited list for mobile subscriber 120 (step 603). If the visited MSC sending the registration notification message is not on the last visited list, the mobile subscriber's (120) service profile is transmitted to the visited MSC in step 605. If the MSC sending the registration notification message is on the last visited list, the subscriber's service profile is not transmitted to the visited MSC. The subscriber's service profile maintenance system transmits an acknowledgment of the registration, but the subscriber's entire service profile is not transmitted to the visited MSC. It should be noted that the service profile will remain on the visited MSC either indefinitely or for a predetermined time period, as determined by a designer of the communications system. After mobile subscriber's 120 service profile is transmitted to visited MSC 104, HLR 121 adds visited MSC 104 to the last visited list stored therein in a step 606. Next, in a step 607, HLR 121 marks the last visited list to indicate mobile subscriber 120 is currently within an area serviced by visited MSC 104. At step 608, the subscriber service profile system transmits a registration cancel message to visited MSC 103, with which mobile subscriber 120 is then currently registered. As will be described below with respect to FIG. 7, when mobile subscriber 120 registers with visited MSC 104 during a previous visit, the profile information associated with mobile subscriber 120 continues to be stored by visited MSC 104. Therefore HLR 121 is not required to send the profile information to visited MSC 104. FIG. 7 illustrates a method performed by visited MSCs, such as MSC 103 and MSC 104, for maintaining subscriber service profile information associated with mobile subscribers in accordance with one embodiment of the present invention. In step 701, a visited MSC such as MSC 103, receives the registration cancel message from HLR 121 In response to receiving the registration cancel message from HLR 121, the visited MSC 103 does not delete the profile information associated with mobile subscriber 120 from its VLR (125). Note, the visiting location registers (VLRs) within the various mobile switching centers (MSCs) may be one of the data storage or memory devices illustrated in FIG. 2. Thereafter, in step 703, visited MSC 103 marks, or tags, the service profile information stored within VLR 125 corresponding to mobile subscriber 120. Therefore, a next time mobile subscriber 120 registers with MSC 103, MSC 103 will note the tagging of the entry associated with mobile subscriber 120 and will send a registration notification message to HLR 121 of MSC 101. When mobile subscriber 120 roams from MSC 104 to MSC 103, the method described above with respect to FIG. 7 is performed within MSC 104. Furthermore, when the methodologies of FIGS. 6 and 7 are executed, the profile information associated with mobile subscriber 120 is not downloaded from HLR 121 of MSC 101 to each of MSCs 103 and 104 each time mobile subscriber 120 registers with these MSCs, if these MSCs were previously visited by mobile subscriber 120 and that previous visit is reflected on the last visited list maintained within HLR 121 of MSC 101. As previously described, the registration process is a well-known process implemented in accordance with the IS41 standard. MSCs 103 and 104 may store subscriber service profile information within corresponding VLRs 125 and 123, indefinitely. Alternatively, the subscriber service profile information may be maintained for a programmable period of time. It should be noted that well-known audit processes may be implemented to periodically delete VLR entries. Such audit processes are well-known to those with skill in the relevant art and will not be described in further detail herein. FIG. 8 illustrates a method for updating the subscriber service profile information associated with a particular mobile subscriber or user. In step 801, HLR 121 of home MSC 101 updates the subscriber service profile information associated with a particular mobile subscriber. Such updating operations may be used to reflect extra services, such as call forwarding, provided to mobile subscriber 120. Thereafter, in step 802, the updated subscriber service profile information is sent from HLR 121 of MSC 101 to a mobile switching center where mobile subscriber 120 is currently registered. In the example described above, the subscriber 120 has relocated from MSC 103 to MSC 104 and is registered with MSC 104. Subsequently, in step 803, HLR 121 of MSC 101 marks all other entries in the last visited list maintained for mobile subscriber 120 as "dirty." Stated another way, the entry in the last visited list foi mobile subscriber 120 associated with MSC 103, which was a mobile switching center previously visited by mobile subscriber 120, will be marked as containing "dirty" profile information. For example, HLR 121 of MSC 101 now notes that the subscriber service profile information stored within the VLR 125 of MSC 103 is not the most current profile information associated with mobile subscriber 120. The marking step executed in step 803 is implemented in one embodiment of the present invention. Additionally, it should be noted that in an alternate embodiment of the present invention, the entries may be deleted by MSC 101. Note that when sending the updated subscriber service profile information in step 802, the communications system of the present invention may merely send a portion of information within the subscriber service profile that has been modified, rather than sending the entire subscriber service profile. With respect to step 606, HLR 121 of MSC 101 may include some type of algorithm (based on SID, proximity of the systems, FIFO, etc.) to decide if an MSC should be added to the last visited list. The processes illustrated in FIGS. 6-8 may each be controlled by software running on a data processing system such as data processing system 500 of FIG. 5. However, the process may, alternately, be performed exclusively by hardware or firmware, or by a combination of hardware, firmware and/or software. When implemented as software, the software is stored within a data storage device, such as storage devices 220 and 240, or on some other transferable storage media such as a CD-ROM, floppy disc or tape, and loaded into RAM 214 for execution. Furthermore, the forgoing steps of the illustrated method are executed by HLR 121 for mobile subscribers homed, or assigned, to MSC 101. The foregoing description is one embodiment of the present invention. Specific details are set forth to provide an understanding of this embodiment. However, those skilled in the art will recognize that the present invention may be embodied in alternate forms, or with modifications, and may be practiced with substitutions and other changes to the present embodiment. Although the present invention and its advantages have been described in detail, it should be understood that various modifications, substitutions and alterations can be made to the embodiment of the invention described herein without departing from the spirit and scope of the invention as defined by the appended claims.
A system and method is implemented within a telecommunications network, such as a cellular telephone network, for maintaining updated profile information for each mobile subscriber registered within the network. Updated profile information about each mobile subscriber is maintained within a particular mobile switching center currently communicating with the particular mobile subscriber. This process is performed with minimal utilization of bandwidth between the various mobile switching centers in the telecommunications network by maintaining subscriber service profile information within mobile switching centers, even though the associated mobile subscriber has roamed from that mobile switching center. When the subscriber service profile information is updated, then the subscriber service profile information is downloaded to a mobile switching center currently serving the mobile subscriber.
7
BACKGROUND In many subterranean environments, such as wellbore environments, downhole tools are used to carry out a variety of procedures. For example, downhole tools may comprise a variety of flow control valves, safety valves, flow controllers, packers, gas lift valves, sliding sleeves, and other well tools. Many of these well tools can be hydraulically controlled via input from hydraulic control lines that are run downhole. Conventional well tools often rely on a dedicated hydraulic control line or lines routed to a specific tool positioned in a wellbore. The number of well tools placed downhole can be limited by the number of control lines available in a given wellbore. The wellbore and/or wellbore equipment, e.g. packers, used in a given application also can provide space constraints or routing constraints which limit the number of control lines. Furthermore, even in applications that would allow the addition of control lines, the additional lines tend to slow installation and increase the cost of installing equipment downhole. Attempts have been made to reduce the number of hydraulic control lines necessary to carry out given well related procedures. For example, multiplexers have been used to limit the number of hydraulic control lines. However, multiplexing systems often rely on an ability to generate multiple levels of pressure that are interpreted downhole. In some custom designed systems, the maximum number of well tools is limited to a number equal to the number of hydraulic control lines. In other attempts, electric/solenoid controlled valves or custom hydraulic devices and tools have been designed to respond to pressure pulse sequences delivered downhole. However, many such systems have proved to be fairly costly and relatively slow to actuate. SUMMARY In general, the present invention provides a system and method for controlling multiple well tools. A plurality of well tools can be actuated between operational positions. The well tools are coupled to a plurality of multidrop modules with each multidrop module typically being coupled to one or two well tools. A plurality of control lines are connected to the multidrop modules, and the number of multidrop modules and attached well tools can be greater than the number of control lines. Also, each well tool can be actuated individually by providing pressure inputs through one or more of the control lines. The pressure inputs can be provided at a single pressure level. BRIEF DESCRIPTION OF THE DRAWINGS Certain embodiments of the invention will hereafter be described with reference to the accompanying drawings, wherein like reference numerals denote like elements, and: FIG. 1 is a schematic view of a well tool actuation system having a plurality of well tools and multidrop modules deployed in a wellbore, according to an embodiment of the present invention; FIG. 2 is a schematic illustration of another example of the well tool actuation system, according to an alternate embodiment of the present invention; FIG. 3 is a schematic illustration of one example of a multidrop module utilized in the well tool actuation system, according to an embodiment of the present invention; FIG. 4 is a view of the multidrop module illustrated in FIG. 3 but with a different flow pattern, according to another embodiment of the present invention; FIG. 5 is a view of the multidrop module illustrated in FIG. 3 but in a different state of actuation, according to another embodiment of the present invention; FIG. 6 is a table illustrating one example of a multidrop module program for individually actuating specific well tools, according to an embodiment of the present invention; FIG. 7 is a table illustrating another example of a multidrop module program for individually actuating specific well tools, according to an alternate embodiment of the present invention; FIG. 8 is a schematic illustration of another example of the well tool actuation system, according to an alternate embodiment of the present invention; FIG. 9 is a schematic illustration of another example of the well tool actuation system, according to an alternate embodiment of the present invention; FIG. 10 is a schematic illustration of one example of a multidrop module utilized in the well tool actuation system illustrated in FIGS. 8 and 9 , according to an embodiment of the present invention; FIG. 11 is a view of the multidrop module illustrated in FIG. 10 but in a different state of actuation, according to an embodiment of the present invention; FIG. 12 is a view of the multidrop module illustrated in FIG. 10 but in a different state of actuation, according to an embodiment of the present invention; FIG. 13 is a table illustrating one example of a multidrop module program for individually actuating specific well tools, according to an embodiment of the present invention; FIG. 14 is a table illustrating another example of a multidrop module program for individually actuating specific well tools, according to an alternate embodiment of the present invention; FIG. 15 is a schematic illustration of one example of a multidrop module with a module program override mechanism, according to an embodiment of the present invention; FIG. 16 is a view of the multidrop module illustrated in FIG. 15 but with a different flow pattern, according to another embodiment of the present invention; FIG. 17 is a view of the multidrop module illustrated in FIG. 15 but with a different flow pattern, according to another embodiment of the present invention; FIG. 18 is a view of the multidrop module illustrated in FIG. 15 but with a different flow pattern, according to another embodiment of the present invention; FIG. 19 is a view of the multidrop module illustrated in FIG. 15 but with a different flow pattern, according to another embodiment of the present invention; FIG. 20 is a schematic illustration of another example of a multidrop module with a module program override mechanism, according to an alternate embodiment of the present invention; FIG. 21 is a view of the multidrop module illustrated in FIG. 20 but with a different flow pattern, according to another embodiment of the present invention; FIG. 22 is a view of the multidrop module illustrated in FIG. 20 but with a different flow pattern, according to another embodiment of the present invention; FIG. 23 is a view of the multidrop module illustrated in FIG. 20 but with a different flow pattern, according to another embodiment of the present invention; FIG. 24 is a view of the multidrop module illustrated in FIG. 20 but with a different flow pattern, according to another embodiment of the present invention; and FIG. 25 is a view of the multidrop module illustrated in FIG. 20 but with a different flow pattern, according to another embodiment of the present invention. DETAILED DESCRIPTION In the following description, numerous details are set forth to provide an understanding of the present invention. However, it will be understood by those of ordinary skill in the art that the present invention may be practiced without these details and that numerous variations or modifications from the described embodiments may be possible. The present invention generally relates to a system and method for controlling well tools. A multidrop module is deployed between a well tool and control lines that extend to the surface. Multiple well tools and associated multidrop modules can be coupled to the control lines, and the multidrop modules require only one level of pressure for operation. Use of the multidrop modules enables selection of one or several well tools for actuation out of all of the well tools deployed. Additionally, each multidrop module is able to memorize the last selection made based on the pressure input delivered downhole via the control lines. Referring generally to FIG. 1 , one embodiment of a well tool actuation system 30 is illustrated. The actuation system 30 may be mounted along or otherwise coupled to equipment 32 used in a subterranean environment, e.g. a wellbore environment. Equipment 32 comprises, for example, a downhole completion or other equipment utilized in a wellbore 34 , such as an oil or gas related wellbore. In the embodiment illustrated, well tool actuation system 30 comprises a plurality of well tools 36 . Actuation of well tools 36 is based on fluid inputs supplied along a plurality of control lines, e.g. control lines 38 , 40 and 42 ( 1 , 2 and 3 ). In this embodiment, three control lines are utilized, and the control lines extend upwardly to, for example, a surface location. The number of well tools 36 that can be controlled independently can be greater and even substantially greater than the number of control lines. In FIG. 1 , the well tool illustrated in dashed lines represents one or more well tools in addition to the other illustrated well tools. The well tools 36 can be actuated by fluid, such as hydraulic fluid flowing through one or more of the control lines 38 , 40 , 42 . Additionally, the plurality of well tools 36 may comprise a variety of well tool types and combinations of tools depending on the application. For example, the well tools 36 may comprise flow control valves, flow controllers, packers, gas lift valves, sliding sleeves, and other tools that can be actuated by a fluid, e.g. hydraulic fluid. In FIG. 1 , the well tools 36 are illustrated as dual-line tools that are actuated via inputs from two control lines. However, the well tools 36 also may comprise single-line tools, as illustrated in FIG. 2 . As illustrated in FIG. 1 , each dual-line well tool 36 is coupled with a multidrop module 44 that may be positioned downhole proximate the corresponding well tool 36 . In the embodiment illustrated in FIG. 2 , a pair of single-line tools can be coupled with each multidrop module 44 . The plurality of multidrop modules 44 serves to control the flow of actuating fluid and thus the actuation of the corresponding well tools 36 . In the embodiments illustrated, each well tool can be actuated individually via single level pressure inputs provided to the multidrop modules 44 through, for example, one of the control lines. Each multidrop module 44 has a specific program, as illustrated schematically in the diagrams labeled with reference numeral 46 in FIG. 1 . For example, each multidrop module 44 can be programmed to respond and to enable actuation of its corresponding well tool 36 upon receipt of a specific number of pressure pulses. The number of pressure pulses, e.g. single level pressure pulses, applied can be detected and tracked by indexers that are unique to specific multidrop modules 44 , as explained in greater detail below. Referring generally to FIG. 3 , one embodiment of a multidrop module 44 is illustrated. In this embodiment, each multidrop module 44 comprises a housing 48 containing a valve 50 , such as a two position valve, that may be positioned between an actuation position and a no-actuation position. By way of example, valve 50 may be mounted within housing 48 for translating/sliding motion along an interior 52 of housing 48 . Valve 50 is operatively coupled with an indexer 54 across a piston 56 . In this example, indexer 54 comprises an indexer sleeve 58 and a cooperating indexer pin 60 that may be mounted to housing 48 . The indexer 54 may be a two-position/x-increments, J-slot indexer programmed to shift the multidrop module 44 to an actuation position at a predetermined number of pressure inputs applied to the indexer 54 via control line 38 . As illustrated, a seal 61 may be positioned about piston 56 to form a seal with an interior surface of housing 48 . Additionally, a return spring 62 can be positioned within housing 48 to act against valve 50 in a direction that provides a bias against the pressure applied to indexer 54 and piston 56 via control line 38 . For example, valve 50 is displaced via piston 56 when a pressure input is applied through control line 38 , and return spring 62 returns valve 50 in an opposite direction once the pressure input is reduced. When pressure is applied to control line 38 , the piston 56 moves against spring 62 and compresses the spring. The stroke of piston 56 is limited by the slot profile of indexer sleeve 58 and the cooperating indexer pin 60 . When pressure is bled from control line 38 , the return spring 62 forces piston 56 in an opposite direction. Again, the slot profile of indexer sleeve 58 and cooperating indexer pin 60 limits the stroke of piston 56 and thus determines its final position. Each time pressure is applied via control line 38 , the indexer 54 is advanced to its next increment. Depending on the specific indexer program, e.g. indexer slot profile, valve 50 either remains at its current position or is shifted to its other position. For example, indexer 54 can be programmed with an appropriate slot profile so the valve 50 is in an “actuation” position at the first increment, i.e. following the first pressure input via control line 38 , and subsequently remains in the “no-actuation” position for the remaining indexer increments. If the indexer 54 has x increments, then x applications of the pressure input, e.g. a single-level pressure input, through control line 38 moves the indexer through its entire profile. In FIG. 3 , valve 50 is positioned in an actuation position that enables actuation of the corresponding well tool 36 . In this position, hydraulic power can be transmitted along control line 40 , through multidrop module 44 , and into a well tool actuation line 64 to actuate well tool 36 in a first direction. For example, if well tool 36 comprises a valve, actuation line 64 may be an “open” line that enables opening of the valve. When multidrop module 44 remains in this actuation position, hydraulic power also can be transmitted along control line 42 , through multidrop module 44 , and into a second well tool actuation line 66 to actuate well tool 36 to a different operational position, as illustrated in FIG. 4 . If well tool 36 comprises a valve, for example, actuation line 66 may comprise a “close” line that enables closing of the valve. In some embodiments, the well tool 36 comprises a fluid volume that is returned during actuation. For example, actuation of well tool 36 via actuation line 64 causes the flow of return fluid along actuation line 66 . Similarly, actuation of well tool 36 via actuation line 66 causes the flow of return fluid along line 64 . Upon application of the predetermined or programmed number of pressure inputs to multidrop module 44 via control line 38 , indexer 54 and multidrop module 44 are shifted to the no-actuation position, as illustrated in FIG. 5 . As illustrated, indexer 54 , via piston 56 , holds valve 50 at a position that prevents actuation of well tool 36 regardless of the pressure inputs applied along control line 40 or control line 42 . The valve 50 remains in the no-actuation position until the appropriate number of pressure inputs are applied through control line 38 to cause shifting of indexer 54 , and thus valve 50 , back to the actuation position illustrated in FIG. 3 . Each indexer may be uniquely programmed, e.g. contain a unique slot profile, to correspond with the desired number of pressure inputs required to transition the multidrop module 44 from an actuation position to a no-actuation position and back again. The indexer program for each multidrop module is unique relative to the indexer program for other multidrop modules. In some embodiments, each multidrop module has its own unique program. Accordingly, every time control line 38 is pressurized with a pressure input, every multidrop module 44 transitions through an increment via its indexer 54 . However, any resulting change in position of a specific valve 50 depends on the unique program or slot profile of its indexer. The indexers 54 of the various multidrop modules 44 can be programmed to enable selection of one tool at a time or several tools at a time. The changes, of course, are predictable based on the predetermined program, e.g. slot profile, of each indexer sleeve. As illustrated in FIG. 6 , for example, a plurality of multidrop modules 44 can be uniquely programmed. In this example, a first pressure input to the multidrop modules 44 causes shifting of the first module to an actuation position, while the second and third modules remain in a no-actuation position. A second pressure input causes the second incremental movement of the indexers 54 in each multidrop module 44 , resulting in shifting of the second multidrop module to an actuation position and the first and third multidrop modules to a no-actuation position. A third pressure input applied to the multidrop modules causes the first and second modules to remain or shift to a no-actuation position, while the third multidrop module is transitioned to an actuation position. However, many different programs can be applied for shifting the multidrop modules between actuation and no actuation positions, as desired for a specific application. Additionally, multiple or all of the multidrop modules can be programmed to shift to an actuation position or a no-actuation position at the same time, as illustrated in FIG. 7 . In this example, the first pressure input and the first incremental movement of the indexers 54 causes all of the illustrated multidrop modules to shift to an actuation position. Subsequent pressure inputs cause the multidrop modules to be individually transitioned between actuation and no-actuation positions, as illustrated. Referring generally to FIGS. 8 and 9 , another embodiment of well tool actuation system 30 as illustrated. In this embodiment, well tools 36 and multidrop modules 44 are controlled via a pair of control lines 68 , 70 . As illustrated, each multidrop module 44 can each be used to control the actuation of, for example, a single dual-line tool, as illustrated in FIG. 8 . Alternatively, the multidrop modules 44 can be used to control the actuation of single-line tools 36 , such as the pairs of single-line tools 36 controlled by each multidrop module 44 , as illustrated in FIG. 9 . An example of a multidrop module 44 that can be utilized in a two control line system is illustrated in FIG. 10 . In this embodiment, each multidrop module 44 again comprises the housing 48 that contains valve 50 . However, valve 50 is a three position valve having three different operational positions comprising a first actuation position, a second actuation position, and a no-actuation position. If the well tool 36 comprises a valve or similar device, the first actuation position can be an “open tool” position and the second actuation position can be a “close tool” position. The three position valve 50 is operatively coupled with an indexer 54 across a piston 56 . In this embodiment, however, indexer 54 comprises a three position indexer, such as a three position/x increment, J-slot indexer, able to shift valve 50 between its three operational positions. When pressure is applied to control line 68 , the piston 56 moves against spring 62 and compresses the spring. The stroke of piston 56 is limited by the slot profile of indexer sleeve 58 and the cooperating indexer pin 60 . When pressure is bled from control line 68 , return spring 62 forces piston 56 in an opposite direction. Again, the slot profile of indexer sleeve 58 and cooperating indexer pin 60 limits the stroke of piston 56 and thus determines its final position. Each time pressure is applied via control line 68 , the indexer 54 is advanced to its next increment. Depending on the specific indexer program, e.g. indexer slot profile, valve 50 either remains at its current position or is shifted to its next position. For example, indexer 54 can be programmed with an appropriate slot profile so the valve 50 is in a “close tool” position at the first increment, in an “open tool” position for the second increment, and in the “no-actuation” position for the remaining indexer increments of the indexer profile. If the indexer 54 has x increments, then x applications of the pressure input, e.g. a single-level pressure input, through control line 68 moves the indexer through its entire profile and back to the “close tool” position. In FIG. 10 , valve 50 is positioned in the first actuation position, e.g. an open tool position, that enables actuation of the corresponding well tool 36 in a first direction. In this position, hydraulic power can be transmitted along control line 70 , through multidrop module 44 (via, in part, a flow passage 72 through valve 50 ), and into the well tool actuation line 64 to actuate well tool 36 in a first direction, e.g. to open the well tool. Return fluid flows can be conducted through actuation line 66 , through multidrop module 44 , and into control line 68 via a secondary flow passage 74 . A check valve 76 is placed along secondary flow passage 74 to allow movement of return flow from multidrop module 44 to control line 68 while blocking the reverse flow of fluid during application of pressure inputs through control line 68 . Upon application of the predetermined number of pressure inputs to multidrop module 44 via control line 68 , indexer 54 and multidrop module 44 are shifted to the no-actuation position, as illustrated in FIG. 11 . Indexer 54 holds valve 50 , via piston 56 , at a position that prevents actuation of well tool 36 regardless of the fluid pressure applied along control line 70 . The valve 50 remains in the no-actuation position until the appropriate number of pressure inputs are applied through control line 68 to cause shifting of indexer 54 , and thus valve 50 , to the second actuation position, e.g. the close tool position, illustrated in FIG. 12 . In this position, hydraulic power can be transmitted along control line 70 , through multidrop module 44 (via flow passage 72 through valve 50 ), and into the well tool actuation line 66 to actuate well tool 36 in a second direction, e.g. to close the well tool. Return fluid flows can be conducted through actuation line 64 , through multidrop module 44 , and into control line 68 via the secondary flow passage 74 . Again, each indexer can be programmed with a unique slot profile that corresponds to the desired number of pressure inputs required to transition the multidrop module 44 between the two actuation positions and the no-actuation position. The indexer program for each multidrop module may be unique relative to the indexer program for other multidrop modules. In some embodiments, each multidrop module may have its own individual program. Accordingly, every time control line 38 is pressurized with a pressure input, every multidrop module 44 transitions through an increment via its indexer 54 . However, any resulting change in position of valve 50 depends on the unique program or slot profile of its indexer. As illustrated in FIG. 13 , for example, a plurality of multidrop modules 44 can be uniquely programmed. In this example, a first pressure input to the multidrop modules 44 causes shifting of the first module to a first actuation position, while the second and third modules remain in a no-actuation position. A second pressure input causes the second incremental movement of the indexers 54 in each multidrop module 44 , resulting in shifting of the first multidrop module to a second actuation position, while the second and third modules remain in a no-actuation position. A third pressure input applied to the multidrop modules causes the second multidrop module to shift to a first actuation position, while the first and third multidrop modules shift or remain in a no-actuation position. A fourth pressure input causes the second multidrop module to move to a second actuation position, while the first and third modules remain in a no-actuation position. A fifth pressure input causes the third multidrop module to shift to a first actuation position, while the first and second multidrop modules shift or remain in a no-actuation position. The sixth pressure input causes the third multidrop module to shift to a second actuation position, while the first and second multidrop modules remain in a no-actuation position. Here again, the pressure inputs can all be provided at the same pressure level. Similar to the first illustrated embodiment, this embodiment allows the use of many different programs for shifting the multidrop modules between first actuation, second actuation, and no-actuation positions, as desired for a specific application. Additionally, multiple or all of the multidrop modules can be programmed to shift to an actuation position or a no-actuation position at the same time. As illustrated in FIG. 14 , for example, the first pressure input and the first incremental movement of the indexers 54 causes all of the illustrated multidrop modules to shift to a first actuation position. The second pressure input through control line 68 shifts the multidrop modules to a second actuation position. Subsequent pressure inputs may cause the multidrop modules to be individually transitioned between first actuation, second actuation, and no-actuation positions, as illustrated. In another embodiment, each multidrop module may comprise an override mechanism that enables selective actuation of all well tools to a default position, e.g. a closed position, at any selected time. The override mechanism may be particularly useful in well actuation systems operating dual-line well tools. Referring generally to FIG. 15 , one embodiment of a multidrop module 44 incorporating an override mechanism 78 is illustrated. In this embodiment, the multidrop module 44 comprises a two position indexer 54 , such as the indexer described with reference to FIG. 3 , and a three position valve 50 , such as the valve described with reference to FIG. 10 . By way of example, the indexer 54 may utilize the J-slot indexer sleeve 58 that cooperates with indexer pin 60 . However, the override mechanism 78 is able to override the J-slot indexer sleeve 58 at any time when a given sequence of pressure is applied. This allows all well tools 36 to be moved to a default position, such as a closed position, at any desired point of time. Override mechanism 78 may have a variety of configurations designed to capture and hold valve 50 at a position that allows fluid flow through the multidrop module 44 to actuate well tool 36 to a desired default position. In the embodiment illustrated, however, override mechanism 78 comprises a locking mechanism 80 mounted within housing 48 and having a portion slidably received in an extended portion 82 of piston 56 . Valve 50 and extended portion 82 can be forced along locking mechanism 80 toward the close-all-tools position. Movement of extended portion 82 along locking mechanism 80 compresses an override mechanism spring 84 . The multidrop module 44 illustrated in FIG. 15 can be shifted between an actuation position, e.g. an open tool position, a no-actuation position, e.g. cannot open tool position, and a close-all-tools position. The indexer 54 is used to selectively transition valve 50 between the first two operational positions. For example, the indexer 54 can be used to transition multidrop module 44 to the actuation position, illustrated best in FIG. 15 . In this position, fluid under pressure can be supplied through control line 40 and routed through valve 50 to actuation line 64 for actuating, e.g. opening, the well tool 36 . Application of pressure inputs through control line 38 moves indexer 54 the desired number of increments to transition valve 50 and multidrop module 44 to the no-actuation position, illustrated in FIG. 16 . The indexer 54 is operated as described above by applying pressure inputs, e.g. single level pressure inputs, via control line 38 which shift piston 56 in one direction, while return spring 62 causes movement in the opposite direction to incrementally shift indexer 54 along its predetermined profile. In the position illustrated in FIG. 16 , tool 36 cannot be actuated even if fluid is supplied via control line 40 and/or control line 42 . Any fluid supplied by control line 42 is blocked from moving through valve 50 by a check valve 86 . However, all of the valves 50 of the plurality of multidrop modules 44 can be shifted to the close-all-tools position by application of a given pressure sequence. For example, sufficient pressure can be applied via control line 42 to act against valve 50 and to cause valve 50 to shift to the left, as illustrated in FIG. 17 by arrow 88 . Check valve 86 prevents pressure from being transmitted to well tool 36 . The translation of valve 50 and piston 56 compresses override mechanism spring 84 until piston extension 82 slides a sufficient distance over locking mechanism 80 , as illustrated in FIG. 18 . While spring 84 is compressed, the two position indexer 54 does not move. Furthermore, while maintaining pressure in control line 42 , pressure is applied through control line 40 to cause translation of locking mechanism 80 in a manner that holds or locks main piston 56 and valve 50 in the close-all-tools position. The piston 56 remains in this position as long as pressure is maintained in control line 40 . At this stage, pressure can be bled from control line 42 which allows the pressurized fluid in control line 40 to shift well tool 36 to a default position, e.g. a closed position, as illustrated in FIG. 19 . The ability to shift all multidrop modules 44 to the close-all-tools position enables all of the well tools 36 to be simultaneously actuated to a desired default position. In other words, the programmed valve positions directed by indexers 54 can be overridden to force all well tools 36 to the default position. If, for example, the well tools 36 comprise downhole valves, all the valves can be forced to a closed position at any time. Another embodiment of multidrop module 44 is illustrated in FIG. 20 . In this embodiment, multidrop module 44 combines the override mechanism 78 with a three position valve 50 and a three position indexer 54 . The three position valve 50 in combination with the three position indexer 54 enables valve 50 and multidrop module 44 to have a first actuation position, e.g. open tool position, a second actuation position, e.g. a close tool position, and a no-actuation position. Additionally, the override mechanism 78 enables all of the valves 50 and all of the multidrop modules 44 in a given well tool actuation system 30 (e.g., see FIG. 1 ) to be moved to a default position simultaneously. As described above, when a given pressure sequence is applied, the override mechanism 78 is able to override the valve positions determined by the indexers 54 . For example, all of the well tools in system 30 can be moved to a closed position simultaneously. In FIG. 20 , valve 50 and multidrop module 44 are positioned in the first actuation, e.g. open tool, position. In this position, hydraulic power can be transmitted along control line 40 , through multidrop module 44 , and into a well tool actuation line 64 to actuate well tool 36 in a first direction. For example, if well tool 36 comprises a valve, actuation line 64 may be an “open” line that enables opening of the valve. Upon input of the predetermined number of pressure inputs to move indexer 54 through a corresponding predetermined number of increments, valve 50 and multidrop module 44 may be shifted to a no-actuation position, as illustrated in FIG. 21 . In this position, valve 50 prevents actuation of well tool 36 regardless of whether tool actuation fluid is supplied through control line 40 or control line 42 . An additional pressure input or inputs via control line 38 causes indexer 54 to shift valve 50 to the second actuation, e.g. close tool, position. In this position, pressurized fluid can again flow through control line 40 , multidrop module 44 , and actuation line 66 to actuate well tool 36 , e.g. close well tool 36 , as illustrated in FIG. 22 . Whether well tool 36 is actuated to the first actuation position or the second actuation position, return fluids can be routed through multidrop module 44 , through check valve 86 , and into control line 42 . The latter embodiment also enables simultaneous shifting of all valves 50 and all multidrop modules 44 to a default position at any selected time upon the application of a given pressure sequence. If well tool actuation system 30 (e.g., see FIG. 1 ) comprises well tools in the form of valves, for example, all the valves can be closed simultaneously at any desired time. To override the programmed tool positions, sufficient pressure is applied via control line 42 to act against valve 50 and cause valve 50 to shift to the left, as illustrated in FIG. 23 . Check valve 86 again prevents pressure from being transmitted to well tool 36 . While maintaining pressure in control line 42 , pressure is applied through control line 40 to cause translation of locking mechanism 80 in a manner that holds or locks main piston 56 and valve 50 in the close-all-tools position, as illustrated in FIG. 24 . At this stage, pressure can be bled from control line 42 which allows the pressurized fluid in control line 40 to shift well tool 36 to the default position, e.g. the closed position, as illustrated in FIG. 25 . Any return fluids can freely flow through actuation line 64 , through check valve 86 , and into control line 42 . All of the well tools 36 can be similarly and simultaneously closed or otherwise actuated to a default position. Well tool actuation system 30 (e.g., see FIGS. 1 , 2 , 8 and 9 ) can be designed in a variety of configurations for use in a variety of wellbores and other subterranean environments. The number of multidrop modules can be greater and even substantially greater than the number of control lines used to control the multidrop modules and their corresponding well tools. Additionally, even if the multidrop modules are greater in number than the control lines, the multidrop modules and their corresponding well tools can be controlled individually with pressure inputs directed to all of the multidrop modules at a single pressure level. Furthermore, the type and configuration of the well tools 36 and the multidrop modules 44 can differ from one application to another (e.g., see FIGS. 3 , 10 and 15 ). The components within the multidrop modules also can be selected according to the desired actuation for a given application or environment. For example, a variety of valve styles and indexer styles can be utilized in a given multidrop module. Additionally, the override mechanism can be constructed in different forms, and a variety of locking mechanisms can be used to hold the valves in the override position. Accordingly, although only a few embodiments of the present invention have been described in detail above, those of ordinary skill in the art will readily appreciate that many modifications are possible without materially departing from the teachings of this invention. Such modifications are intended to be included within the scope of this invention as defined in the claims.
Systems and methods for downhole completions. A downhole running tool can have a body having a bore formed therethrough. A latch member can be disposed on a first portion of the body. A reset member can be disposed on a second portion of the body. A conduit can be formed within a sidewall of the body. The conduit can be located between the first and second portions of the body. A pressure relief port can be disposed at a first end of the conduit; and a first flow port can be disposed at a second end of the conduit. The pressure relief port and first flow port can be in communication with an outer diameter of the body.
4
This application is entitled to and hereby claims the priority of co-pending U.S. Provisional application, Ser. No. 60/519,252 filed Nov. 13, 2003. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is related to the field of inter-computer networking and more particularly to a methodology and/or protocol that requires network header metadata, such as access control identifiers (ACIs), to be transitioned and operated upon among a plurality of separately defined computer network domains. The present invention is also related to the field of encrypted computer network communication and, more particularly, to a methodology for implementing functions that require unencrypted data in a secure computer network. 2. Description of the Related Art A network typically requires the transmission of access control identifiers (ACIs) at various layers of a communication stack to enable successful completion of an end-to-end (E2E) transmission. Across that E2E path, however, are various service facilities that utilize the ACIs, whether in the header or embedded in the payload, for functions such as routing, inspection, user or location identification, forwarding, etc. When such a service facility, e.g., a proxy server, post office or other application-based traversal mechanism, is utilized, the ACIs are lost and are no longer available to a session protocol. This loss of ACIs, for example in IP identifiers, occurs due to the layer mechanisms inherent in the protocol stack. Specifically, the processing elements operating at a particular layer can operate only on ACIs available to that particular layer and not at layers above or below. As a result, the intervening service facility causes services such as access control capability to be lost and/or terminated, leaving only routing data available for reuse. Various prior art methods have been proposed which teach that a singular self-contained service can be used to inspect the payload and compare it against a store of known rules prior to forwarding. Service facilities disclosed for such methods can operate on predefined network topologies and are used within these topologies to provide some service, e.g. forwarding or inspection. These prior art approaches provide no inheritance of the ACIs across services within the communications path and are limited to cascading services performed within a single network domain. In sum, existing service facilities within networks are uni-directional, self-contained and/or require known network-specific topologies. Services based on the existing art have limited session facilities on the network, requiring service functions to be embedded within the application itself or within a series of applications as part of the application codes/functions. Session persistence is only maintained by the application and is otherwise terminated when the session-layer ACIs are lost between applications or service facilities. The existing art does not provide service mechanisms that allow bi-directional movement of the ACIs as is required in a session-based service. Additionally, a secure computer network requires the transmission of encrypted data with associated ACIs from a data source to a specified data destination. However, many computer network functions such as intrusion detection, load balancing, TCP/IP acceleration, etc. need to operate on cleartext or unencrypted data and will not perform properly when processing encrypted data. Thus, functions requiring cleartext, when embedded within a conventional secure network, do not perform properly. A mechanism for providing access control on network communications used by the Department of Defense is to place identifiers on Internet Protocol (IP) data streams. These identifiers can be checked at the source and destination host machines to determine if the sender can send that type of information and whether the receiver can receive that type of information. In a standard client server environment, where all systems between the two host systems operate only on the IP layer, this access control mechanism has been shown to work well and has many government approvals for its operation. However, when a proxy, service facility or other application-based traversal mechanism is utilized, IP identifiers that are placed on the individual packets are lost and thus network-level access control mechanisms cannot be utilized. This loss is consistent with the operation of the standard TCP/IP and IPsec protocol stacks which operate in a layered fashion where processing elements operating at a particular layer can see all data at that level and above, but none below. Since the proxy/application is at the application layer, it cannot generally see information at the IP layer. Therefore, a need exists for a system and method by which header data at different layers of the communications protocol stack is maintained throughout a network session that traverses multiple networks and domains. SUMMARY OF THE INVENTION In view of the foregoing, one object of the present invention is to provide a session-level bridging mechanism to retain, operate on and forward ACIs across a plurality of functionalities. Another object of the present invention is to provide an inter-networking method that provides for metadata utilization for the life of a session even on unknown networks being traversed, allowing for metadata utilization, reutilization, and modification in both the send and receive paths (bi-directional), and allowing for transport over segments requiring that ACIs be embedded at different layers of the communications stack. A further object of the present invention is to provide a session-level service-to-service mechanism that traverses from within one network domain to other known or unknown network domain, enforcing and utilizing header metadata across the combined inter-network. A still further object of the present invention is to provide an inter-networking service-to-service mechanism that allows ACIs to be transmitted and utilized among networks where the method of transfer of the ACIs may be at different layers of the network stack. Yet another object of the present invention is to provide a mechanism to retain ACIs across a functionality that requires cleartext within an encrypted communication. A still further object of the present invention is to provide a function embedding unit including an ACI virtual private network (VPN) that performs decryption and retains the ACIs, and an ACI VPN that performs encryption and reinserts the ACIs which were traversed across an embedded function requiring non-encrypted data. In accordance with these and other objects, the present invention is directed to a session-level bridging mechanism to retain, operate on and forward ACIs across a plurality of functionalities. This plurality of functionalities defines a session as utilized on multi-tier applications that operate across multiple E2E network services. In this manner, a service-to-service protocol invention, with an accompanying retention store that allows ACIs to transition from one peer-to-peer connection to another peer-to-peer connection, is defined. As a session protocol, the present invention is utilized bi-directionally, both on the forward communication path as well as on the return path, without requiring any application awareness or internal mechanisms to transition between network connections. As used herein, this service-to-service mechanism is referred to as the F-Function. The F-Function according to the present invention is a session protocol, and becomes a network service for application developers who can thread and bind multiple existing applications (processes) and directories, or any other network service, into a cohesive transaction without application awareness or modification. The present invention may be used advantageously in multi-tier applications that are prevalent in service-oriented architectures or web-service architectures. For example, a content-based access control may be enforced across a multi-tier structure. In the first connection of the session, the client connects to the application tier with network or data ACIs transported in the IP option field. The ACIs are then re-utilized by the application server to connect to a database server. The service facility, having maintained the session data including the ACIs, utilizes an F-Function that applies rules based on the received ACIs so that the proper data at the database server, i.e., data having content which the client is authorized to receive in accordance with the established content-based access control, is accessed and returned to the application server for forwarding to the client. The present invention may also be used advantageously to allow an encrypted network that requires an intermediate node to utilize cleartext functions, such as inspection, by maintaining the ACIs through the application of the F-Function. The F-Function is able to first read the ACIs from the inbound IP stream, retain the ACIs during the inspection processing, and then to place the ACIs on each outbound IP stream such that there is no loss of the ACIs originally placed on the data packets due to the decryption mechanism. Thus, the present invention also provides a mechanism to terminate IP/IPsec data streams that contain ACIs at the device, read and store the ACIs from the inbound IP packets, provide these identifiers on the outbound IP packets and utilize the identifiers to instantiate a secure channel with the destination system. The F-Function protocol and mechanism according to the present invention provides a new network mechanism for creating session controls across an inter-network of networks rather than requiring application-aware internal controls to accomplish session connectivity. These together with other objects and advantages which will become subsequently apparent reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of a multi-domain network connection system that provides multiple service facilities across an E2E session where an F-Function embeds, stores, forwards and processes ACIs between service facilities on both forward and return paths, according to a first embodiment of the present invention. FIG. 2 is a block diagram of the architecture of the F-Function services within the service facilities, according to the present invention. FIG. 3 is a block diagram of the process flow through multiple F-Function services operating within a single service facility and includes multiple E2E connections within the session, according to the present invention. FIG. 4 is a block diagram of the process flow through multiple F-Function services operating among multiple service facilities and includes multiple E2E connections within the session, according to a further embodiment of the present invention. FIG. 5 is a block diagram of the modular design of the service facility providing F-Function based services of FIGS. 1-4 . FIG. 6 is a block diagram of an F-Function transitioning method for transporting ACIs from one connection to another connection at the same layer of the communications protocol stack, according to the present invention. FIG. 7 is a block diagram of an F-Function transitioning method for transporting ACIs from one connection at a first layer to another connection at a higher layer of the communications protocol stack, according to the present invention. FIG. 8 is a block diagram of an F-Function transitioning method for transporting ACIs from one connection at a first layer to another connection at a lower layer of the communications protocol stack, according to the present invention. FIG. 9 shows a block diagram of an embodiment for embedding functions requiring cleartext within a secure network that provides encryption, according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In describing a preferred embodiment of the invention illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose. The specific configurations described in the proceeding discussion of the present invention are illustrative of the invention's methods and in fact these methods can be used to construct many complex structures and topologies and are building blocks for a network. As shown in FIG. 1 , the present invention is directed to a system and a methodology/protocol for enabling interconnected networks, each defined as a separate domain 51 , 52 , 53 , 54 , to carry, replicate and reutilize ACIs within the packet headers across the multiple domains 51 - 54 along communications path 100 . Service facilities 11 , 12 , 13 within these networks provide various services, such as inspection, and also provide for the forwarding of ACIs. FIG. 1 illustrates specific network service applications 21 , 22 , 23 that are incorporated into self-contained network service facilities 11 , 12 , 13 and which provide one or more inter-service mechanisms referred to as F-Functions 61 , 62 . These specific service applications 21 , 22 , 23 in conjunction with the F-Functions 61 , 62 provide the bridging transport mechanism and retention capabilities for ACI utilization and re-utilization across a plurality of networks and computer applications (nodes) typically utilized in a session. The service facilities also provide the capability to transfer the ACIs at different layers of the communications stack 99 of communications path 100 (see FIGS. 6-8 ). The F-Functions 61 - 64 operate within or across one or more service applications 21 , 22 , 23 , 32 , 33 in one or more service facilities 11 , 12 , 13 as shown in FIGS. 2-4 . These service applications can occur in the same or different network domains 51 - 54 . Within service facility 11 , “service A” 21 and “service B” 31 are two of any number of service applications that may be included within a given service facility. As shown in FIG. 5 , these service applications, directed by a service manager 20 , generally include ACI forwarding services, ACI retention storage services, ACI transformation rules services (e.g. tagging, modification), and ACI rules-based forwarding services (based on retention data, e.g. modified ACIs). In the architecture shown in FIG. 2 , “service A” 21 is operating in the forward path. Within facility 12 , “service B” 32 is another service application that can be the same, similar to or a different ACI service application from that of “service A”. “Service B” 32 of service facility 12 is operating in the return path. FIGS. 3 and 4 illustrate the ability of the present invention to interconnect service applications 21 , 22 , 31 , 32 within a service facility 11 and among service facilities 11 , 12 , respectively. FIG. 4 further illustrates implementation of the invention when an intervening application 9 exists between service facilities 11 , 12 . FIG. 3 illustrates an inter-connecting services method that utilizes F-Function 65 for inspecting, modifying/translating, storing and forwarding of ACIs. The method can equally be applied when ACIs are embedded within the payload instead of in the header or when ACIs are in differing layers within the headers. FIG. 3 further illustrates multiple session service applications 21 , 31 in a single domain 51 within a single service facility 11 . FIG. 4 goes on to illustrate the present invention in multiple domains 51 , 52 and with multiple service facilities 11 , 12 , each having multiple session service applications 21 , 22 , 31 , 32 . In FIG. 3 , a client computer/data source 7 a transmits a communications request over a communications channel 100 a to destination 8 b . The service facility 11 with intermediary destination node 8 a intercedes and performs a service on the request prior to re-transmittal of the request from intermediate data source node 7 b . Upon receipt of the request, the service facility 11 retains the session's ACI metadata (or other metadata) at the “service A” 21 ACI store 41 and also utilizes the F-Function 65 to transfer the ACIs from the “service A” 21 ACI store 41 to the “service B” 31 ACI store 44 , where the ACIs are retained for possible use by the “service B” 31 or other service applications later in the session's path. Any of the service applications within the service facility 11 can be applied in this store-then-forward process. The service facility 11 also utilizes the F-Function 65 to place ACIs (or other metadata) back on the outbound communications channel 100 a for connection to the data's destination 8 b. Once the service facility 11 has acted upon the client's request from source 7 a for delivery or request for reply (request for data or processing on data), the request is forwarded to the destination 8 b . The session is then terminated if the request was only for a delivery service. In the event that data was requested, however, the session continues with a reply to the originating client 7 a. Still with reference to FIG. 3 , when data or data processing has been requested, the reply with the requested data in its payload is transmitted on the return path, communications channel 100 b , from the original client destination 8 b back to the client, source 7 a . The service facility 11 again intercedes, with “service B” 31 applying the designated service applications on the stored ACIs retrieved from the “service B” 31 ACI store 44 , and utilizing the F-Function 65 to place ACIs (or other metadata) back on the communication channel 100 b for connection to the data's return destination, namely source 7 a. FIG. 4 illustrates two additional elements of the present invention. First, FIG. 4 illustrates how F-Functions 61 , 63 , 65 , 66 are utilized when cascading inter-connecting service applications 21 , 22 , 31 , 32 are required in a multi-domain 51 , 52 network. Secondly, FIG. 4 also illustrates use of the present invention where a multi-tier application processing architecture is in use between service facilities 11 , 12 . Cascading inter-connecting services operate independently, with or without an application 9 in the communications path 100 . In FIG. 4 , the client computer/data source 7 a transmits a communications request over the forward (or outbound) communications channel 100 a to application server 9 and destination 8 b within network domain 52 . The service facility 11 with intermediate destination node 8 a intercedes prior to delivery to the application server 9 , and retains the session's ACI metadata (or other metadata) at “service A” 21 ACI store 41 . The service facility 11 applies the designated service applications on the request and forwards the extracted ACIs to the “service B” 31 ACI store 44 for later session use. The service facility 11 also utilizes the F-Function 61 to transfer ACI metadata from the domain 51 “service A” 21 ACI store 41 to the domain 52 “service A” 22 ACI store 42 where the ACI metadata is retained and can be utilized by domain 52 “service A” 22 service applications later in the session's path. Any of the service applications within the service facilities 11 , 12 can be applied in this store-or-forward process. In both FIGS. 3 and 4 , as well as any other implementations of the present invention, the transfer of the ACIs from the “service A” ACI store 41 to the “service B” ACI store 44 may occur by “pushing” thereof as has already been described. Alternatively, this transfer may be deferred, with only the ACI store 41 retaining the ACIs on the inbound path. Then, when a reply has been requested and is returned along the return communications path 100 b , the “service B” service application may “pull” the ACIs retained in the ACI store 41 to the ACI store 44 for use on the return path. Such “push” and “pull” technologies for information retrieval and forwarding are known to persons of ordinary skill in the art. Furthermore, while the ACI stores 41 , 42 , 44 , 45 are shown herein as separate storage areas for the purposes of clarity in description, these areas are logical stores and may in fact be embodied together in a single memory device as would be known by persons of ordinary skill in the art. Continuing with FIG. 4 , the service facility 11 further utilizes the F-Function 65 to transfer ACI metadata from the domain 51 “service B” 31 ACI store 44 to the domain 52 “service B” 32 ACI store 45 where the ACI metadata is retained and can be utilized by domain 52 “service B” 32 service applications in the next connection in the session along communications path 100 . Any of the service applications within the service facilities 11 , 12 as described above can be applied in this store-or-forward process. Finally, the service facility 12 utilizes the F-Function 63 to place ACIs (or other metadata) on the communication channel 100 a in domain 52 for connection to the data's destination 8 b. At this point the client's request for data from source 7 a in domain 51 has been forwarded to its destination 8 b in domain 52 and is processed. In addition to the forward communication service applications 21 , 22 there are return communication service applications 31 , 32 as part of the overall session illustrated in FIG. 4 . In a similar manner to the forwarding of ACI/metadata, the retained ACIs within the stores 41 , 42 , 44 , 45 can be reutilized on the return communication path 100 b . The F-Functions 63 , 65 , 66 continue to be utilized to transfer the ACIs between service applications 21 , 22 , 31 , 32 and their associated storage areas 41 , 42 , 44 , 45 across the service facilities 11 , 12 on the return path 100 b. Continuing in FIG. 4 , a reply with the requested data in its payload is transmitted on the return path, communications channel 100 b , from the original destination 8 b back to the client, source 7 a . The service facility 12 intercedes by utilizing domain 52 “service B” 32 , and applies the designated service applications from the retained ACIs at the “service B” 32 ACI store 45 prior to delivery to the application server (business application) 9 where the reply is then processed. The service facility 12 utilizes the F-Function 66 to transfer ACIs from the domain 52 “service B” 32 ACI store 45 to the domain 51 “service B” 31 ACI store 44 where the ACI metadata is retained and can be utilized by service facility 11 service applications in domain 51 in the next connection in the session's path. After processing by application 9 , the domain 52 service facility 12 utilizes the F-Functions 63 , 66 to place ACIs (or other metadata) on the communication channel 100 b for connection to the data's return destination, source 7 a. Once back in domain 51 , the intervening service facility 11 utilizes domain 51 “service B” 31 and applies the designated service applications on the retained ACI retrieved from the “service B” 31 ACI store 44 prior to delivery of the reply to the client 7 a . The service facility 11 also utilizes the F-Function 65 to place ACIs (or other metadata) on the communication channel 100 b for connection to the data's return destination, source 7 a. As generally applicable to both FIGS. 3 and 4 , ACI re-utilization may be filtered if an ACI rules-based service application is incorporated in the service. Furthermore, the ACI stores 41 , 42 , 44 , 45 contain the ACIs from other services 21 , 22 , 31 , 32 in the services facilities 11 , 12 from the outbound (forward) path and metadata from the inbound (return) path which are placed in the headers of the next link in the communications path unless filtered by a rules-based service application. Also, as generally applicable to both FIGS. 3 and 4 , the session end-point terminates the ACI utilization, after which ACI metadata is no longer maintained. Multi-request sessions operate as independent requests for utilization of the F-Function facilities that are provided by the present invention. FIG. 5 details the modular structure of a service facility 11 , the same structure being applicable to service facilities 12 , 13 , etc. The service facility includes an ACI policy manager 17 , a session service manager 20 with multiple service applications 21 , 31 (A, B, C . . . n), and a communications channel manager 13 . The ACI policy manager 17 manages the organization and schema of the ACIs, and provides rules that can be applied to the ACIs, including administrative and metadata maintenance rules insertion, deletion and modification facilities. These rules are preferably input using a policy manager console 200 . The ACI policy manager 17 also provides ACI reader 18 and ACI writer 19 services. The ACI reader facility 18 allows for the transfer of the ACI metadata from the communications channel manager 13 to the ACI policy manager 17 . The ACI writer facility 19 allows for the transfer of the ACI metadata from the ACI policy manager 17 to the communications channel manager 13 for transfer to another service facility 12 or for transfer of data from the ACI policy manager 17 to the ACI store 41 , 44 . The communications channel manager 13 provides header reader 14 and header writer 15 services. The header reader 14 service interprets the header data at various layers of the communications stack 99 and forwards it to the ACI policy manager 17 . The header writer 15 service transfers ACIs from the ACI store 41 utilizing the ACI policy manager 17 and then creates the header data at various layers of the communications stack 99 . The services described in FIG. 5 are used to read and write at various layers within the header communications stack 99 through the header reader 14 and header writer 15 services. These services provide inter-stack services capability for networks that must be transitioned across during the session but which operate at different layers within the communications stack 99 , even when encryption and deencryption services must also operate and occur at different communication layers. In FIGS. 6-8 , the ability of the service facility 11 to transfer ACIs at the same or a different layer of the header communications stack 99 using one or more F-Functions 67 , 68 , 69 is illustrated. Layered network mechanisms representative of those currently in use include ethernet, Internet protocol (IP), traverser and original data. First, as illustrated in FIG. 6 , the service facility 11 may be utilized to receive ACIs from the headers at layer 3 (or any other layer) within the stack 99 on the incoming communications path 100 and to transmit the same, modified or filtered ACIs on an outgoing communications path 100 in the headers at the same layer of the communications stack. Second, the service facility 11 may be utilized to receive ACIs from the headers at layer 3 (or any other layer) within the stack 99 on the incoming communications path 100 and to transmit the same, modified or filtered ACIs on an outgoing communications path 100 in the headers at a higher layer of the communications stack, representatively layer 4 , as illustrated in FIG. 7 . Third, the service facility 11 may be utilized to receive ACIs from the headers at layer 3 (or any other layer) within the stack 99 on the incoming communications path 100 and to transmit the same, modified or filtered ACIs on an outgoing communications path 100 in the headers at a lower layer of the communications stack, representatively layer 2 , as illustrated in FIG. 8 . As described herein, the present invention may be used in multi-tier applications that are prevalent in service-oriented architectures or web-service architectures to enforce a content-based access decision across a multi-tier structure. In the first connection of the session, the client may connect to the application tier with network or data ACIs transported at the network layer (layer 3 ). These ACIs are retained by an intervening service facility and then re-utilized by the application server to connect to a database server, with the service facility utilizing an F-Function that applies rules based on the received ACIs so that the proper data at the database server is accessed and returned to the application server while retaining the session data applied by the F-Function as ACI data to the client connection. With the present invention, ACI data can be transitioned by any layer in the communications stack, for any layer above that layer that does not transition such data. As shown in FIG. 9 , the present invention is further directed to a system and methodology for enabling computer network functions requiring cleartext, such functions being designated herein by the letter FX, to be embedded and effectively operated within a secure network that provides encryption, while retaining associated ACIs from the data source to the data destination. Inbound IP data streams are initiated by a data source 101 . Associated with the data source 101 , is a first ACI virtual private network (VPN) 201 that encrypts the data at the data source 101 and includes all associated network information, including data source and destination-peculiar ACIs. An embedding unit 301 receives the inbound encrypted data from the first ACI VPN 201 . The embedding unit 301 includes a second ACI VPN 321 at the input, an embedded FX function 341 , and a third ACI VPN 361 at the output. In order to read the ACIs that are placed on the IP data stream, the embedding unit 301 is able to first read the identifiers from each inbound IP stream and then to place these identifiers on each outbound IP stream such that the ACIs originally placed on the data packets are not lost. Thus, according to the present invention, the second ACI VPN 321 performs decryption on the incoming data. The ACIs extracted from the decrypted data are stored in a storage device such as a table or other storage element. The FX function 341 is injected, such FX function operating upon the decrypted data such that the FX function is performed correctly, with the stored ACIs being traversed across the FX function without interfering therewith. At the output of the embedding unit 301 , the third ACI VPN 36 then re-encrypts the data stream and re-introduces the traversed ACIs into the outbound encrypted data stream for effective network level access control. A fourth ACI VPN 401 decrypts the data in the outbound data stream at the data destination 501 and uses the ACIs, which have been successfully maintained through the operation of the embedding unit 301 , to ensure proper delivery. As described, the present invention provides a mechanism by which IP/IPsec data streams that contain access control identifiers are terminated at the embedding unit without loss of the ACIs. The data from the inbound IP packets is unencrypted and the ACIs associated therewith are read and stored. The FX function injected in the data stream is performed on the cleartext, after which the data is again encrypted and the stored ACIs are subsequently reintroduced to the outbound IP packets to instantiate a secure channel with the destination system. The foregoing descriptions and drawings should be considered as illustrative only of the principles of the invention. The invention may be implemented in a variety of configurations and is not limited by the configurations illustrated herein. Numerous applications of the present invention in connection with network communications will readily occur to those skilled in the art. Therefore, it is not desired to limit the invention to the specific examples disclosed or the exact construction and operation shown and described. Rather, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
An inter-networking system and method that provides for access control identifier (ACI) metadata utilization for the life of a session even on unknown networks being traversed, allowing for ACI metadata utilization, reutilization, and modification in both the send and receive paths (bi-directional), and allowing for metadata transport over network segments requiring that ACIs be embedded at different layers of the communications stack.
8
FIELD OF THE INVENTION This invention relates to artificial valves, specifically those placed percutaneously by a catheter. The artificial valve disclosed may replace existing valves such as are in the heart or esophagus, or may be placed where fluid flow needs to be maintained in one direction only. BACKGROUND OF THE INVENTION The disclosed invention involves a percutaneously placed artificial valve to maintain bodily fluid flow in a single direction. It opens and closes with pressure and/or flow changes. The invention may be placed anywhere flow control is desired. To facilitate the discussion of the disclosure, use as a heart valve will be addressed. Heart valves are selected because they provide the highest risk to the patient during placement, and in terms of lowering the risk while providing a superior device the advantages of this valve are clearly presented. It is understood that the device and method disclosed are available to all valvular needs. Cardiac valve prostheses are well known in the treatment of heart disease. The normal method of implantation requires major surgery during which the patient is placed on a heart-lung machine and the patient's heart is stopped. Once the surgery is complete, the patient can expect an extended hospital stay and several more weeks of recuperation. A mortality rate of five percent (5%) is common. For some patients, surgery is not an option because age or some other physical problem prevents them from being able candidates for surgery due to the inherent dangers and the likelihood of death therefrom. The valve devices themselves fall into two categories, either biological or mechanical. Biological heart valves are either homograft (a recent human harvest), allograft (a stored human harvest) or xenograft (a stored animal harvest). Homografts are rare because of the well known problems of locating and matching human donors in both tissue type and size. Allografts are also in short supply because of lack of donors. Xenografts are common and well accepted, usually from bovine or porcine donors, and many times the actual heart valve from the animal is used. These devices may be accompanied by immunological rejection from the human body when sutured directly to human tissue and require the patient to take anti-rejection drugs which suppress the immune system. Generally, the valves are treated to reduce the antigenicity of the valve tissue, but the effect is to limit the life of the valve to about ten years. Mechanical valves may be either a ball valve or a leaflet valve having one to three leaflets. One leaflet valve, U.S. Pat. No. 5,469,868, closely resembles a biological valve having three synthetic resin leaflets. Mechanical valves are susceptible to clot formation and require the patient to maintain a strict regiment of anticoagulant drugs which carry their own associated risks. Furthermore, some mechanical valves are prone to wear leading to failure, and some materials for mechanical valves are subject to supply problems. The majority of these artificial valves require surgery and the stopping of the heart as discussed above. During implantation, the valve must be sewn in place either at the natural valve location or at a location adjacent to the natural valve. Even new laproscopic techniques, while substantially less invasive, require general anesthesia and a heart-lung machine. There are artificial valves which claim to have overcome the problems of implantation of the commonly used valves. Three artificial valves which claim the ability to be placed percutaneously comprise the nearest prior art. They are the Tietelbaum valve, U.S. Pat. No. 5,332,402; the Pavcnik valve, U.S. Pat. No. 5,397,351; and the Andersen valve, U.S. Pat. No. 5,411,552. Each of these devices allow placement by minimally invasive techniques. However, each of the devices have disadvantages upon which the disclosed invention greatly improves. The Teitelbaum valve uses nitenol to form each of the two major elements of the valve. It is a mechanical valve, and as such is prone to embolism formation. The two types of stoppers, a ball and seat and an umbrella and seat, each reduce the passageway diameter through the valve thereby reducing the efficiency of blood flow through the valve, and the efficiency of the cardiovascular system itself. Being of two separate components, the movement adds extra complexity leading to wear and improper seating. The abundance of metal in direct contact with the tissue requires a hydrophilic coating which may or may not prevent stenosis in the valve passageway. This valve may only be placed in the natural valve's position and not elsewhere in the vascular system. Also, the nitenol design proposed requires cooling to make it sufficiently compliant to fit within the placement catheter. Cooled nitenol does not exhibit sufficient force upon warming and reformation of its intended shape to maintain a seal between the stent and the tissue. Lastly, both elements must be inserted independently of the other requiring multiple delivery catheters. The Pavcnik valve is also a mechanical valve of ball and seat design. It utilizes a Gienturco stent (U.S. Pat. No. 4,580,586) capped by a cage to comprise a complex restraining element for the ball which is difficult to manufacture. The restraining element must be attached to the seat by a connecting member to maintain the proper distance between the two. The ball is made of latex which can cause a reaction with living tissue. The seat is comprised of two rings, one smaller than the other, displaced from each other by nylon mesh. Both the seat and the restraining element are stainless steel which must be fairly stiff and non-compliant to maintain sufficient outward bias thereby severely restricting the natural movement of the cardiovascular system at the point of implantation. There are multiple joints which must be soldered together increasing the potential for joint failure and breakage. This device requires hooks to maintain patency in the tissue, requiring surgery to remove once deployed. Repositioning is not possible because of the hooks. The balloon must be inserted in a deflated state and filled after placement within the cage and seat. The filling liquid is a silicone rubber which can have detrimental effects on the health of the patient if leaked into the blood stream. In whole, this is a complex design which is highly susceptible to thrombi emboli and improper function over time. The Andersen valve comprises a stainless steel stent to secure a biological valve. The stent is formed of two or more wavy rings sutured to each other with the top loop requiring projecting apices to secure the commissural points of the valve. The valve claims reduced weight but looses this advantage by requiring multiple rings to attain patency against the tissue. The device requires a special trisection balloon with three or more projecting beads to secure the valve within the deployment catheter during placement, and the stent does not exert sufficient force against the tissue to remain in place without a balloon expanding the stent tightly into the tissue wall. The stiffness of stainless steel does not comply with the natural movement of the cardiovascular system which may lead to stenosis at the implantation point. Furthermore, the suture points connecting the multiple rings are subject to movement and wear against each other and therefore the sutures or the rings may break at the connecting points. One drawback of all three of these valves is that none of the devices may be removed or repositioned once they are expressed from their placement catheter. Any misplacement or failure requires major open heart surgery equal to or greater than that now required by standard procedures. Many patients which receive the valve percutaneously because of their intolerance to surgery would face a very uncertain outcome from misplacement or failure. Also, none of these devices seal to the living tissue at the outside wall of the prosthesis. Leaks, and therefore emboli, are likely results after implantation. The need remains for an artificial heart valve which is placed percutaneously through a single minimally invasive entry point; which will seal at the outside wall of the valve with the living tissue of the patient; which may be placed percutaneously at any point as well as directly over an existing vascular or cardiac valve; which will not cause thrombi emboli to form at the valve thereby removing the need for anticoagulant drugs; which will comply with the natural motion of the tissue to which it is attached; which will not cause stenosis; which does not require general anesthesia or stopping the heart or using a heart-lung machine during placement; which will reduce the recuperation time after placement both in and out of the hospital; and which may be repositioned or removed after placement in the event of such a need. SUMMARY OF THE INVENTION A percutaneously implanted artificial valve maintains patent one way flow within a biological passage and includes a tubular graft having radially compressible annular spring portions for biasing proximal and distal ends of the graft into conforming fixed engagement with the interior surface of a generally tubular passage. The graft material is attached to and encloses the annular spring preventing contact between the spring and living tissue. A valve is sealingly and permanently attached to the internal tubular portion of the valve graft. The artificial valve graft may be completely sealed to the living tissue by light activated biocompatible tissue adhesive between the outside of the tubular graft and the living tissue. A BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1a is an perspective view of the super elastic spring stent in its permanent shape prior to attaching the ends to form the cylindrical walls. FIG. 1b is an perspective view of the super elastic spring stent in its permanent shape after attaching the ends to form the cylindrical walls. FIG. 1c is a top view of the super elastic spring stent in its permanent shape after attaching the ends to form the cylindrical walls. FIG. 2 is an elevational view of the valve stent fully deployed within the mitral valve. FIG. 3 is an elevational view of the valve stent fully deployed within the aorta above the aortic valve. FIG. 4 is a sectional view showing the biological valve within the stent. FIG. 5 is a perspective view of the deployment means of the present invention. FIG. 6 is a sectional view thereof taken generally along the line 6--6 in FIG. 5. FIG. 7a is a perspective view showing a spool apparatus and retrieval means of the present invention. FIG. 7b is an enlargement of the circled portion A in FIG. 7a showing the arrangement of a suture loop connecting the invention. FIG. 8 is an elevational view showing a micro-embolic filter tube of the present condition in its deployed position. FIGS. 9a-9d are a series of elevational views depicting a method of deploying the valve stent in the mitral valve position. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 4 shows the preferred embodiment of valve stent 20, comprised of three elements. The three elements are stent 26, biological valve 22, and graft material 24. FIGS. 3, 5, 7A, and 7B illustrate accessories and options associated which the preferred embodiment, including the deployment catheter 100, the bioadhesive material 56 or bioadhesive packets 62, the spool apparatus 170, and the microembolic filter tube 182. For purposes of the disclosed invention and its apparatuses, the distal end is the end first inserted into the patient and the proximal end is the end last inserted into the patient. Stent 26 is shown in FIGS. 1a-1c. FIG. 1a shows stent 26 formed of a single piece of super elastic wire, preferably nitenol wire, with two crimping tubes 50. The crimping tubes 50 is preferable of the same material as the wire to avoid problems which occur when dissimilar materials are in electrical contact with each other, however other materials known in the art may be used. Stent 26 is in its permanent shape, although it has not yet had its two ends attached to itself to form cylindrical wall 64 (FIG. 1C) which will support the other elements of valve stent 20. The top and bottom portions are substantially symmetrical to each other having a zig-zag 40 or wavy form. The preferred embodiment has six (6) zig-zags 40 which optimizes its compressed diameter and outward force, but more or less may be used. At each end of stent 26 is a short extension 58 beginning another zig or wave. Short extension 58 is to close and attach the end to the first zig or wave closest to connecting bar 29. Short extension 58 and the portion of stent 26 to which crimping tubes 50 enclose are substantially parallel to each other to facilitate their connection. The connection is achieved through a crimping tube 50 as shown in FIG. 1b, or by permanent adhesives or welding which are not shown. As is seen in FIG. 1c, the crimped connection is made such that the short extension 58 falls substantially within the area of cylinder wall 64 formed when the connection is complete. FIG. 1b shows stent 26 in its completed form with crimping tubes 50 crimped. This form creates an imaginary cylinder 48 which will exert an approximate outward force of 350 grams or more at each end. An outward force of 350 grams at the mitral valve position is sufficient to secure the valve stent, however stent 26 may be manufactured with more or less outward force to accommodate other placement positions. The super elasticity of the material allows it to deform to forces exerted on it only at those points experiencing the deforming force. All other points will seek their permanent shape. This allows stent 26 to conform to and seal against the dramatically different structures occurring within vessel walls and valve locations with one basic stent shape. Stent 26 is a continuous super elastic nitenol wire having a distal end and a proximal end. Both the distal end and the proximal end are substantially identical, both forming a cylinder wall 64 of six zig-zags 40 or waves. Each end is pre-sized in diameter to be approximately thirty percent (30%) larger in diameter than the largest diameter of the tissue against which the valve stent 20 (FIG. 3) will seal. The overall length of stent 26 is also pre-sized to be sufficient to maintain patency against fluid flow in the vessel or natural valve position, as well as completely support the biological valve (or mechanical or synthetic valve) without causing valve 22 to suffer prolapse or insufficiency. The nitinol wire used to form stent 26 is a super elastic straight annealed material formed substantially of titanium and nickel. It may be coated with a biocompatible material, such as titanium oxide, which will reduce the tissue's reaction to the nickel and improve radiopacity. A layer of PTFE may also cover stent 26 to reduce the risk of blood clotting and corrosion. Furthermore, stent 26 may be treated with iridium 192 or other low dose Beta radiation emitting material to reduce post-surgical cell proliferation in the vessel or valve position. Valve stent 20 may have radio opaque markers in predetermined positions to aid in deployment and placement. Each zig-zag 40 or wave is equidistant from the next in its set and all are of the same height. The peaks and valleys forming the waves are all of a predetermined radius to maximize the spring bias and prevent sharp transitions which create weak points in stent 26. Once crimped, stent 26 forms two cylinders, one at each end of stent 26. Each cylinder is substantially directly above or below the other cylinder. The cylinders are spaced a predetermined distance from each other by a connecting bar 29 which is the central part of the continuous wire from which stent 26 is formed. Connecting bar 29 is also biased outward to conform to the living tissue so as to minimally disrupt blood or other fluid flow, thereby minimizing the possibility of clotting. It is also covered by and sutured to graft material 24 (FIG. 4). Connecting bar 29 provides torsional stability for valve stent 20. FIG. 2 presents a complete pre-sized valve stent 20 fully deployed in the location of mitral valve 14. Also refer to FIG. 4 to identify elements in the following discussion. Mitral valve 14 has been prepared for deployment by valvuloplasty to remove plaque and fistulas if necessary. Valve stent 20 comprises a malleable graft material 24 enclosing deformable self-expanding stent 26 to which a biological valve 22 is attached. Stent 26 biases the proximal and distal ends of valve stent 20 into conforming and sealingly fixed engagement with the tissue of mitral valve 14. The deployed valve stent 20 creates a patent one way fluid passageway. Graft material 24 is a thin-walled biocompatible, flexible and expandable, low-porosity woven fabric, such as polyester or PTFE. It is capable of substantially conforming to the surface of the living tissue to which stent 26 coerces it. Graft material 24, through its low porosity, creates the one-way fluid passage when sutured to the cylindrical form of stent 26. The middle portion of graft material 24 is tapered to a smaller cross-sectional area than its ends to prevent bunching of the material once placed within the patient. Stent 26 is sutured within graft material 24 using polyester suture 60. Prior to sewing, graft material 24 is arranged to surround stent 26 and is heat pressed to conform to the distal and proximal cylindrical ends of stent 26 using an arcuate press surface (not shown). The arcuate press surface is heated to 150 degrees Fahrenheit and corresponds in curvature to the distal and proximal ends. A preferred stitching pattern involves two generally parallel stitches, one on each side of the wire, and a cross-over stitch (not shown) around the wire for pulling the stitches together. This achieves tight attachment of graft material 24 to stent 26 thereby preventing substantially all contact between stent 26 and living tissue. The stitching also will be reliable over the life of the patient. Where other vessels or passages leave the vessel receiving valve stent 20 at a placement site, or when valve stent 20 must flair at one or both ends as is shown in FIG. 2, graft material 24 may be cut out between the plurality of distensible fingers 46 formed by zig-zags 40 of stent 26. Distensible fingers 46 form a conical tip when compressed together which facilitates loading valve stent 20 in the deployment catheter (FIG. 5) prior to the procedure and if retrieval after deployment is necessary. Valve stent 20 may be placed such that other vessels are not blocked by placing distensible fingers 46 on either side of the vessel junction. Stent 26 is pre-sized to open beyond the width of the natural valve mouth and will flair sufficiently to conform and seal to the tissue. Biological valve 22 is preferably a porcine valve treated and prepared for use in a human. It has two or more commissural points 68 as is seen in FIG. 4. Biological valve 22 is attached to stent 26, to graft material 24, or both with sutures 60 or biocompatible adhesive or a combination of the two. Biological valve 22 is pre-sized to fit within the internal diameter of cylinder 48 formed by stent 26 attached to graft material 24. Attachment is along biological valve's 22 commissural points 68 and around its base. Whereas a biological valve is preferred, a mechanical valve or a synthetic leaflet valve may also be employed. A preferred deployment catheter 100 is illustrated in FIGS. 5 and 6. Deployment catheter 100 is generally long and tubular permitting percutaneous delivery of valve stent 20 to the placement site. Deployment catheter 100 has a proximal end remaining outside of the patient and a distal end which is inserted into the patient. The proximal end allows access to a plurality of lumens, syringes, filter tube 182, spool apparatus 170, and other apparatus as necessary for implantation of the disclosed invention. Outer sheath 106 has an axially extending sheath passage 108 and receives an elongated compression spring push rod 112 within sheath passage 108. A push rod 112 also has a passage extending through its longitudinal axis created by the spring coils. Inner catheter 110 is slidably mounted within push rod 112 passage. Outer sheath 106 is made of a low friction and flexible material, preferably PTFE. Other suitable materials such as polyurethane, silicone, polyethylene may be used instead of PTFE. The material is preferably clear to allow inspection of valve stent 20 and deployment catheter 100 prior to use. The size of outer sheath 106 depends on the size of valve stent 20 to be implanted. Common sizes range from 12 FR to 20 FR. Collapsing distensible fingers 46 of valve stent 20 together forms a conical tip which allows for easy loading by sliding outer sheath 106 over the tip and on until valve stent 20 resides within outer sheath 106 and beyond by approximately five millimeters. The conical tips allow a reduction in the profile of valve stent 20 of 2 FR, which allows a smaller diameter outer sheath 106 to be used. This results in a smaller entry incision and less trauma to the patient's access passageway. Outer sheath 106 has a side port means 116 near its proximal end. Side port means 116 provides access for transporting fluid, such as heparin or contrast dye, through outer sheath 106 passage and into the patient. Side port means 116 includes a manually operated valve in fluid communication with outer sheath 106 passage through a flexible tube adapted to receive suitable fluid injection means (not shown). Proximal to side port means 116, outer sheath 106 has at least one latex-lined homeostasis valve (not shown) for forming a fluid seal around push rod 112 to prevent blood or other fluid from leaking out of the delivery catheter at the proximal end. Biological valve 22 should be in an open position when valve stent 20 is loaded into outer sheath 106. This reduces overall profile and stress on biological valve 22 and its attachment to stent 26 and cover material. An open valve 22 also allows inner catheter 110 to pass through valve 22 prior to and during deployment with negligible chance of damage to the valve 22. Valve stent 20 is loaded either end first into outer sheath 106, the correct choice depending upon the access path taken and the fluid flow direction at the placement site. After placement, biological valve 22 should open in the direction of blood flow. Inner catheter 110 is longer than either outer sheath 106 or push rod 112 permitting it to extend beyond outer sheath 106 and push rod 112 at both ends. Inner catheter 110 may be made of 8 FR catheter tubing. As is seen in FIG. 6, inner catheter 110 comprises an embedded, kink resistant nitinol core wire 122, a first inner track 124, a second inner track 126, and a third inner track 128, all extending lengthwise thereof. Referring to FIG. 5, a first end port means 130 for transporting fluid to first inner track 124 includes a threaded adapter 132 for mating with suitable fluid injection means (not shown) and communicating with a proximal end of first inner track 124 through a flexible tube. A second end port means 136 for transporting fluid to second inner track 126 includes a manually operable valve communicating with the proximal end of second inner track 126 through a flexible tube and adapted to receive a suitable fluid injection means. Similarly, a third end port means for transporting fluid to third inner track 128 includes a manually operable valve communicating with a proximal end of third inner track 128 through a flexible tube and adapted to receive a suitable fluid injection means. A preferred option of core wire 122 is a gradual tapering from a diameter of approximately 0.031 inches at its proximal end to a diameter of approximately 0.020 inches at its distal end, with the distal tip of core wire 122 being rounded and smooth. This feature provides that the proximal end of inner catheter 110 is strong and the distal end of inner catheter 110 is less likely to puncture or rupture the access passage yet will not deflect significantly under the force of blood flow. Additional to being kink resistant and strong, core wire 122 displays superior torsional rigidity translating into substantial rotational equivalence along the entire length of core wire 122 when turning inner catheter 110 in either direction at the proximal end. Second inner track 126 and third inner track 128 communicate with balloons at the distal end of inner catheter 110. Second inner track 126 allows filling and emptying tip balloon 152 and third inner track 128 allows filling and emptying expansion balloon 154. Expansion balloon 154 is larger in diameter and shaped according to the placement site Tip balloon 152 is essentially round and of necessary diameter to block blood flow to the placement site if needed. Balloons are preferably polyurethane and act in a calibrated pressure compliant manner such that injecting a known amount of fill fluid into balloons relates to a known expansion in the diameter of balloons. Also, withdrawing a known amount of fill fluid from balloons relates to a known contraction in the diameter of balloons. Fill fluid is preferable filtered carbon dioxide because of it radiopacity. Fill fluid is injected into second inner track 126 and third inner track 128 by separate fluid injection means, respectively. Fluid injection means may comprise a transparent volume-marked syringe with slidable plungers for observably controlling the plenum volume of the syringe filling or emptying a balloon. Tapered head 156 resides between tip balloon 152 and expansion balloon 154. It allows a calm and smooth atraumatic transition from the profile of inner catheter 110 to the profile of outer sheath 106 or to the profile of microembolic filter tube 182 (FIG. 8). Tapered head 156 preferably defines a first annular abutment lip 158 arranged to engage the distal end of outer sheath 106 which prevents tapered head 156 from entering outer sheath 106 passage. Tapered head 156 may contain a second abutment lip (not shown) of slightly larger diameter than first abutment lip 158 or a flair from a smaller to a larger diameter beginning at the first abutment lip 158 for preventing the advancement of the distal end of microembolic filter tube 182 when it is being employed. Push rod 112 is a metallic compression spring having a combination of flexibility and axial compression strength to enable it to follow a tortuous path without loosing its ability to act as a push rod for exerting force against valve stent 20 during deployment. Push rod 112 is smaller in diameter than outer sheath 106 such that both are independently slidable relative to the other. Push rod 112 has an internal path larger in diameter than inner catheter 110 such that both are independently slidable relative to the other. The distal end of push rod 112 defines a plunging seal 162 for stopping fluid flow into the deployment catheter 100 proximal to plunging seal 162. If spool apparatus 170 (FIG. 7a) is employed, either plunging seal 162 must be left out, or suture loops 174 must pass through the opening inner catheter 110 passes through, or one of the lumens or an extra lumen provides passage for suture loops 174. Push rod 112 may also include damping means (not shown) near its distal end, such as a thin heat-shrunken polyolifin or polyimid coating, which dampens undesirable recoil of push rod 112. Valve stent 20 has several preferred options. One is light activated bioadhesive material 56 on the outside of graft material 24 shown in FIG. 2. Bioadhesive material 56 remains inert and will not bind until it is exposed to light waves of a specific frequency. Bioadhesive 56 will not react to sunlight or to standard bulbs found at home or in the operating room. Once deployment is complete and positioning and function verified, a light source (not shown) is inserted and energize. The source emits light of the proper frequency such that when bioadhesive 56 is exposed to the light it sets, binding valve stent 20 to the living tissue and sealing any small microleaks. Another variation is bioadhesive material 56 which is contained in photosensitive polyurethane packets 62 as shown in FIG. 3, which degrade and release the adhesive when exposed to light of the proper frequency. Packets 62 are affixed to the outside of graft material 24 which will contact the living tissue. Again, once valve stent 20 is positioned and functioning, a light source is inserted and energized. Packets 62 then degrade and the bioadhesive 56 fills any microcracks in the seal and binds valve stent 20 in place. In this embodiment, bioadhesive 56 may or may not be photosensitive. In either case, bioadhesive material 56 slowly degrades as it is replaced with living tissue which binds to valve stent 20 securing its location. Types of bioadhesive material 56 which may be used are cryroparticipate, fibrin glue or isobutyl 2 cyanoacrylate. There are also other bioadhesive materials 56 which will suffice such as are used and known in the dental and medical industry. FIGS. 7a and 7b show another preferred option of the invention. A spool apparatus 170 may be provided as part of deployment catheter 100. Spool apparatus 170 allows valve stent 20 to be retrieved into outer sheath 106 if repositioning or removal is necessary. Referring to FIG. 7a, spool apparatus 170 is mounted adjacent the proximal end of outer sheath 106 by a mounting arm 172. Spool apparatus 170 includes a plurality of suture loops 174 wound around a spool cylinder 176 and arranged to extend through a central axial passage of push rod 112. FIG. 7b shows how suture loops 174 extend through the central axial passage, and through and around the peaks of stent 26 at its proximal end. Included with spool apparatus 170 is a hand crank 178 and a releasable pawl (not shown) which work to rotate and fix spool cylinder 176 of spool apparatus 170. An optional blade 180 may be mounted on the body of the spool apparatus 170 for selectively and simultaneously cutting all suture loops 174 at one point to enable removal from valve stent 20 and deployment catheter 100. A final preferred option of the invention is illustrated in FIG. 8. A micro-emboli filter tube 182 may be uses with deployment catheter 100 (FIG. 5) for trapping thrombus, plaque or other particles dislodged or occurring during either the valvuloplasty procedure or the deployment procedure. Filter tube 182 is sized to freely slide over outer sheath 106 and may include one or more pocket filters 184. All pocket filters 184 include a plurality of flexible spokes 188 defined by a series of axially extending slits substantially equispaced around the circumference of filter tube 182. Nylon mesh fabric 190 or the like is affixed along the bottom portion of spokes. When filter tube 182 is axially compressed by pushing its proximal end, spokes 188 of filter tube 182 flair and open pocket filters 184 which extend out and abut the vessel wall. The pockets thereby catch any passing thrombus. The distal end of filter tube 182 is held in place by either expanded tip balloon 152, expansion balloon 154 or tapered head 156. The proximal end of filter tube 182 is retracted to collapse flared spokes 188 and pocket filters 184, which in turn entraps any thrombus residing in pocket filters 184. Pocket filters 184 may be partially or fully collapsed during removal of deployment catheter 100. If necessary, filter tube 182 may be removed independently of deployment catheter 100. FIGS. 9a-9d illustrate a method of surgically implanting valve stent 20. It is assumed that necessary mapping of the placement site and access path have been performed, and that an appropriately sized valve stent 20 has been selected and pre-loaded within the distal end of outer sheath 106 passage of appropriately sized deployment catheter 100. It is further assumed that certain equipment used for monitoring and visualization purposes is available for use by a surgeon skilled in the art. Such equipment includes a freely positional C-arm having high resolution fluoroscopy, high quality angiography, and digital subtraction angiography capabilities. Finally, it is assumed the patients heart has been slowed and blood pressure dropped if necessary. Depending on the placement site, an access passage is chosen to minimize trauma to the passage and the patient. If the placement site is in the aorta or aortic valve 10, entry may be made through the largest femoral artery in the groin area and into the aorta. A high flow pig tail angiography catheter may be placed in the pathway and advanced into the thoracic aorta and an angiogram is performed. The angiography catheter may be left in place. A flexible guide wire with a tip balloon 152 is inserted through the same entry point and advanced to immediately above aortic valve 10 or into left ventricle 12. Deployment catheter 100, prefilled with heparinized solution through side port means 116, is then inserted through the entry point and into the patient by inserting first inner track 124 of inner catheter 110 over the flexible guide wire and slowly advancing the deployment catheter 100 to the placement site. Tip balloon 152 may be partially inflated during insertion of deployment catheter 100 to dilate the vessel if necessary. Tip balloon 152 may then be advanced independent of push rod 112 and inflated to perform valvuloplasty on the existing valve by known methods. Microembolic filter tube 182 may also be employed prior to the valvuloplasty to capture any emboli during the procedure. If valve stent 20 is to be placed in the aorta, tip balloon 152 may be inflated in the aorta closer to the heart than the placement site to block blood flow during the placement procedure. If valve stent 20 is to be placed at mitral valve 14, entry may be made through the right internal jugular vein. A guide wire is advanced through the entry site to the right atrium and interatrial septum 16. A catheter and needle combination (not shown) is advanced over the guide wire to interatrial septum 16 and used to puncture septum 16 and access left atrium 18. The guide wire is advanced into left atrium 18 and through mitral valve 14 and the catheter and needle combination is removed. Deployment catheter 100 loaded with heparinized solution through side port means 116 is introduced by inserting first inner passage over the guide wire and slowly advancing deployment catheter 100 through the right atrium, interatrial septum 16 and into left atrium 18. Tip balloon 152 may be partially inflated in advance of deployment catheter 100 at the new passage in interatrial septum 16 to allow outer sheath 106 or microembolic filter 182 tube to pass through. Microembolic filter tube 182 may now be employed by advancing the proximal end of tube 182 until the filters flair. Tip balloon 152 is then placed within mitral valve 14 and valvuloplasty is performed by a known procedure. From this point on, deployment of valve stent 20 is procedurally the same for all potential placement sites. Contrast media may now be injected through first port means to the distal end opening of first inner track 124. Deployment catheter 100 is positioned so outer sheath 106 is extending through mitral valve 14 approximately one (1) centimeter as is seen in FIG. 9a. Deployment catheter 100 is rotated to match distensible fingers 46 to the structure of mitral valve 14 if necessary. Deployment of the distal end of valve stent 20 is initiated by withdrawing outer sheath 106 approximately 11 to 13 mm while holding push rod 112 stationary. Distensible fingers 46 on the distal end of valve stent 20 will distend as the distal end is released from outer sheath 106 as is shown in FIG. 9b. While valve stent 20 is beginning to protrude from outer sheath 106, deployment catheter 100 may again be rotated and slightly advanced or withdrawn to optimize placement of valve stent 20. Inner catheter 110 is then moved to position expansion balloon 154 on the distal side of biological valve 22 yet within the distal end of valve stent 20 just deployed. The leaflets of biological valve 22 may be slightly overlapped by expansion balloon 154, but the base of biological valve must be free from contact with expansion balloon 154. Proper placement of valve stent 20 is verified by known means, including the introduction of additional contrast dye through the first inner port as described above. Expansion balloon 154 is then inflated to a pressure sufficient to hold the distal end of valve stent 20 secure against the living tissue as seen in FIG. 9c. This ensures proper placement is maintained during the remainder of the deployment procedure and allows valve stent 20 to mold itself quickly into the living tissue at the placement site and achieve a patent seal. With expansion balloon 154 maintaining a friction fit against distal end of valve stent 20, outer sheath 106 is again withdrawn from valve stent 20 while maintaining the position of push rod 112. The proximal end of valve stent 20 is released once outer sheath 106 clears the proximal end of valve stent 20. Verification is once again performed, and if proper placement is attained, expansion balloon 154 is deflated as seen in FIG. 9d. Inner catheter 110 is withdrawn such that expansion balloon 154 is on the proximal side of the biological valve but within proximal end of valve stent 20 just deployed. Expansion balloon 154 may then be inflated again to seat the proximal end of valve stent 20 just deployed. Once more proper placement is verified. Inner catheter 110 is now withdrawn such that it is clear of valve stent 20. If tip balloon 152 has been inflated to block blood flow during the procedure, it is deflated in small decremental steps to slowly increase blood pressure and flow downstream. This prevents damage to the downstream vessels and migration of valve stent 20 from sudden increased blood pressure. Valve stent 20 is now monitored for proper function and patency. The placement site is also monitored to ensure no damage has occurred to the living tissue. Tip balloon 152 or expansion balloon 154 may be advanced to either side of valve stent 20 and reinflated to further mold valve stent 20 to the living tissue if necessary. This should not be needed, however, because of the continuous outward force of super elastic stent 26. If at any time it is necessary to retrieve valve stent 20 for repositioning or removal, the following procedure may be used. This procedure is applicable whether valve stent 20 is fully or partially deployed from outer sheath 106. First advance outer sheath 106 and push rod 112 to the proximal end of valve stent 20. Take up slack in suture loops 174 as outer sheath 106 is advanced by turning the spool handle in the appropriate direction. Take care not to extend the seal at the distal end of push rod 112 out of outer sheath 106. Next, while holding outer sheath 106 and push rod 112 stationary, turn the spool handle until distended fingers 46 of the proximal end of valve stent 20 are compressed to the diameter of outer sheath 106. Finally, again while holding push rod 112 stationary, advance outer sheath 106 over valve stent 20 and through the natural valve position until outer sheath 106 completely covers valve stent 20. Valve stent 20 may now be repositioned or removed. It may not be necessary to advance outer sheath 106 completely over valve stent 20 if repositioning is desired. In this case, advancing outer sheath 106 to collapse the distal end of valve stent 20 so that it is clear of living tissue may be sufficient. Either way, the procedure is simple and is harmless to valve stent 20. Once properly placed, valve stent 20 function and leakage are verified, microembolic filter tube 182 is collapsed such that pocket filters 184 are flush against outer sheath 106, and suture loops 174 are cut and removed using optional blade 180 if provided. Then deployment catheter 100 is removed leaving the guide wire in place. A light emitting catheter capable of emitting light at the proper frequency to activate tissue bioadhesive 56 or packets 62 containing tissue bioadhesive 56 is inserted and energized. Bioadhesive 56 is exposed to the light sufficient to activate it and the light emitting catheter removed. An optical or other catheter may be inserted to verify any microleaks are closed or closing. Finally, any remaining catheters and the guide wire are removed and the entry site attended by standard procedure. If necessary, prior to removing the guide wire and closing the entry site, a stapling device (not shown) may be introduced to secure valve stent 20 to the tissue. An alternative to staples is using the laproscopic suturing device (not shown) to percutaneously enter the vessel and place sutures around the sections of stent 26 if leaks occur after closing the entry site. Again, these are precautions which should not be necessary because of the superior sealing qualities of stent 26 which will maintain patency over the life of the patient. Also, either of these devices may be used to repair an internal puncture access if one was made.
An artificial valve stent for maintaining patent one way flow within a biological passage is disclosed. The artificial valve includes a tubular graft having radially compressible annular spring portions for biasing proximal and distal ends of the graft into conforming fixed engagement with the interior surface of a generally tubular passage. Also disclosed is a deployment catheter including an inner catheter having a nitinol core wire, a controllable tip balloon at its the distal end for dilation and occlusion of the passage, and a controllable graft balloon in the vicinity of and proximal to the tip balloon for fixedly seating the spring portions in conformance with the interior surface of the passage. A spool apparatus for adjusting or removing an improperly placed or functioning artificial valve, and a microembolic filter tube are usable with the deployment catheter. The artificial valve may be completely sealed to the living tissue by light activated biocompatible tissue adhesive between the outside of the tubular graft and the living tissue. A method of implanting the artificial valve is also disclosed.
0
INTRODUCTION [0001] A ventilator is a device that mechanically helps patients breathe by replacing some or all of the muscular effort required to inflate and deflate the lungs. When a patient is undergoing mechanical ventilation, his or her condition is likely to change during the course of treatment. Changes in patient condition are often expressed as raw numerics or waveforms. Oftentimes, the breadth and complexity of change in patient condition renders the raw numerics or waveforms difficult to comprehend and utilize. Furthermore, the raw numerics and waveforms may make it difficult to ascertain trends in the history of a patient's condition. A need exists for an easily understandable manner of conveying trend history of a patient's condition. Pictorial Representation of Patient Condition Trending [0002] The disclosure describes improved systems and methods for displaying a trend history of the patient condition using pictorial representations that dynamically change as the clinician advances and reverses through an independent variable parameter. The present application displays changes in patient condition as an animation or series of illustrations instead of or in addition to a changing number or the drawing of a waveform. By displaying changes in patient condition pictorially as an animated series of illustrations or images, a clinician may be able to quickly understand how the dependent parameters have changed as a function of an independent variable parameter. Moreover, a clinician may be able to determine when one parameter is changing in relation to another parameter. As the pictorial representation changes, it animates from one condition to the next to more effectively indicate changes in patient condition. A representation of the normal or desired condition for a parameter is shown as a static illustration that is overlaid with the dynamically changing trend. In this manner the clinician can determine how the patient condition is changing relative to a desired state. [0003] This disclosure describes systems and methods for displaying trend history of a patient's condition on a ventilator. In one embodiment, the disclosure may utilize a graphical user interface to display one or more component elements of a respiratory system. Each component element of the one or more component elements further comprising at least one line outlining the components, wherein thickness of the line corresponds to a numeric value of at least one ventilatory parameter. The graphical user interface further comprises first line having a thickness corresponding to a predetermined reference value of a first ventilatory parameter and a second line, adjacent to the first line, having a thickness corresponding to a measured value of the first ventilatory parameter. An increased thickness of the second line corresponds to an increase in the measured value of the ventilatory parameter. A decreased thickness of the second line corresponds to a decrease in the measured value of the ventilatory parameter. The increase and decrease in line thickness may be measured over an independent variable, such as time. [0004] In another embodiment, the disclosure relates to a method for animating patient trend history on a graphical user interface on a ventilator. The method comprises first displaying a graphical user interface with an original thickness for a first line. The ventilatory parameters are then monitored and a determination is made as to whether ventilatory parameter associated with the first line has changed. If a change is detected the graphical user interface is updated. The graphical user interface is then displayed with a new thickness for the first line. [0005] These and various other features as well as advantages which characterize the systems and methods described herein will be apparent from a reading of the following detailed description and a review of the associated drawings. Additional features are set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the technology. The benefits and features of the technology will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings. [0006] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. BRIEF DESCRIPTION OF THE DRAWINGS [0007] The following drawing figures, which from a part of this application, are illustrative of described technology and are not meant to limit the scope of the invention as claimed in any manner, which scope shall be based on the claims appended hereto. [0008] FIG. 1 is a diagram illustrating an embodiment of an exemplary ventilator connected to a human patient. [0009] FIG. 2 is a block-diagram illustrating an embodiment of a ventilatory system having a graphical user interface for displaying trend history of a patient's condition. [0010] FIG. 3 is an illustration of an embodiment of a user interface for pictorially displaying trend history of a patient's condition at a first point in time. [0011] FIG. 4 is an illustration of an embodiment of a user interface for pictorially displaying trend history of a patient's condition at a second point in time. [0012] FIG. 5 is an illustration of an embodiment of a user interface for pictorially displaying trend history of a patient's condition at a third point in time. [0013] FIG. 6 is an illustration of an embodiment of a user interface for pictorially displaying trend history of a patient's condition at a fourth point in time. [0014] FIG. 7 depicts a method for animating patient trend history on a graphical user interface in association with a ventilator. DETAILED DESCRIPTION [0015] Although the techniques introduced above and discussed in detail below may be implemented for a variety of medical devices, the present disclosure will discuss the implementation of these techniques for use in a mechanical ventilator system. The reader will understand that the technology described in the context of a ventilator system could be adapted for use with other therapeutic equipment having user interfaces, including graphical user interfaces (GUIs), for improved display of patient parameters. [0016] The present disclosure provides an institution or clinician with optimal control over routine ventilatory settings. Specifically, routine patient trend configuration settings may be preconfigured according to a hospital-specific, clinic-specific, physician-specific, or any other appropriate protocol. Moreover, patient trend configuration settings may be changed and edited in response to a particular patient's changing needs and/or condition. [0017] FIG. 1 illustrates an embodiment of a ventilator connected to a human patient 150 . The ventilator includes a pneumatic system 102 (also referred to as a pressure generating system 102 ) for circulating breathing gases to and from patient 150 via the ventilation tubing system 130 , which couples the patient to the pneumatic system via an invasive patient interface (e.g., endotracheal tube). [0018] Ventilation tubing system 130 may be a two-limb (shown) or a one-limb circuit for carrying gas to and from the patient 150 . In a two-limb embodiment as shown, a fitting, typically referred to as a “wye-fitting” 170 , may be provided to couple the patient interface to an inspiratory limb 132 and an expiratory limb 134 of the ventilation tubing system 130 . Pneumatic system 102 may be configured in a variety of ways. In the present example, system 102 includes an expiratory module 108 coupled with the expiratory limb 134 and an inspiratory module 104 coupled with the inspiratory limb 132 . Compressor 106 or other source(s) of pressurized gases (e.g., air, oxygen, and/or helium) is coupled with inspiratory module 104 to provide a gas source for ventilatory support via inspiratory limb 132 . [0019] The pneumatic system may include a variety of other components, including sources for pressurized air and/or oxygen, mixing modules, valves, sensors, tubing, accumulators, filters, etc. Controller 110 is operatively coupled with pneumatic system 102 , signal measurement and acquisition systems, and an operator interface 120 that may enable an operator to interact with the ventilator (e.g., reset alarms, change ventilator settings, select operational modes, view monitored parameters, etc.). Controller 110 may include memory 112 , one or more processors 116 , storage 114 , and/or other components of the type commonly found in command and control computing devices. [0020] The memory 112 is computer-readable storage media that stores software that is executed by the processor 116 and which controls the operation of the ventilator. In an embodiment, the memory 112 includes one or more solid-state storage devices such as flash memory chips. In an alternative embodiment, the memory 112 may be mass storage connected to the processor 116 through a mass storage controller (not shown) and a communications bus (not shown). Although the description of computer-readable media contained herein refers to a solid-state storage, it should be appreciated by those skilled in the art that computer-readable storage media can be any available media that can be accessed by the processor 116 . Computer-readable storage media includes volatile and non-volatile, removable and non-removable media implemented in any method or technology for storage of information such as computer-readable instructions, data structures, program modules or other data. Computer-readable storage media includes, but is not limited to, RAM, ROM, EPROM, EEPROM, flash memory or other solid state memory technology, CD-ROM, DVD, or other optical storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store the desired information and which can be accessed by the computer. [0021] As described in more detail below, controller 110 may monitor pneumatic system 102 in order to evaluate the condition of the patient and to ensure proper functioning of the ventilator based on various parameter settings. The specific parameter settings may be based on preconfigured settings applied to the controller 110 , or based on input received via operator interface 120 and/or other components of the ventilator. In the depicted example, operator interface 120 includes a display 122 that is touch-sensitive, enabling the display to serve both as an input and output device. [0022] FIG. 2 is a block-diagram illustrating an embodiment of a ventilatory system 200 having a graphical user interface for trend history of a patient's condition. [0023] The ventilator 202 includes a display module 204 , memory 208 , one or more processors 206 , user interface 210 , and ventilation module 212 . Memory 208 is defined as described above for memory 112 . Memory 208 may further may be used to store multiple illustrations, images or pictures for use in presenting the pictorial representation of patient trends and reference bands, as will be discussed in further detail below. Similarly, the one or more processors 206 are defined as described above for the one or more processors 116 . Ventilation module 212 may oversee ventilation as delivered to a patient according to the ventilatory settings prescribed for the patient. For example, ventilation module 212 may deliver pressure and/or volume into a ventilatory circuit, and thereby into a patient's lungs, by any suitable method, either currently known or disclosed in the future. [0024] The display module 204 presents various input screens and displays to a clinician, including but not limited to display of trend history of a patient's condition, as will be described further herein. The display module 204 is further configured to communicate with user interface 210 . The display module 204 may provide various windows and elements to the clinician for input and interface command operations. Additionally, user interface 210 may accept commands and input through display module 204 and may provide useful trend history information relating to a patient's condition to the clinician through display module 204 . Display module 204 may further be an interactive display, whereby the clinician may both receive and communicate information to the ventilator 202 , as by a touch-activated display screen. Alternatively, user interface 210 may provide other suitable means of communication with the ventilator 202 , for instance by a keyboard or other suitable interactive device. [0025] The monitor module 230 monitors both the independent variable parameter and animated parameters used to provide a trend history of a patient's condition. As will be discussed in further detail below, one or more animated parameters are expressed as a function of the independent variable parameter. The animated parameters are the specific parameters utilized to display a trend history of a patient's condition. The monitor module 230 , therefore, is communicatively coupled to the ventilation module 212 to determine values for the independent variable and animated parameters and to determine when an event has occurred, and is further communicatively coupled to display module 204 to provide the with the values necessary to create a trend history of a patient's condition. [0026] FIG. 3 is an illustration of an embodiment of a pictorial trend user interface 300 for displaying trend history of a patient's condition. As will be discussed in detail below, pictorial trend user interface 300 may be used to depict how a patient's condition has improved or deteriorated in relation to an independent variable. For the purposes of the following discussion regarding FIG. 3-6 , the independent variable is time. However, it will be appreciated various parameters may be utilized as the independent variable, such as the monitored parameters such as pressures, volumes or flows and clinician set parameters such as oxygen concentration setting or the positive end expiratory setting. [0027] As discussed above, the independent variable is used to depict trend history of the patient's condition. The patient's condition may be affected by one or more measured parameters. As will be appreciated, any number of parameters may affect the patient's condition including but not limited to resistance, compliance, respiratory muscle pressure, carbon dioxide elimination. For the purposes of this disclosure, parameters that are displayed in pictorial trend user interface 300 are referred to as animated parameters. For example, FIGS. 3-6 include animated parameters of resistance (R), compliance (C), or respiratory muscle pressure (P mus ). These animated parameters will be displayed as a function of the independent variable parameter. As the independent variable parameter in pictorial trend user interface 300 is time, each animated parameter will display the patient measurement for that animated parameter at a given time. In other words, at time 10 hours, the animated parameters of resistance, compliance, and respiratory muscle pressure, are measured at 5.3 cm H 2 O/L/s, 100 mL/cm H 2 O, and 8.1 cm H 2 O respectively. [0028] Pictorial trend user interface 300 may be accessed via any suitable means, for example via a main ventilatory user interface on display module. Pictorial trend user interface 300 may provide one or more independent or embedded windows for display and one or more elements for selection and/or input. Windows may include one or more elements and, additionally, may provide graphical displays, instructions, or other useful information to the clinician. Elements may be displayed as buttons, tabs, icons, toggles, or any other suitable visual access element, etc., including any suitable element for input selection or control. [0029] Pictorial trend user interface 300 may include a parameter display icon 302 for displaying data relating to the chosen independent variable. As discussed above, the parameter used with relation to pictorial trend user interface 300 is time. The parameter display icon 302 , as depicted in pictorial trend user interface 300 , may display how much time has elapsed since the pictorial trend user interface 300 began monitoring the patient condition. In another embodiment, the parameter display icon 302 , may display the amount of time remaining until the pictorial trend user interface 300 ceases monitoring the patient condition. In yet another embodiment, parameter display icon 302 may illustrate the amount of time remaining in an interval for display on pictorial trend user interface 300 . For example, parameter display icon 302 displays that 10 hours remain in the patient monitoring interval for display on pictorial trend user interface 300 . As will be appreciated, the parameter display icon 302 may be selectable wherein, upon selection, more information regarding the parameter is displayed to a user. [0030] As discussed above, pictorial trend user interface 300 provides a pictorial display of the patient's condition in relation to an independent variable. The pictorial trend user interface 300 may also provide a pictorial display of how a change in one animated parameter affects another animated parameter. The pictorial display may be any symbol, representation, graphic, etc. that provides the user with an illustrative understanding of the patient's condition. In one embodiment, the pictorial display is an illustration of a respiratory system 304 . The respiratory system 304 includes multiple components such as airways 306 , a lungs 308 , and a diaphragm 310 . As will be appreciated, the airways 306 , lungs 308 , and diaphragm 310 are all essential components of a respiratory system as depicted by respiratory system 304 . [0031] One or more of the components of respiratory system 304 may include multiple sets of lines outlining the component. For example, in pictorial display user interface 300 , the airway 306 includes both a lighter line 312 and a darker, thicker line 314 . As will be appreciated, any method of contrasting the lines, such as pattern, color, shape, and use of 3-dimensional effect, may be utilized in the spirit of the present application in lieu of lightness and darkness. In one embodiment, the lighter line 312 , represents a reference band, indicating a desirable zone for an animated parameter, and the darker line 314 represents patient measurements. For example, the lighter line 312 represents a reference band indicating the desirable zone for the resistance (R) 316 animated parameter. The desirable zone may be a patient specific or standardized value or range of values. The lighter line 312 may be placed next to the darker line 314 to graphically contrast the reference band with the patient measurements. In one embodiment, the reference band is contrasted with the patient measurements by changing the thickness of the darker line 314 . As will be appreciated any method of indication such as pattern, color, and use of 3-dimensional effect, may be utilized in the spirit of the present application in lieu of thickening the lines. If the patient measurements exceed the desirable zone, the darker line 314 may be depicted as thicker than the lighter line 312 . On the other hand, if the patient measurements fall below the desirable zone, the darker line 314 may be depicted as thinner than the lighter line 312 . In one embodiment, the lines may be laid over one another. For example, the darker line may be displayed as within the lighter line. As depicted with regard to pictorial trend user interface 300 , the measured patient resistance (R) 316 animated parameter is 5.3 cm H 2 O/L/s. This patient measurement for resistance exceeds the desirable zone as is depicted by the darker line 314 thicker than the lighter line 312 . [0032] Components of respiratory system 304 may also be depicted without a reference band. For example, the line 322 outlining lungs 308 relates to the compliance 318 animated parameter. This line 322 , however, is not contrasted with a reference band. Likewise, the line 324 outlining diaphragm, which is associated with the respiratory muscle pressure value 320 is also not contrasted with a reference band. However, even though lines 322 and 324 are not displayed adjacent to a reference band, the lines 322 and 324 are still useful in displaying historical trend of patient condition, as will be discussed in further detail below. [0033] FIG. 4 is an illustration of an embodiment of a pictorial trend user interface 400 for displaying trend history of a patient's condition. Pictorial trend user interface 400 describes like elements of pictorial trend user interface 300 . However, pictorial trend user interface 400 depicts patient measurements at time T-9 hours, as depicted by parameter icon 402 . [0034] As depicted by pictorial trend user interface 400 , at time T-9 hours, the patient's resistance 416 and respiratory muscle pressure 420 have both increased in value while compliance 418 remains the same as at time T-10 hours depicted by pictorial trend user interface 300 . Specifically, resistance has increased from 5.3 cm H 2 O/L/s to 10.1 cm H 2 O/L/s and respiratory muscle pressure has increased from 8.1 cm H 2 O to 11.2 cm H 2 O. This increase in resistance and respiratory muscle pressure is illustrated by thicker lines 414 and 424 respectively than at time 10 hours. In one embodiment, the change in animated parameters may be accompanied by an audio cue. For example, when the resistance and respiratory muscle pressure increase, the ventilator may emit a wheezing sound. [0035] FIG. 5 is an illustration of an embodiment of a pictorial trend user interface 500 for displaying trend history of a patient's condition. Pictorial trend user interface 500 describes like elements of pictorial trend user interfaces 300 and 400 . However, pictorial trend user interface 500 depicts patient measurements at time T-8 hours, as depicted by parameter icon 502 . [0036] As depicted by pictorial trend user interface 500 , at time T-8 hours, the patient's resistance 516 and respiratory muscle pressure 520 have both increased in value while compliance 518 remains the same as at time T-9 hours depicted by pictorial trend user interface 400 . Specifically, resistance has increased from 10.1 cm H 2 O/L/s to 14.4 H 2 O/L/s and respiratory muscle pressure has increased from 11.2 cm H 2 O to 14.6 cm H 2 O. This increase in resistance and respiratory muscle pressure is illustrated by thicker lines 514 and 524 respectively than at time T-9 hours. In one embodiment, the change in animated parameters may be accompanied by an audio cue. For example, when the resistance and respiratory muscle pressure increase, the ventilator may emit a wheezing sound. [0037] Pictorial trend user interface also includes event marker 526 . Event marker 526 is displayed when the patient has undergone a treatment or procedure. For example, event marker 526 may be used to indicate that the patient has received a delivery of aerosol medication. Any number of event markers may be utilized in the spirit of the present application, including but not limited to event markers indicating lung recruitment mechanisms, change in ventilator settings, use of sedatives, suctioning, etc. [0038] FIG. 6 is an illustration of an embodiment of a pictorial trend user interface 600 for displaying trend history of a patient's condition. Pictorial trend user interface 600 describes like elements of pictorial trend user interfaces 300 - 500 . However, pictorial trend user interface 600 depicts patient measurements at time T-7 hours, as depicted by parameter icon 602 . [0039] As depicted by pictorial trend user interface 600 , at time T-7 hours, the patient's resistance 616 and respiratory muscle pressure 620 have both decreased in value while compliance 618 remains the same as at time T-8 hours depicted by pictorial trend user interface 500 . Specifically, resistance has decreased from 14.4 H 2 O/L/s to 10.4 cm H 2 O/L/s and respiratory muscle pressure has decreased from 14.6 cm H 2 O 13.0 cm H 2 O. This decrease in resistance and respiratory muscle pressure is illustrated by thinner lines 614 and 624 respectively than at time T-9 hours. In one embodiment, the change in animated parameters may be accompanied by an audio cue. For example, when the resistance and respiratory muscle pressure decrease, the wheezing sound may subside. [0040] In one embodiment, pictorial trend user interfaces 300 - 600 may be periodically redrawn to depict real-time patient conditions. For example, pictorial trend user interfaces 300 - 600 may be redrawn once a minute to reflect real time patient conditions. As will be appreciated, pictorial trend user interfaces may redrawn at any variety of frequencies to reflect real-time patient conditions. [0041] As will be appreciated, in addition to being displayed on a ventilator during the delivery of therapy, the pictorial trend user interfaces 300 - 600 may be “played” in order. In other words, the pictorial trend user interfaces 300 - 600 may be displayed sequentially to animate the history trend of the patient's condition. The speed of playback and duration of display may be controlled manually (i.e. via speed of rotation of an input knob) or automatically (i.e. selecting an interval for replay of the trend pictorial). In addition, the pictorial trend user interface can be changed in near real time to depict changes that may be occurring at a faster interval (i.e. from one breath to another). When the pictorial trend user interfaces 300 - 600 are played back, a user may be provided with a clearer understanding of the patient's condition. For example, the thickening of lines relating to resistance and respiratory muscle pressure in pictorial trend user interfaces 300 - 500 will indicate that the resistance and respiratory muscle pressure are increasing. Moreover, the thinning of lines relating to resistance and respiratory muscle pressure in pictorial trend user interface 600 may indicate that the resistance and respiratory muscle pressure are decreasing. Furthermore, the played back animation may depict the relationship between animated parameters. For example, in pictorial trend user interfaces 300 - 500 , an increase in resistance might cause an increase in respiratory muscle pressure. In addition, the event marker 526 at pictorial trend user interface 500 , may indicate to a user that the reason the resistance and respiratory muscle pressure decreased was because an aerosolized medication was administered to the patient. [0042] FIG. 7 depicts a method 700 for animating patient trend history on a graphical user interface in association with a ventilator. [0043] At operation 702 , a user interface is displayed with an original thickness for a first line. As discussed above, the first line may be associated with a respiratory component. For example, the first line may outline the airway. The thickness of the first line may reflect a value for a ventilatory parameter. For example, the thickness of the first line may reflect a measured resistance value. Once the user interface has been displayed, flow proceeds to operation 704 . [0044] At operation 704 , the ventilator monitors one or more parameters. These parameters may be associated with the parameters displayed on the user interface. For example, the ventilator may monitor resistance, compliance, and respiratory muscle pressure. In addition to measuring respiratory parameters, the ventilator may also measure the onset or cessation of an event. For example, the ventilator may monitor when an aerosol treatment is administered to a patient. Flow then proceeds to operation 708 . [0045] At operation 706 , a determination is made as to whether a change in a parameter associated with the first line has been detected. Using the example discussed above, the first line may be associated with the airway and the thickness of the first line may reflect a measured resistance value. The ventilator may determine whether this measured resistance value has changed. In one embodiment, this determination may be made on an hourly basis. However, as discussed above, any period of measurement is contemplated within the scope of the present application. Additionally, a determination may be made as to whether an event has been detected. If a determination is made that the value of the measured parameter has not changed, or that an event has not been detected, flow proceeds to operation 704 . If a determination is made that the value of the measured parameter has changed, or that an event has been detected, flow proceeds to operation 708 . [0046] At operation 708 , the user interface is updated based on the changed parameter. Using the example discussed above, the user interface may be updated to reflect an increase or decrease in measured resistance. The increase or decrease in measured resistance may be reflected in a thickening or thinning of the first line. Additionally, the user interface may be updated to reflect detection of an event. For example, the user interface may be updated to depict an event marker indicating that an aerosol treatment has been administered. Once the user interface has been updated, flow proceeds to operation 710 . [0047] At operation 710 , the user interface is displayed with a new thickness for the first line. Using the example discussed above, the user interface may display a thicker first line to indicate that resistance has increased. The user interface may also display an event. For example, the user interface may display an event marker to indicate that aerosol treatment has been administered. Flow then proceeds to monitor operation 704 . [0048] It will be clear that the systems and methods described herein are well adapted to attain the ends and advantages mentioned as well as those inherent therein. Those skilled in the art will recognize that the methods and systems within this specification may be implemented in many manners and as such is not to be limited by the foregoing exemplified embodiments and examples. In other words, functional elements being performed by a single or multiple components, in various combinations of hardware and software, and individual functions can be distributed among software applications at either the client or server level. In this regard, any number of the features of the different embodiments described herein may be combined into one single embodiment and alternative embodiments having fewer than or more than all of the features herein described are possible. [0049] While various embodiments have been described for purposes of this disclosure, various changes and modifications may be made which are well within the scope of the present invention. Numerous other changes may be made which will readily suggest themselves to those skilled in the art and which are encompassed in the spirit of the disclosure and as defined in the appended claims.
The disclosure describes improved systems and methods for displaying a trend history of the patient condition using pictorial representations that dynamically change as the clinician advances and reverses through an independent parameter. The present application displays changes in patient condition as a pictorial instead of a number or waveform. By displaying changes in patient condition in a pictorial, a clinician may be able to quickly understand how the dependent parameters have changed as a function of an independent parameter. As the pictorial changes, it animates from one condition to the next to more effectively indicate changes in patient condition. A representation of the normal or desired condition for a parameter is shown as a static pictorial that is overlaid with the dynamically changing trend. In this manner the clinician can determine how the patient condition is changing relative to a desired state.
6
CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation of Ser. No. 09/035,226 which was filed on Mar. 5, 1998, which is a continuation-in-part of Ser. No. 08/813,695 which was filed Mar. 7, 1997, now abandoned which was a continuation of Ser. No. 08/544,336 filed Oct. 17, 1995 and issued Mar. 3, 1997 as U.S. Pat. No. 5,609,006. BACKGROUND OF THE INVENTION The present invention relates to wall studs generally replacing wooden studs utilized in framing structures such as houses. Wooden studs are common in the construction industry. For many years, lumber was plentiful and inexpensive. Over the years, however, the supply of lumber has diminished. Consequently, lumber is more expensive and good quality lumber suitable for wall studs is more scarce. Furthermore, traditional wood studs are not always the desired material in all applications. For example, fire resistant housing is essential in many areas. Traditional wood studs are also undesirable in areas infected with termites. In addition, it is difficult to run electrical wires and plumbing equipment through walls having solid wooden studs. Designing around these studs can be time consuming and expensive. Previous attempts to design a substitute for wooden studs have been unsuccessful. As with wooden studs, it is difficult to install electrical and plumbing equipment through solid metal studs. Modifying such wall studs is time consuming and can cause structural defects. Because metal is a good conductor of heat, prior art metal studs are also poor insulators. Finally, prior art metal studs are not easily adapted to accommodate electrical outlets and switches and carpenters cannot use nails and screws for adapting the studs in woodwork and molding applications. Therefore, the primary objective of the present invention is the provision of an improved wall stud. A further objective of the present invention is the provision of an improved wall stud that is a good insulator. Another objective of the present invention is the provision of an improved wall stud that provides for the easy installation of electrical and plumbing equipment. A further objective of the present invention is an improved wall stud that is suitable for use with carpenter's nails and screws. Another objective of this invention is the provision of a wall stud which can utilize cost efficient sold wood substitutes, such as oriented strand board (OSB). A further objective of the present invention is the provision of an improved wall stud which is efficient in operation, economical in manufacture, and durable in use. SUMMARY OF THE INVENTION The foregoing objectives are achieved in the preferred embodiment of the invention, by an elongated wall stud mounted in a vertical position. The wall stud is comprised of two elongated C-shaped frame members, a top core element positioned within the cavity formed by the frame members toward the top end of the stud, and a bottom core element similarly positioned within the cavity between the frame members toward the bottom end of the stud. The core elements are rigid and accept nails and screws. If the wall studs are utilized in framing an outside wall, the embodiment of the invention may include an insulative material positioned within the cavity between the frame members and between the top and bottom core elements. Metal by itself is a good conductor of heat and is therefore a poor insulator. Incorporating an insulative material such as polyurethane or oriented strand board into the stud provides good insulation for outside walls. In addition, the insulative material reinforces the wall stud to ensure that the stud maintains its structural integrity when placed under large loads in outside wall applications. For inside walls, the invention may include additional core elements spaced apart between the top and the bottom end of the stud. These core elements are slidably mounted between the frame members and can easily be adjusted to a desired height to accommodate electrical outlets and switches. A substantial portion of the cavity remains hollow, allowing pipes and electrical wiring to be easily installed in the wall. The core elements are particularly well suited for accepting carpenters nails and screws. As a result, carpenters can interchange wall studs of the present invention and wooden wall studs. A core element made from polyethylene is strong and does not split when deformed or compressed. To frame the stud, a U-shaped track is provided for aligning the studs and securing them to either the top or bottom structural surface. As an alternative, a user with traditional building needs may wish to utilize a more traditional approach. An alternative embodiment uses only wood and steel, but benefits both economically and structurally by using a reinforced oriented strand board. This embodiment achieves all the insulative and structural benefits of wood, but because the care of oriented strand board may be thinner, it is cost effective. Further, by using OSB, the problems of new growth wood now used in traditional studs are avoided. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of the preferred embodiment of the wall stud showing the wall stud used in framing outside and inside walls. FIG. 2 is a perspective view of the wall stud of FIG. 1 . FIG. 3 is a perspective view of the wall stud of FIG. 1 showing a core element slidably mounted. FIG. 4 is a perspective view of the wall stud showing insulative material stored within the cavity of the wall stud. FIG. 5 is a sectional view taken along line 5 — 5 of FIG. 2 . FIG. 6 is a sectional view taken along line 6 — 6 of FIG. 2 . FIG. 7 is a sectional view taken along line 7 — 7 of FIG. 4 . FIG. 8 is a partial perspective view showing wall studs used to frame an outside wall and an inside wall mounted to a lower track. FIG. 9 is a partial perspective view showing an alternative embodiment of the invention. FIG. 10 is a sectional view taken along line 10 — 10 of FIG. 9 . FIG. 11 is an exploded and partial sectional view of an alternative embodiment of the invention. FIG. 12 is a perspective view of one end of the invention. FIG. 13 is a perspective, sectional view of the invention. FIG. 14 is a sectional view taken along line 14 — 14 of FIG. 13 . FIG. 15 is a partial perspective view showing a wall stud with a circuit box mounted thereto. FIG. 16 is a partial perspective view showing a wall stud with a formed circuit box attached thereto. FIG. 17 is a sectional view of another embodiment of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 shows a plurality of wall studs 10 A and 10 B used in framing an outside wall 12 and an inside wall 14 , respectively. The wall stud 10 B used in framing the inside wall 14 , has two elongated C-shaped frame members 16 . Each frame member 16 has an inside surface 18 . The inside surfaces are spaced apart and facing to form an internal cavity 20 . A bottom core element 22 is positioned within the cavity 20 at the bottom end 24 of the wall studs 10 A and 10 B. The inner surfaces 18 of the frame members 16 partially enclose the bottom core element 22 . To ensure that the frame members 16 do not separate from the bottom core element 22 , keepers 26 on each frame member 16 extend inward and ride between slits 28 in the bottom core element 22 . The top core element 30 is similarly constructed and positioned between frame members 16 at the top end 32 of the wall studs 10 A and 10 B. A center core element 33 is positioned in the center of the stud 10 B within the cavity 20 . Additional core elements 34 and 35 are positioned within the cavity 20 between the top core element 30 and the center core element 33 and between the center core element 33 and the bottom core element 22 , respectively. Center core element 33 and additional core elements 34 and 35 give the wall stud 10 B additional support and also provide a structure for mounting electrical boxes 36 . The electrical box 36 is used to house such things as electrical switches and electrical outlets. The electrical box 36 attaches to the core elements 33 , 34 , and 35 in a variety of ways. Preferably, the electrical box 36 is glued to the core elements. Screws 38 and/or nails 40 can also be used. Although the center core element 33 is fixed in position along the wall stud 10 B, additional core elements 34 and 35 are left slidably mounted. Thus, the electrical box 36 can be easily adjusted to different heights along the wall stud 10 B by sliding the additional core elements 34 and 35 either up or down the wall stud (see FIG. 3 ). Although the core elements 22 , 30 , 33 , 34 , and 35 can be made from a variety of materials such as wood, polyethylene is the preferred material. Polyethylene will not crack when screws and nails are inserted into the core element. Further, polyethylene is a fire resistant and strong material. Because the wall studs 10 A and 10 B are designed to facilitate the use of carpenter's nails and screws, a carpenter can easily interchange studs 10 A and 10 B and wooden studs. This is particularly important in customized window and door applications where wooden studs are often preferred. For outside wall applications, a substantial portion of the cavity 20 in the wall stud 10 A is hollow. As a result, electrical wiring 42 and pipe 44 are easily inserted and installed inside the cavity 20 . The wall stud 10 A used in outside wall applications is similar to the wall stud 10 B used in inside wall applications. The top and bottom core elements 30 and 22 are positioned at the ends of the wall stud 10 A. In framing an outside wall, it is desirable that the wall be a good insulator. Thus, wall studs 10 A also contain an insulative material 46 positioned within the cavity 20 between the top core element 30 and the bottom core element 22 . A variety of insulative materials can be used. The preferred material, however, is polyurethane. Polyethylene has an R-factor of approximately 7, more than three times that of wood. Furthermore, when wood absorbs moisture, its insulating factor is even lower. In addition to providing good insulation, outside walls must also be able to support large loads. Polyurethane is a strong material and inserting polyurethane into the cavity 20 of the wall stud 10 A reinforced the stud and ensures that the stud maintains its structural integrity. Polyurethane and other insulative materials can easily be cut and shaped to provide access for electrical wires 42 and pipe 44 . The electrical box 36 can be mounted to the insulating material 46 using glue, nails, screws, and the like, or any combination. FIG. 5 is a sectional view of the frame members 16 . Each frame member has a back wall 48 , side walls 50 and 52 , and keepers 26 . The inside surfaces 18 of the frame members 16 partially enclose the core elements 22 , 30 , 33 , 34 , and 35 and the insulative material 46 (see FIGS. 6 and 7 ). The preferred material for the frame members 16 is galvanized steel. It is relatively inexpensive to increase the size of the wall studs 10 A and 10 B from, for example, a 2×4 to a 2×8. The same frame members 16 and only slightly larger core elements and insulative material are used. In contrast, increasing the size of a wooden stud results in a significant additional cost. Once center core element 33 is slid into position in the center of the wall stud 10 B, the center core element 33 is secured by punching through side walls 50 and 52 of the frame members 16 . The resulting punch 54 secures the center core element 33 along the wall stud 10 B. Using a punch to secure the center core element 33 is only one means of securing the core element along the stud 10 B. Top and bottom core elements 22 and 30 are similarly secured at the top end 32 and bottom end 24 of the wall stud 10 A and 10 B, respectively. Additional core elements 34 and 35 are left slidably mounted along the wall stud 10 B so they can be easily adjusted in height to accommodate electrical boxes 36 . As shown in FIG. 1, the top and bottom core elements 22 and 30 of the wall studs 10 A and 10 B can be nailed or screwed to wooden plates 56 . This represents a significant advantage over prior art metal studs that cannot easily be attached to wood. Although the embodiment as shown in FIG. 1 works well in a variety of appplications, there are many instances in which wood is not the desired material. An alternative means of mounting the studs 10 A and 10 B is shown in FIG. 8 . The wall studs 10 A and 10 B are positioned in a lower U-shaped track 58 . The lower track 58 is made of galvanized steel or similar material. The lower track 58 has a back wall 60 and side walls 62 and 64 projecting upward. The bottom end 24 of the wall studs 10 A and 10 B abuts the back wall 60 . The side walls 50 and 52 of the frame members 16 fit against the side walls 62 and 64 of the lower track 58 . Nails or screws 66 are inserted through the back wall 60 and into the bottom core element 22 to secure the wall stud 10 A or 10 B in the lower track 58 . Similarly, a screw or nail 66 can be inserted from the bottom core element 22 and into the back wall 60 . The lower track 58 can be secured to the foundation using a variety of attachment mechanisms. Note that wooden studs, in addition to wall studs 10 A and B, can also be easily mounted in the lower track 58 . Consequently, the same lower track 58 can be used with a wall consisting of both wooden studs and wall studs 10 A and 10 B. Replacing the customarily used wooden plate 56 with a metal lower track 58 has many advantages. The metal lower track 58 is fire resistant, resilient, and light weight. In areas where termites are especially troublesome, replacing wood with metal also prolongs the life of the wall. Similarly, an upper track can also be used to align and position the wall studs 10 A and 10 B at their top ends 32 . As previously stated, it is particularly important that wall studs 10 A used in outside wall applications be able to support large loads. As the studs increase in size, additional support is often desired to withstand twisting and bending forces. This is particularly important when the design of the present invention is rotated and used as a joist. FIG. 9 illustrates an alternative embodiment of the invention. Except as described below, the structural member 68 is identical to the wall stud 10 A. Because the structural member 68 may be rotated to a horizontal position in operation, top and bottom core elements 30 and 22 are now referred to as the first and second core elements 70 and 72 (not shown), respectfully. Similarly, the top and bottom ends 32 and 24 of the frame members 16 are referred to as the first and second ends 74 and 76 (not shown). The insulative material 46 is reinforced with a truss 78 that extends along the longitudinal axis of the frame members 16 within the cavity 20 between the frame members. The truss 78 is immersed within the insulative material 46 (see FIG. 10 ). Molding the insulative material 46 around the truss 78 reinforces the insulative material, which in turn reinforces the structural member 68 . This enables the structural member 68 to withstand large twisting and bending forces. The preferred material for the truss 78 is metal. FIGS. 11 shows another embodiment of wall stud 10 C which, like wall studs 10 A and 10 B can be used in framing either an outside wall 12 or an inside wall 14 . The wall stud 10 C has two elongated generally C-shaped frame members 16 , and due to the unique shape of the channels 80 , varying depths of core material 82 can be utilized. The preferred material for the core 82 is OSB, or oriented strand board. For example, FIG. 11 shows a core material 82 which is approximately half the depth of a traditional wall stud. However, given the additional strength added by the channels 16 , the improved wall stud of the present invention has equal or greater strength. Further, oriented strand board is more cost efficient than traditional wooden studs and can be impregnated with fire and insect resistant chemicals or additives. It also is much less likely to warp than current new growth wood studs. The C-shaped channels 80 extend substantially the entire length of the wall stud 10 C. A wooden cap 84 can be placed at either end of the core material 82 and can be mounted by screws, nails, adhesives, and the like to provide a solid base. C-shaped channels 80 are provided with a lip 86 for additional support of the cap 84 when mounted on the core material 82 . As shown in FIG. 11, cap 84 is secured to the core material 82 by a nail 88 or rivet 89 . Likewise lip 86 is attached to cap 84 by a nail or rivet 89 . A filler 90 or wooden level which approximates the shape of the space between the two C-shaped channels can also be added at the ends of the wall stud 10 C to provide a generally traditional wall stud cross section. A similar filler 90 is placed on the opposite side and can be mounted to core material 82 by screw 92 . C-shaped channel 80 can be mounted to core material 82 through the use of nails or rivets 89 , or by use of adhesive or epoxy. As best shown in the FIG. 14, C-shaped channel 80 has an external side 94 which runs generally perpendicular to the core material 82 . This external side 94 is preferably the standard width of a wall stud, but can be varying sizes depending on the needs of the user. Diagonal portions 96 extend from the external side 94 toward the core material 82 . Flange 98 extends from the diagonal portion 96 of the C-shaped channel 80 and is used to hold the core material 82 in place or to attach the channel 80 to the core material 82 . Flange 98 can extend away from the external side 94 of the C-shaped channel 80 as shown in FIG. 13 or can extend inwardly as shown in FIGS. 14 and 17. As mentioned above, rivet 89 extends through flange 90 to attach channel 80 to the core material 82 . In addition, an adhesive or epoxy (not shown) can be used on the surface of flange 98 closest to core material 82 in addition to, or in lieu of, rivet 89 . As with the previous embodiments, the core material 82 may be provided with passages 100 for electrical wiring, plumbing, and the like. In addition, circuit boxes 36 may be mounted on fillers 90 as found at the ends of the stud 10 C and as shown in FIG. 15 . In addition, circuit boxes and other attachment can be molded to specifically fit the angle of the channel 80 as shown in FIG. 16 . The embodiments of the present invention have been set forth in the drawings and specification, and although specific terms are employed, these are used in a generic or descriptive sense only and are not used for purposes of limitation. Changes in the form and proportion of parts as well as in the substitution of equivalents are contemplated as circumstances may suggest or render expedient without departing from the spirit and scope of the invention as further defined in the following claims.
A wall stud utilized in framing structures, the wall stud including C-shaped frame members supported by core elements. The walls studs can be aligned and secured in a track mounted adjacent the top and bottom ends of the wall studs. The wall studs provide good insulation, support, and easy access for the installation of electrical and plumbing equipment.
4
FIELD OF THE INVENTION The present invention relates to a method for reducing the sound output at the back of an aircraft bypass turbojet engine and to a turbojet engine improved by implementing this method. BACKGROUND OF THE INVENTION It is know that bypass turbojet engines comprise a nacelle defining an air inlet at the front and axially containing a cold stream fan, a central hot stream generator and a fan duct of annular section provided, at the rear, with a jet pipe nozzle for said cold stream, and that, in at least some of these turbojet engines: said cold stream jet pipe nozzle is formed by an outer fan cowl and by an inner fan cowl of which the initial rear parts are respectively convex and concave and converge toward one another until they meet to form an initial outlet orifice for the cold stream; a sound deadening coating of annular section that has to have a preset optimum thickness in order effectively to deaden the noise generated by said fan and carried along in said cold stream, said coating being borne internally by said inner fan cowl at the location where the distance between said converging parts of said inner and outer fan cowls is at least equal to said optimal thickness of the sound deadening coating; said hot stream generator is enclosed in an axial engine cowl that has at least approximately the shape of a divergent front conical surface and of a convergent rear conical surface opposing one another on a common base which lies forward of said initial cold stream outlet orifice, the initial jet pipe nozzle throat and the initial cold stream outlet section being delimited between the initial rear part of the inner fan cowl and the rear conical surface of said engine cowl, said rear conical surface comprising, in its rear part, at least one opening which is positioned on the outside with respect to said cold stream initial outlet orifice and which is intended to discharge to the outside a stream of ventilating air bled from said cold stream and introduced into said engine cowl to regulate the temperature of said hot stream generator; and said fan duct is delimited between said inner fan duct and said engine cowl. In a turbojet engine such as this, the rear part of the cold stream jet pipe nozzle may have noise-deadening characteristics that are not optimal because throughout that part of it in which the distance between the converging rear parts of said inner and outer fan cowls is smaller than said optimal thickness of said noise deadening coating, there is no space to house said coating. SUMMARY OF THE INVENTION It is an object of the present invention to remedy this disadvantage by allowing a greater area of sound deadening coating to be housed between said convergent rear parts of the inner and outer fan cowls. To this end, according to the invention, starting out from a turbo jet engine initial status, which turbo jet engine comprises inner and outer fan cowl rear parts, a cold stream outlet orifice, a jet pipe nozzle throat and a cold stream outlet section all arranged in the initial way described hereinabove, the method is notable: in that, without making any modifications to said axial engine cowl: said concave initial rear part of the inner fan cowl is modified: by progressively diverting it away from the axis of said turbojet engine and lengthening it rearward beyond said initial cold stream outlet orifice, then by extending it rearward in the form of a convex rear end part the rear edge of which defines a modified cold stream outlet orifice, the latter orifice being positioned near said opening through which the ventilation air is discharged, but forwards thereof, and by shaping said convex rear end part in such a way that it, with said rear conical surface of the axial engine cowl, delimits: a modified jet pipe nozzle throat the area of which is equal to that of said initial jet pipe nozzle throat, and a modified cold stream outlet section the area of which is equal to that of said initial cold stream outlet section; and said convex initial rear part of said outer fan cowl is modified: by progressively diverting it away from the axis of said turbojet engine and lengthening it rearward to beyond said initial cold stream outlet orifice, then by extending it rearward in the form of a concave rear end part the rear edge of which meets said rear edge of said convex rear end part in order jointly to form said modified cold stream outlet orifice, and by shaping said modified convex rear part in such a way that it, with the modified concave rear part of the inner fan cowl, delimits an intermediate space of which the thickness is, just beyond said initial cold stream outlet orifice, at least equal to said optimum thickness for said sound deadening coating, and in that said sound deadening coating is placed in all of said intermediate space. Thus, by virtue of such a transverse expansion and such a lengthening of the cold stream jet pipe nozzle it is possible for the axial length (parallel to the axis of said turbojet engine) of the sound deadening coating that can be installed at the periphery of the fan duct to be increased considerably rearward. This then results in excellent reduction in the noise output by the fan at the back of the turbojet engine. In addition, implementing the method according to the present invention yields the advantageous results that the increase in axial length obtained for the noise deadening coating is greater than the ensuing increase in axial length (distance between the initial and modified cold stream outlet orifices) of the cold stream jet pipe nozzle. Experience has shown that this increase in axial length of the sound deadening coating may be up to 25% greater than the increase in axial length of the cold stream jet pipe nozzle. It must be pointed out that the modification, according to the present invention, to the convex initial rear part of the outer fan cowl leads to the formation of a zone of inflection where it meets the concave rear end part. The variation in curvature that occurs in this zone of inflection needs not to cause an inversion of the pressure gradient, as this would have the effect of causing boundary layer separation in the rear part of the outer fan cowl. To avoid such a disadvantage, steps are taken to ensure that the shape parameter Hi of the zone of inflection remains lower than 1.6. Of course, the present invention additionally relates to a turbojet engine that is improved in accordance with the abovementioned method. BRIEF DESCRIPTION OF THE DRAWINGS The figures of the attached drawing will make it easy to understand how the invention may be embodied. In these figures, identical references denote elements that are similar. FIG. 1 is a schematic axial section of a bypass turbojet engine. FIG. 2 is a schematic and partial transversely expanded half-section of the rear part of the initial cold stream jet pipe nozzle of the turbojet engine of FIG. 1 , the modified rear part being depicted in dotted line. FIG. 3 is a schematic and partial transversely expanded half-section of the rear part of the modified cold stream jet pipe nozzle, said FIG. 3 being comparable with FIG. 2 and the initial rear part being depicted therein in dotted line. DETAILED DESCRIPTION OF THE INVENTION The bypass turbojet engine 1 of longitudinal axis L-L depicted in FIG. 1 comprises a nacelle 2 delimiting an air inlet 3 at the front and axially containing a fan 4 generating the cold stream symbolized by arrows 5 , a central generator 6 generating the hot stream symbolized by arrows 7 and an annular-section fan duct 8 provided with a jet pipe nozzle 9 for said cold stream 5 . As also shown, and on a larger scale, in FIG. 2 , the cold stream jet pipe nozzle 9 is formed by an outer fan cowl 10 and by an inner fan cowl 11 of which the rear parts 10 R and 11 R, which are respectively convex and concave, converge toward one another toward the rear to form the cold stream 5 outlet orifice 12 . A noise deadening coating 14 , of annular cross section, for example of the known cellular type, is borne internally by the inner fan cowl 11 . In order effectively to deaden toward the rear the noise generated by the fan 4 and carried along in the cold stream 5 , the sound deadening coating 14 has to have an optimum thickness equal to E. As a result, the sound deadening coating 14 cannot be fitted into the annular rear tip 15 of the nacelle 2 , adjacent to the outlet orifice 12 and beginning in the rearward direction at the transverse plane 15 P, in which tip the distance between the convergent parts of the cowls 10 and 11 is less than the thickness E. The hot stream generator 6 is enclosed in an axial engine cowl 16 that has at least approximately the shape of a divergent front conical surface 16 A and of a convergent rear conical surface 16 R which are opposed to one another on a common base 17 which lies forward of the cold stream 5 outlet orifice 12 . The rear part 11 R of the inner fan cowl 11 and the rear conical surface 16 R of the engine cowl 16 between them delimit the cold stream 9 jet pipe nozzle throat 18 and the outlet section 19 for said cold stream 5 , said throat 18 and said outlet section 19 each being formed by a slightly conical annular surface coaxial with the axis L-L of the turbojet engine 1 . The rear conical surface 16 R comprises, to the rear of and on the outside of the cold stream outlet orifice 12 , at least one opening 20 (for example in the form of an annular slot) intended to discharge to the outside a ventilation air stream symbolized by the arrows 21 and bled (in a known way that has not been depicted) from the cold stream 5 and introduced into the engine cowl 16 (again in a known way that has not been depicted) in order to regulate the temperature of said hot stream generator 6 . The fan duct 8 is thus delimited between said inner fan cowl 11 (or the sound deadening coating 14 ) and said engine cowl 16 . According to the present invention, in order to be able to increase the length of the sound deadening coating 14 , of optimum thickness E, rearward parallel to the axis L-L of the turbojet engine 1 and thus reduce the noise at the rear of said turbojet engine without thereby detracting from engine performance: no modification is made to the engine cowl 16 of the hot stream generator 6 but, as illustrated by FIG. 2 : said concave initial rear part 11 R of the inner fan cowl 11 is modified: by progressively diverting it away from the axis L-L of said turbojet engine and lengthening it rearward beyond said initial cold stream outlet orifice 12 (see dotted line 11 RM), then by extending it rearward in the form of a convex rear end part 22 the rear edge of which defines a modified cold stream outlet orifice 12 M, the latter orifice 12 M being positioned near said opening 20 through which the ventilation air is discharged, but forwards thereof, and by shaping said convex rear end part 22 in such a way that it, with said rear conical surface 16 R of the axial engine cowl 16 , delimits: a modified jet pipe nozzle throat 18 M the area of which is equal to that of said initial jet pipe nozzle throat 18 , and a modified cold stream outlet section 19 M the area of which is equal to that of said initial cold stream outlet section 19 ; and in addition said convex initial rear part 10 R of said outer fan cowl 10 is modified: by progressively diverting it away from the axis L-L of said turbojet engine and lengthening it rearward to beyond said initial cold stream outlet orifice 12 (see dotted line 10 RM), then by extending it rearward in the form of a concave rear end part 23 the rear edge of which meets said rear edge of said convex rear end part 22 in order jointly to form said modified cold stream outlet orifice 12 M, and said modified convex rear part 10 RM is shaped in such a way that it, with the modified concave rear part 11 RM of the inner fan cowl 11 , delimits an intermediate space 24 of which the thickness is, just beyond said initial cold stream outlet orifice 12 , at least equal to said optimum thickness E for said sound deadening coating 14 , and said sound deadening coating 14 is placed in all of said intermediate space 24 , as far as the plane 24 P beyond which, rearward, the thickness of said space becomes smaller than the optimum thickness E for the coating 14 (see also FIG. 3 ). Thus, the sound deadening coating 14 can extend as far as the transverse plane 24 P positioned to the rear of the initial cold stream outlet orifice 12 . In FIG. 3 , in which the rear part 9 RM of the jet pipe nozzle 9 , modified as indicated hereinabove, has been depicted in solid line, with the outline of the initial jet pipe nozzle 9 indicated in dotted line, it may be seen that the lengthening ΔL of the axial length of the coating 14 thus obtained exceeds the lengthening Δl of the jet pipe nozzle in the rearward direction. It will be noted that, where the modified convex part 10 RM and the concave rear end part 23 meet, a profile of inflection 25 is formed on the outer fan cowl. This profile of inflection 25 is additionally shaped in such a way as to cause no boundary layer separation. To do this, the shape parameter Hi of the profile of inflection 25 is chosen to be equal to 1.6 at most.
Disclosed is a method for producing a modified aircraft bypass turbojet engine having reduced sound output, in which the method is based on modifying an initial configuration of a rear portion of the turbojet engine to produce a modified rear portion of the turbojet engine. The modified rear portion includes a modified outer convex rear part shaped with a modified concave inner rear part that delimits an intermediate space beyond an initial cold stream outlet orifice. The intermediate space has a thickness at least equal to the thickness (E) of a sound deadening coating, which is placed in the intermediate space.
8
This application is a division of application Ser. No. 314,014, filed Oct. 22, 1981, now U.S. Pat. No. 4,456,657. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to substrates comprised of a reinforced polymeric material overcoated with metal, and, more especially, to such substrates adapted for producing printed circuits. The topic metallized substrates are typically generically designated as "metal-clad". 2. Description of the Prior Art Such metallized substrates are well known to those skilled in this art (compare U.S. Pat. No. 4,110,147). They generally comprise an electrically insulating support material and a conducting metal foil adhering to one or both of its face surfaces. This metal foil can be, in particular, a copper, aluminum, nickel or stainless steel foil having a thickness of between 10 and 100μ, depending upon the type of printed circuit desired to be produced. The metallized substrates in question can be rigid, semi-rigid or flexible, depending upon the composition of the insulating support material. The expression "semi-rigid substrate" designates a material which can withstand elastic deformation, by bending, down to a very small radius of curvature. In the case of the rigid or semi-rigid metallized substrates, to which the present invention relates more particularly, the insulating support material is typically formed by stacking together a certain number of prepregs which each result from the association, known per se, of a reinforcing filler of elongate structure with a polymeric material. In the case of a common reinforcing filler, such as, for example, a glass fabric weighing 200 g/m 2 , an average of about 12 prepregs are used. The usual prepregs are comprised of cellulose papers, cotton fabrics or glass fabrics impregnated with synthetic polymers. Phenol/formaldehyde resins, polyester resins and especially polyepoxy resins are the products most frequently employed. The reinforcing filler, namely, paper or glass fabric, is generally impregnated with a solution of polymer in an appropriate solvent, and this enables the polymeric binder to penetrate thoroughly between the fibers of the filler. The impregnated structure is then passed through an oven heated to a temperature which enables the solvent to evaporate therefrom. The manufacture of the metallized substrates consists of placing the stack of prepregs, covered with a metal foil on one or both of its face surfaces, depending upon whether it is desired to obtain a monometallized or bimetallized substrate, between the platens of a press. The stack is then compressed at a temperature which permits the association or consolidation of the various constituents. In certain cases, it is necessary to use an adhesive in order for the metal foils to adhere permanently to the prepregs. SUMMARY OF THE INVENTION In view of the fact that the demand for metallized substrates for printed circuits is ever increasing, it is a major object of the present invention to provide for the increased manufacturing output thereof, by reducing the number of individual elements, in particular the number of prepregs, from which same are fabricated. This simplification at the manufacturing level consistent with this invention is also accomplished without detracting from the mechanical and electrical properties of the resultant substrates under the influence of heat. Another object according to the present invention is to provide metallized substrates, the manufacture of which does not give rise to environmental pollution. As indicated hereinabove, the preparation of the insulating support material typically entails a process in which a series of reinforcing structures are impregnated with a solution of polymer in an appropriate solvent. In order to obtain a prepreg which can be used for the remainder of the operations, the solvent must be removed by drying. This solvent removal, despite all precautions which may be taken to recover same, is frequently a cause or source of pollution. Other additional disadvantages related to the use of solvent are, on the one hand, its purchase price, and, on the other hand, the large amount of energy required for drying. The reduction in the number of prepregs as above outlined for purposes of simplifying the manufacture of the subject metallized substrates, therefore, is one means to solve this pollution problem. Another object of the present invention is to solve this problem completely, by dispensing with the collodion method for preparing the remaining prepregs. Yet another object of the invention is to provide metallized substrates for printed circuits, which can easily be pierced by simple punching, and the internal composition of which enables, by applying this simplified piercing technique, obtaining smooth-walled holes for the passage therethrough of the electrical connections between the two face surfaces. Other objects and advantages of the present invention will become more apparent from the description which follows. Briefly, it has now been found that the above and other objects of the invention are attained by providing a metallized substrate characterized in that it comprises: (A) an electrically insulating support material comprising three layers, namely: (i) a central core (a) formed by the consolidation of: (1) a major proportion by weight of a filler fabricated from either a cellulosic material or from mica shavings, flakes or splits, with (2) a minor proportion of a resin prepared from a thermosetting polymeric material, and (ii) two skins (b) and (b') disposed on either side of the central core (a) and formed by the consolidation of: (3) a reinforcing filler fabricated from either a woven fabric or a non-woven fabric (in particular, mats and felts) of glass fibers, asbestos fibers or heat-stable synthetic polymer fibers, such as, for example, polyamide-imide fibers or aromatic polyamide fibers, with (4) a resin fabricated from a thermosetting polymeric material, which is identical to or different from the resin (2) comprising said central core (a); and (B) an electrically conducting metal foil (c) located against the exposed face surface of one or the other of the skins (b) and (b') (the other face surface of the said skin being in contact with said central core). By the expression "cellulosic material" there is intended paper in the form of a pulp or strip, or woven fabrics, knitted fabrics or layers of fibers shaped from natural cellulose or chemically modified cellulose. DETAILED DESCRIPTION OF THE INVENTION More particularly according to this invention, the mica flakes or splits utilized are products which are usually commercially available. These splits can be employed in the crude form, but in certain cases, in order to improve the bond between the mica and the resin, it is advantageous to subject them to appropriate surface treatment, per se known to the art. According to one preferred embodiment of the invention, the metallized substrates as described above also possess a second metal foil (c') disposed against the free face surface, which has not yet been metallized, of the second skin (b') or (b). The various layers (a) (b) (b') (c) or (a) (b) (b') (c) (c') are permanently bonded to one another either by chemical bonding or adhesive bonding. The central core (a) has a weight which advantageously constitutes 50 to 95% of the weight of the metallized substrate. Its essential function is to serve as a filler for the metallized substrate, such as to provide same with the required thickness, which is generally between 1 and 3 mm. The substrates most frequently employed have a thickness of 1.5 to 1.6 mm. The essential functions of the two skins (b) and (b') are, on the one hand, to ensure the rigidity of the metallized substrate, and, on the other hand, to define an adhesive layer for the metal foils (c) and (c'). The total thickness of the two skins (b) and (b') in the metallized substrate ranges from about 0.01 to 0.3 mm. In the central core (a), the proportion by weight of cellulosic material or of mica splits, relative to the filler+resin together, typically ranges from 60% to 95% and preferably from 65 to 90%. The resin, which is a constituent of the central core (a) and also of the skins (b) and (b'), is comprised of a thermosetting polymeric material. Suitable resins which are exemplary are: phenolic resins, such as, for example, condensation products of phenol, resorcinol, cresol or xylenol with formaldehyde or furfural; unsaturated polyester resins, prepared, for example, by reacting an unsaturated dicarboxylic acid anhydride with a polyalkylene glycol; epoxy resins, such as, for example, the reaction products of epichlorhydrin with bisphenol A; and polyimide resins, such as, for example, those obtained by reacting an unsaturated dicarboxylic acid N,N'-bis-imide with a primary polyamine and, if appropriate, with a suitable adjuvant. As indicated above, the resin forming part of the central core (a) can be identical to or different from that which comprises the skins (b) and (b'). The resin can be in the form of a thermosetting prepolymer (which has a softening point and is still soluble in certain solvents) for an intermediate stage of production of the metallized substrate, or in the completely cross-linked form (which is infusible and totally insoluble) in the finished component, as it is normally used. Preferably, the resin comprising the central core (a) is of the same type as that which comprises the skins (b) and (b'), and it consists of a polyimide resin obtained by reacting an unsaturated dicarboxylic acid N,N'-bis-imide with a primary polyamine in accordance with the details set forth in U.S. Pat. Nos. 3,562,223 and 3,658,764 and in U.S. Pat. Re. No. 29,316, the disclosures of which are hereby expressly incorporated by reference. The polyimide resin can also be obtained by reacting the bis-imide with the polyamine and with various adjuvants, such as, for example, mono-imides (according to U.S. Pat. No. 3,717,615), monomers, other than imides, containing one or more polymerizable groups of the type CH 2 ═C< (according to U.S. Pat. No. 4,035,345), unsaturated polyesters (according to U.S. Pat. No. 3,712,933) or hydroxylated organosilicon compounds (according to U.S. Pat. No. 4,238,591), the disclosures of which also being expressly incorporated by reference. In the case where such adjuvants indeed are used, it should be appreciated that the polyimide resin can be obtained either by directly heating the three reactants (bis-imide, polyamine and adjuvant) together, or by heating the reaction product, or a mixture, of the adjuvant and a prepolymer, prepared beforehand, of bis-imide and polyamine. In the following text, the expression "thermosetting prepolymer", when it refers to the preferred polyimides, is to be understood as connoting a polymeric material which has a softening point and is still soluble in certain solvents and which can be: either the reaction product of a bis-imide and a polyamine; or the reaction product of a bis-imide, a polyamine and an adjuvant; or the reaction product of a prepolymer of bis-imide and polyamine, and an adjuvant; or also a mixture of a prepolymer of bis-imide and polyamine, and an adjuvant. Even more preferably, the polyimide resin used in the present invention is prepared by reacting a bis-maleimide, such as N,N'-4,4'-diphenylmethane-bis-maleimide, with a primary diamine, such as 4,4'-diaminodiphenylmethane, and, if appropriate, with one of the various adjuvants mentioned above. It should be appreciated that the polyimide resin comprising the central core (a) can, if appropriate, have a chemical composition which is identical to or different from that of the polyimide resin comprising the skins (b) and (b'). Thus, if the central core (a) includes a filler of a cellulosic material, it is very especially preferred that the polyimide resin comprising the said central core preferably be a polyimide resin originating from the reaction of the bis-imide with the polyamine and with one of the above-mentioned adjuvants, in particular a hydroxylated organosilicon compound. As regards the polyimide resin comprising the skins (b) and (b'), it can then have the same chemical composition or can simply result from the reaction of the bis-imide with the polyamine. Examples of suitable hydroxylated organosilicon compounds are α,ω-dihydroxy-methylphenylpolysiloxane oils having from 4 to 9% by weight of hydroxyl groups. As regards the skins (b) and (b'), the proportion by weight of reinforcing filler, relative to the reinforcing filler+resin together, typically ranges from 20% to 90% and preferably ranges from 40 to 70%. The metal foil or foils employed have all of the characteristics known to those skilled in the art and referred to above. It is preferred to use copper foils having a thickness ranging from 15 to 70μ. The most common thickness is 35μ. The present invention also relates to a technique for the manufacture of metallized substrates of the above type. This technique essentially comprises successively stacking together: (i) a metal foil; (ii) a first prepreg comprising a woven fabric or a non-woven fabric of glass fibers, asbestos fibers or heat-stable synthetic polymer fibers, impregnated with a thermosetting prepolymer; (iii) a felt or a composite comprising a cellulosic material or mica splits and a thermosetting prepolymer; and (iv) a second prepreg as defined under (ii), and then in compressing the stack at a temperature which permits the consolidation of the various elements. This provides a substrate metallized on only one face surface. According to another embodiment of the invention, a second metal foil (v) can be added to the layer (iv) of the stack, such as to provide a substrate metallized on both face surfaces. As indicated above, the skins (b) and (b') are formed by the association of a reinforcing filler with a resin. More precisely, this association is an impregnation. The impregnation of the filler can be carried out, in a conventional manner, by a collodion method, namely, by means of a solution of a thermosetting prepolymer in a suitable solvent, for example, a polar solvent such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diethylformamide or N-acetylpyrrolidone. However, in order to dispense with the use of solvent and to completely solve the pollution problem referred to above, it is possible to impregnate the filler under dry conditions by dusting it with the thermosetting prepolymer or by means of an aqueous dispersion of prepolymer; if a polyimide prepolymer is involved, the various techniques described in U.S. Pat. No. 4,038,450 and in British Pat. No. 1,400,512 can be followed. These processes lead to the preparation of the prepregs (ii) and (iv) formed by a reinforcing filler and a prepolymer. During the subsequent treatments (compression and heating of the stack referred to above), these prepregs are converted to the skins (b) and (b') by cross-linking of the prepolymer. The material which is converted, during the said subsequent treatments, to a central core (a) (or precursor material of the central core) is a felt or a composite comprised of a cellulosic material or mica and a thermosetting prepolymer. The felt is produced by a papermaking method and the composite is produced by a dry method. According to the papermaking method, all of the ingredients, namely, at one and the same time the water, the filler (cellulosic material or mica) and the binder (thermosetting prepolymer) in powder form, are incorporated directly into a mixer referred to in the papermaking industry as a "beater". The felt is then formed on a paper machine from the pulp obtained, and the water is extracted from the felt, on the one hand by draining and applying a vacuum, and on the other hand by drying at a temperature on the order of 70° to 10° C., generally by passing the felt through a ventilated oven. In this felt, the binder is still at the prepolymer stage. The felt prepared in this way has a density of between 0.3 and 2, whereas, at the final stage, namely, after compression of the felt and curing of the prepolymer, the density of the central core ranges from about 1.5 to 2.7. It will be appreciated that the proportions by weight of the filler (for the felt or the composite) of the reinforcing filler (for the prepregs) and of the thermosetting prepolymer which are used for the fabrication of the constituents (ii), (iii) and (iv) correspond to those indicated hereinabove concerning the definition of the central core (a) and the skins (b) and (b'). It will also be appreciated that the constituent (iii) which is the precursor of the central core (a) must have a weight which generally represents 50 to 95% of the weight of the final metallized substrate. According to the dry method, the filler and the thermosetting prepolymer are simply mixed under dry conditions to provide a pulverulent composite. The composite thus obtained is either directly molded with the prepregs (ii) and (iv) and one or both of the metal foils (i) and (v), or, preferably, is subjected beforehand to a preliminary sintering operation in order to make it easier to handle for the purpose of preparing the metallized substrate. According to the dry method, if the filler is mica, it is very especially preferred to use mica splits which have been subjected to a surface treatment beforehand. This treatment consists, in particular, in coating the mica splits with an alkoxysilane containing one or more ethylenically unsaturated groups, the amount of treating agent generally representing 0.1 to 3% of the weight of the micaceous filler. Examples of suitable alkoxysilanes are vinyltriethoxysilane, methylvinyldiethoxysilane and vinyl-tris-(methoxyethoxy)-silane. To produce the metallized substrates according to the invention, the constituents (i), (ii), (iii), (iv) and, if appropriate (v), defined above, are placed on a platen of a press. The assembly is then strongly compressed. More precisely, the assembly is compressed, typically between 10 and 300 bars, at a temperature which enables the prepolymer present in the various constituents to soften. In the case of the preferred polyimide prepolymers obtained from a bis-imide, a polyamine and, if appropriate, one of the above-mentioned adjuvants (generally having a softening point between 50° and 200° C.), the compression temperature is advantageously between 70° and 280° C. Preferably, in order to permit effective bonding (or joining) of the various constituents, the temperature is above 150° C. These compression temperature conditions also apply to the other type of thermosetting prepolymers falling within the scope of the present invention. In general, heating the prepolymers makes it possible to successively soften and then cure them. It is of course possible to bake the assembly, for example, for a few hours at 200° C. or above. The aforesaid technique for the manufacture of the metallized substrates according to the invention has numerous advantages. As has already been mentioned, this manufacture is simplified by virtue of using a restricted number of constituents, and it makes it possible to wholly or partially dispense with processes for impregnating a reinforcing structure by a collodion method, which processes cause pollution. However, there are other advantages. The preparation of the precursor of the central core (a) by a papermaking method (felt) is a high-efficiency process. Furthermore, the papermaking method makes it possible to recycle the waste; there is no disadvantage in re-introducing, into the beater, the felt waste formed before drying. Likewise, the dry method (composite), which proceeds via a sintered preform, also eliminates the existence of waste. Furthermore, it is noted that there is virtually no flow of polyimide during the final hot compression. In brief, this possibility of recycling, together with virtually zero flow during compression, ensures a very small loss of resin during manufacture. The quality of the characteristics of the metallized substrates according to the present invention (in particular: mechanical characteristics; peel strength of the metal foils; heat resistance; water resistance; and electrical characteristics) is totally satisfactory and compatible for use in the electronics industry In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative. EXAMPLE 1 In this example, a detailed description is given of the technique for the manufacture of a bicoppered substrate (also referred to as a copper-clad) comprising a central core made from a paper felt, sandwiched between two skins made from an impregnated glass fabric. (1) Production of the paper felt: The following ingredients were charged into the mixer (referred to as the beater) of a paper machine: (i) an unbleached kraft-type paper pulp consisting of 276 g of cellulosic material dispersed in 8 liters of water; (ii) 83 g of a powder of a prepolymer prepared from N,N'-4,4'-diphenylmethane-bis-maleimide and 4 4'-diaminodiphenylmethane (molar ratio bis-imide/diamine=2.5) and having a softening point of 70° C.; (iii) 35.5 g of α,ω-dihydroxy-methylphenylpolysiloxane oil containing 7% by weight of hydroxyl groups; and (iv) 15.1 g of an aqueous solution containing: 1.5 g of polyvinyl alcohol (Rhodoviol 20/140 from RHONE-POULENC), 1.8 g of propylene glycol and 0.09 g of sorbic acid. Polyvinyl alcohol, propylene glycol and sorbic acid are well-known ingredients in the various processes for the preparation of papers. The entire mass was homogenized by agitation for about 1 hour. In order to facilitate malaxation, the pulp was diluted by adding a small amount of water (about 3 liters). After malaxation, the pulp was introduced in portions of about 2,800 g into a paper machine of the following type: a "Franckformer" equipped with a square-shaped grid having a side length of 300 mm, with a square mesh having a side length of 120μ. The water was removed each time by natural draining and by applying a vacuum (pressure reduced to 50 mm of mercury). The various felts obtained were dried at 90°-100° C. for two hours in a ventilated oven. These felts had dimensions of about 300×300×10 mm and each weighed between 110 g and 140 g. Same comprised about 70% by weight of cellulosic fibers and 30% by weight of polyimide prepolymer (bis-imide/diamine prepolymer+organosilicon compound). The other components, namely, polyvinyl alcohol, propylene glycol and sorbic acid, being soluble in water, were totally eliminated in the aqueous phase, which was recycled. (2) Production of the impregnated glass fabric: A collodion was prepared which comprised 50% by weight of N-methylpyrrolidone and 50% by weight of a polyimide prepolymer prepared from N,N'-4,4'-diphenylmethane-bis-maleimide and 4,4'-diaminodiphenylmethane (molar ratio bis-imide/diamine=2.5) and which had a softening point of 100° C. This collodion was deposited with a paint brush on both face surfaces of a glass fabric of the Tissaverre 278 type (cloth weighing 200 g/m ), so as to have a weight ratio glass fabric/polyimide prepolymer of 65/35. The collodion was deposited in two stages separated by drying for 1 minute at 140° C. After the second application drying was carried out for 10 minutes at 140° C. in a ventilated oven. Two pieces having the following dimensions: 300×300×0.25 mm, and each weighing 27.5 to 28 g, were cut out of the web of prepreg; these were intended to form the two supports enclosing the paper felt. (3) Production of the copper-clad: The following lamina were successively stacked on the platen of a press: (i) a first 35μ thick copper foil of the TC Foil type, having a square shape with a side length of 300 mm; (ii) one of the prepregs; (iii) a felt weighing 124 g; (iv) the second prepreg; and (v) a second 35μ copper foil, and the assembly was then compressed: for 15 minutes at 160° C. under 25 bars (with degassing in the 3rd and 5th minute), and then for 2 hours at 180° C. under 25 bars (the temperature of 180° C. being set after the 15 minutes without interrupting the cycle). There was no flow of pure resin. This provided a 300×300×1.6 mm copper-clad weighing 237 g. In this article, the weight of the central core was about 52% of the total weight of the copper-clad. The mechanical flexural strength properties of the copper-clad were as follows (measurements according to ASTM Standard Specification D 790): (a) flexural strength at about 20° C.: 34.5 kg/mm 2 , (b) flexural modulus at about 20° C.: 1,900 kg/mm 2 . (c) The peel strengths of the copper were as follows: (the peeling was carried out, perpendicular to the bonding plane, on a 1 cm wide strip of copper-clad): ______________________________________ After After After 250 hours 500 hours 1,000 hours Time 0 at 150° C. at 150° C. at 150° C.______________________________________Averages in 1.77 1.85 1.87 1.92kg/cm______________________________________ The peel strengths were very homogeneous and the heat aging was overall favorable. EXAMPLE 2 In this example, a detailed description is given of the technique for the manufacture of a copper-clad comprising a central core made from a mica felt, sandwiched between two skins made from an impregnated glass fabric. (1) Production of the mica felt: The following ingredients were charged into the mixer (referred to as the "beater") of a paper machine: (i) 63.8 g of mica splits of the Suzorite 60 S type; (ii) 11.2 g of polyimide prepolymer prepared from N,N'-4,4'-diphenylmethane-bis-maleimide and 4,4'-diaminodiphenyl- methane (molar ratio bis-imide/diamine=2.5) and having a softening point of 70°; and (iii) 0.5 liter of water. The entire mass was homogenized by agitation for 10 minutes and then introduced into the Franck paper machine, this time equipped with a disc-shaped grid having a diameter of 200 mm, with a square mesh having a side length of 120μ. The circular felt obtained was dried at 100° C. for 2 hours in a ventilated oven. It had a thickness of about 2.5 mm and weighed 71 g. It about 85% by weight of mica and 15% by weight of polyimide prepolymer. For the remainder of the operations, a square (inscribed) of felt having a side length of 140 mm and weighing 45 g was cut out of this circular felt of diameter 200 mm. (2) Production of the impregnated glass fabric: Reference should be made to Example 1, part (2). It should be noted that two square prepregs having a side length of 140 mm were cut out of the web obtained. (3) Production of the copper-clad: The procedure indicated above in Example 1 was followed, but two 35μ thick, square copper foils having a side lengths of 140 mm were used. The compression conditions were as follows: 15 minutes at 160° C. under 40 bars (with degassing in the 3rd and 5th minute); and then 1 hour at 180° C. under 40 bars (the temperature of 180° C. being set after the 15 minutes without interrupting the cycle). There was no flow of pure resin. The shaped article obtained was then baked for 24 hours at 200° C. The characteristics of the copper-clad were as follows: dimensions: 140×140×1.6 mm; weight: 69.8 g; the weight of the central core corresponding to about 64% of the total weight of the copper-clad. flexural strength: at about 20° C.: 20.7 kg/mm 2 , at 180° C.: 18.4 kg/mm 2 . flexural modulus: at about 20° C.: 3,250 kg/mm 2 , at 180° C.: 2,755 kg/mm 2 . peel strength (time 0): 1.6 kg/cm (average value) coefficient of expansion: 10×10 -6 cm/cm/°C. EXAMPLE 3 In this example, a detailed description is given of the technique for the manufacture of a copper-clad comprising a central core made from a sintered mica composite, sandwiched between two skins made from an impregnated glass fabric. (1) Production of the sintered composite: The following ingredients were dry-mixed in an industrial CNTA-type mixer: (i) 85 parts by weight of mica splits of the Muscovite Adriss 16 mesh type, treated with 1% of vinyltriethoxysilane (the treatment typically consisted of mixing the filler with the silane and then leaving the mixture obtained to stand in contact with air for about 3 days), and (ii) 15 parts by weight of polyimide prepolymer prepared from N,N'-4,4'-diphenylmethane-bis-maleimide and 4,4'-diaminodiphenylmethane (molar ratio bis-imide/diamine=2.5) and having a softening point of 70° C. The duration of this mixing operation was about 5 minutes. 80 g of the pulverulent composite thus obtained were then introduced into a 220×120×20 mm mold (between two aluminum sheets in order to facilitate the subsequent release of the molding), the mold and its contents were then heated to a temperature of 120° C. and a pressure of 200 bars was applied for 5 minutes. The molded shaped article was then released hot. The sintered molding obtained weighed 80 g. It comprised about 85% by weight of mica and 15% by weight of polyimide prepolymer. (2) Production of the impregnated glass fabric: The procedure indicated in Example 1, part (2) was followed. It should be noted that two 220×120 mm rectangular prepregs were cut out of the resultant web. (3) Production of the copper-clad: 35μ thick, 220×120 mm copper foils were used. The following elements were successively stacked on the platen of a press: the first copper foil, one of the prepregs, the sintered molding, the second prepreg and the second copper foil, and the assembly was then compressed for 45 minutes at 250° C. under 200 bars. There was no flow of pure resin. The article obtained was then baked for 24 hours at 200° C. The characteristics of the copper-clad were as follows: dimensions: 220×120×1.6 mm; weight: 107 g; the weight of the central core corresponded to about 75% of the total weight of the copper-clad. flexural strength: at about 20° C.: 22.5 kg/mm 2 , at 200° C.: 17.8 kg/mm 2 , at 250° C.: 14.5 kg/mm 2 . flexural modulus: at about 20° C.: 2,285 kg/mm 2 , at 200° C.: 1,905 kg/mm 2 , at 250° C.: 1,660 kg/mm 2 . peel strengths: ______________________________________ After After After 141 hours 500 hours 1,000 hours Time 0 at 200° C. at 200° C. at 200° C.______________________________________Averages in 1.82 1.93 1.67 1.93kg/cm______________________________________ weight variation (in %, relative to the initial weight) during the aging at 200° C.: after 141 hours: ΔW=-0.1% after 1,000 hours: ΔW=-1.5%. test for water uptake after 24 hours (weight variation in %, relative to the initial weight): in steam: ΔW=+0.38% immersion in boiling water: ΔW=+0.74%. electrical characteristics: ______________________________________ After 24 hoursProperties measured Initial values in water______________________________________Dielectric strength 23 13in KV/mmPermittivity ε at 1 MHz 3.6 3.9Tangent of the loss 8.4 × 10.sup.-3 50 × 10.sup.-3angle at 1 MHzResistance in Ω × cm 12 × 10.sup.14 2.5 × 10.sup.14______________________________________ coefficient of expansion: 10×10 -6 cm/cm/°C. While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims.
A metallized, laminated substrate well adapted for the production of printed circuits is comprised of: (A) an electrically insulating support element which comprises (a) a central core member comprising a major proportion by weight of a cellulosic or mica filler and a minor proportion by weight of a thermosetting resin, and (b) and (b') a pair of skin laminae coextensively secured to each face surface, respectively, of said central core (a), each of said skin laminae comprising a fibrous glass, asbestos or heat-stable synthetic polymer reinforcing filler, and a thermosetting resin impregnant, which thermosetting resin may either be the same as or different from the thermosetting resin comprising said central core member (a); and (B) an electrically conducting metal foil (c) coextensively adhered to the exposed face surface of one or the other of said skin laminae (b) or (b').
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates generally to design of handicap accessible buildings and more particularly to the design of buildings permitting handicap barrier-free access to multiple building levels without the use of mechanical lifting devices. 2. Background Art Barrier-free access to building environments especially to living environments is an absolute essential for persons having limited mobility. The degree of limited mobility depends, of course, on the nature of an individual's handicap. However, the single most commonly faced problem by handicapped individuals is the requirement to negotiate stairs which interconnect the living environments in their residence. For some the barrier of the stairs is a minor impediment, but for others stairs present a significant, if not overwhelmingly impossible, barrier to overcome. Significantly, the construction cost, both for new construction and for retrofit construction, for providing barrier-free access is very expensive well exceeding the standard costs for non barrier-free construction. Before the instant invention, the design of barrier-free handicap accessible living environments was accomplished in one of three principle ways: (1) Single level design; (2) mechanical lifting devices; or (3) ramps connecting full-height living levels. In the case of single level design, the entire building environment must be built on one level (“ranch” style design). This design option requires a building foot-print that is of a size equal to the total building environment. In comparison to multi-level designs, the ranch design uses the most land, and therefore will not fit on many building lots where multi-level designs will fit. A ranch design, in comparison to a multi-level design, requires the greatest amount of excavation, foundation, exterior walls, concrete floor slab and roof in proportion to the total livable space. As a consequence of this inherent inefficiency, ranch designs cost more than multi-level building designs to build for the same area of livable space. The ranch design eliminates the need for mechanical lifting devices because there are no multiple levels but at a higher construction cost and restriction on the building lot size availability. Mechanical devices can be used to provide access between multiple levels. For example multiple building levels can be interconnected and thereby accessed by means of mechanical devices that lift an individual or a wheel-chair from one level to another. A lifting device such as an elevator, wheel-chair lift, stair-climbing chair, moving stairway, etc. can be incorporated into the design. Mechanical devices such as these permit the designer to enjoy the cost and land saving benefits that derive from multi-level building design. However, all mechanical designs require significant initial costs for: (1) structural improvements required to accommodate the devices; (2) the devices themselves; and (3) installation of the devices. Additionally, mechanical designs are subject to on-going expenses, risks and inherent design limitations related to inspection, maintenance, repair, replacement, and limited lifting capacity and the limited area that moves between the multiple building levels. For example, at the time of initial construction, a person may require a small elevator suitable only for one person to stand. Subsequently, increased disability may require the use of a wheelchair that requires a larger sized and increased weight-lifting capacity elevator. Also mechanical devices require electricity and have wearing parts and can, therefore, become inoperative because of power failure or mechanical breakdown. Handicapped individuals may become stranded or trapped in life-threatening circumstances in the event of power failure or mechanical breakdown. Ramps are the third design option that permits barrier-free access to building environments. Ramps are sometimes used to interconnect multiple building levels for both commercial and residential uses. However, to be accessible for both able and disabled individuals, ramps can not exceed certain design limitations regarding their slope. For example, there are physical limits on how steep a slope can be for comfortable use by an able-bodied individual as well as partially disabled individuals. There are also physical limits on how steep a slope can be, in combination with the spacing of intermediate landings, for practical and comfortable use by individuals who propel themselves by hand-power in a wheel chair. There are also safety limits on how steep a slope can be used by persons in either hand-powered or motorized wheel chairs. This safety issue arises because there is a risk that a wheel chair may topple forward or backward or sideways because such chairs have a relatively high and therefore inherently unstable center of gravity. In this connection, the American Disabilities Act Accessibility Guidelines (“ADAAG”) as amended in 1998 contains specifications for publically accessible new construction that are widely accepted throughout the United States of America for ramp design. The ADAAG defines a ramp as “walking surface which has a slope in the direction of travel that is greater than 1:20” (5% grade) (reference ADAAG 3.5). ADAAG section 4.8.2. specifies ramp design as follows: 4.8.2* Slope and Rise. The least possible slope shall be used for any ramp. The maximum slope of a ramp in new construction shall be 1:12. The maximum rise for any run shall be 30 in (760 mm). Additionally, the ADAAG requires a level maneuvering space that is at least five feet long at the bottom and top of every ramp. These design parameters result in a significantly long ramp where the total rise from one living level to another is nine feet (or one hundred eight inches). Because the maximum rise per run may be no more than thirty inches, a one hundred eight inch rise requires four ramp segments, each connected to the other by a sixty inch level landing. The total run of ramps also requires an additional sixty-inch level maneuvering area at the top and bottom of the highest and lowest ramps in the run of ramps. Five landings are therefore required, for a total of three hundred inches of level run for all landings. Additionally, the four ramps comprise a total horizontal run of one thousand, two hundred, ninety-six inches (108″×12=1,296″). The total required run of ramps and landings is therefore one thousand, five hundred, ninety-six inches, or a total horizontal run of one hundred thirty-three feet. Typically ramps designed to the full ADAAG standard become so long that it is impractical to fit them into most allowable housing footprints or residential building lots. In some cases, although the ramp may fit within the allowable footprint, the cost of the ramp in proportion to the other costs of the building's usable space becomes prohibitive. In residential construction, shorter length ramps with greater slope may be used depending on the nature and extent of the person's disability. What is required therefore is a way to incorporate relatively shallow ramps in residential construction at reasonable cost to provide access to multi-level dwellings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a split-level ramp-well, isometric schematic view, depicting how the ramps are built side-by-side and are stacked one above the other, thereby providing access to building environments that are off-set at half-story increments. FIG. 2 shows a split-level ramp-well, schematic side view, depicting how the ramps are stacked one above the other, thereby providing access to building environments that are off-set at half-story increments. FIG. 3 A and FIG. 3B show a split-level ramp-well, plan view, depicting how the ramps are built side-by-side, thereby providing access to building environments that are off-set at half-story increments. Additionally, FIG. 3B depicts how the split-level ramp-well does not have to be in one straight orientation, but rather can have any desired angle that interrupts the direction of travel along the ramp-well. FIG. 4 shows a plan view of a single-family residential building design that incorporates this invention, depicting levels A and B and indicating the location within this design of sectional views that are themselves depicted in FIGS. 6 , 7 and 8 . FIG. 5 shows a plan view of a single-family residential building design that incorporates this invention, depicting levels C and D and indicating the location within this design of sectional views that are themselves depicted in FIGS. 6 , 7 and 8 . FIG. 6 shows a sectional view of a single-family residential building design that incorporates this invention, depicting levels A, B, C and D, and also depicting how the split-level ramp-well provides access to building environments that are off-set at half-story increments. FIG. 6 depicts ramps AB and CD, which are stacked above one-another. FIG. 6 does not depict ramp BC which is built beside ramps AB and CD and therefore is out of the plane that is depicted by FIG. 6 . FIG. 7 shows a sectional view of a single-family residential building design that incorporates this invention, depicting levels A, B, C and D, and also depicting how the split-level ramp-well provides access to building environments that are off-set at half-story increments. FIG. 7 depicts ramp BC. FIG. 7 does not depict ramps AB and CD which are built beside ramp BC and therefore are out of the plane that is depicted by FIG. 7 . FIG. 8 shows a sectional view of a single-family residential building design that incorporates this invention, depicting levels A, B, C and D, and also depicting how the split-level ramp-well provides access to building environments that are off-set at half-story increments. FIG. 8 depicts ramps AB, BC and CD. FIG. 8 depicts how levels A and C are stacked above one-another, while levels B and D are also stacked above one-another. FIG. 8 additionally depicts how these two groups of stacked levels are offset from one-another by half-story increments. FIG. 9 shows an exterior front elevation of a single-family residential building design showing all four building levels that incorporates this invention, as depicted in FIGS. 4 , 5 , 6 , 7 and 8 . FIG. 10 shows an exterior rear elevation of a single-family residential building design showing all four building levels that incorporates this invention, as depicted in FIGS. 4 , 5 , 6 , 7 and 8 . FIG. 11 shows an exterior left elevation of a single-family residential building design showing all four building levels that incorporates this invention, as depicted in FIGS. 4 , 5 , 6 , 7 and 8 . FIG. 12 shows an exterior right elevation of a single-family residential building design showing all four building levels that incorporates this invention, as depicted in FIGS. 4 , 5 , 6 , 7 and 8 . DESCRIPTION OF THE INVENTION The present invention uses similarly sloped vertically stacked ramps to connect multiple building levels with oppositely sloped vertically stacked ramps that connect the intermediate levels, each building level being separated from each other by one-half story as shown schematically in FIG. 1 . The total horizontal run of ramps required to provide access from one building level to another is thereby reduced by fifty percent. This means that the total run of ramps and level maneuvering spaces required to meet the maximum ADAAG design guidelines for access to different living levels reduces from one hundred thirty-three feet to sixty-six and one half feet. This reduced requirement for building lot length and the cost to construct is so significant that using ramps as a way to interconnect multiple building levels becomes a practical option instead of an impractical or impossible goal. Few building designs can accommodate a ramp run of one hundred thirty-three feet because of the size of building lots and the extra cost required for foundations, roof and the construction of such a long ramp system. By reducing the size and cost requirements by fifty percent, this invention makes the use of ramps as a means of connecting building levels both more affordable and also more practical because of building lot sizes. As shown in FIG. 1 and FIG. 2 , this invention off-sets, successive building levels by half-story increments of four and one half feet rather than the nine feet typically found in multiple story residential construction. In this respect, a residence built according to this invention resembles a split-level house. As noted, if a building were built to ADAAG standards using this invention, the total run would only be sixty-six and one half feet long. Also, as noted, shorter ramps with a greater slope may be used in residential construction depending on the nature and extent of the person's disability. For instance, a steeper slope of 16.07% is practical for walking purposes. Furthermore, this slope can be negotiated easily by a motorized wheelchair. Furthermore, a 16.07% slope does not pose a risk for off-balance tipping for users of motorized wheel chairs. When a 16.07% slope is used, a total rise of four and a half feet requires only a 28 foot ramp. Incorporating a recommended level landing half way divides the ramp into two 14 foot sections. In addition to the preferred intermediate landing, a preferred design requires two level maneuvering spaces of 5 feet each (1 bottom and 1 top) at either end of the ramp. These spaces are part of each residential level which should be kept clear of obstacles. All totaled, the three spaces (intermediate landing, top and bottom maneuvering spaces) add an additional 15 feet to the total run of the ramp system. Thus, using a 16.07% slope, the total horizontal run of the ramps and required landings is forty-three feet. Of course, a shorter total distance is possible if the landing size and maneuvering spaces are reduced and if a greater slope is used. In the design of the present invention shown schematically in FIG. 1 , ramps connecting the half levels are constructed in a ramp well much as stairs are constructed in stair wells in typical multiple story construction. However, ramps joining each successive level are offset from one another in a side-by side configuration as shown in FIG. 4 and FIG. 5 . (In some houses an intermediate landing for steps is used with a switch-back layout which reverses the direction of the stairs midway and also places the steps in a side by side arrangement.) The side by side ramp design therefore occupies twice the width of standard stairway wells, but the same amount of width as switch-back stairs. However, as a consequence of this design, it is important to note that for each ramp there is a full standard height of approximately 8 feet between the ramp surface and the ceiling above the ramp surface formed by the bottom of the ramp starting two levels above. This can be clearly seen in the schematic of FIG. 1 . Thus, even though the ramps span just a half level each, full height above each ramp is preserved. The building that is depicted in FIG. 4 through FIG. 12 uses a 16.07% slope. This present design for incorporating ramps that are both affordable and of reasonable length into residential multi-level building construction has heretofore not been known. Very little additional construction costs over that of a standard multiple story dwelling are encountered with the design of the present invention. Additionally, smaller and more affordable buildings can be designed using this method, providing safe and comfortable non-mechanical access between multiple building levels. From a functional point of view, the ramp-well either can be located between or can cut across the various levels. Because of the striking visual effect when the ramps are in the middle of the house, this is the preferred design. For those cases for people requiring the shallowest slopes, thereby increasing the length of the ramps that are required, in order not excessively extend the side-to-side or front-to-back dimensions of the house, the ramps can be built with a 90 degree angle (or with other angles A as shown in FIG. 3B as desired) at the intermediate landing. However, multiple turns within the ramp-well (approximating spirals and other configurations found in buildings such as in parking garages) so increase the construction complexity, the building footprint, and the total building costs that such designs involving multiple turns within the ramp-well are impractical for most residential designs. A barrier-free residential house having four floors would be designed and constructed according to the following schematic procedure: 1. Create two or more full-ceiling-height building levels that are stacked one above the other in a group; 2. Create two or more :such vertically stacked groups; 3. Off-set the two groups of such vertically stacked full-ceiling-height groups of building levels in such a way that the relative building levels of each such vertically stacked group is one-half of a level of height higher (or lower) than the other vertically stacked group; 4. Create one or more sets of stacked half-height ramps that are similar in lay-out to what is depicted in FIGS. 1 , 2 and 3 to form a split-level ramp-well. 5. Connect these off-set groups of building levels by using half-level-high ramps (with or without intermediate landings within the ramps) which ramps are themselves built side-by-side as well as above one-another, thereby minimizing the footprint of the ramp-well within the entire building. Clearly, it can be seen that this procedure can be extended to accommodate anywhere from 3 or more building levels. In general there are two different and cost-effective ways to position the groups of stacked full-ceiling-height building levels in relationship to one-another and in relationship to the split-level ramp-wells. Specifically, the groups of building levels can be positioned side-by side with the connecting split-level ramp well positioned perpendicular to the axis that separates the two off-set groups of building levels; or, in the alternative, the groups of stacked building levels can be positioned on either side of (i.e. parallel to) the split-level ramp-well as is the case in the building example that is depicted in FIG. 4 through FIG. 12 . The design of the present invention constructively combines split-level building design with stacked ramps to minimize the length and area used by ramps, thereby providing the lowest-cost solution to non-mechanical barrier-free access to multi-level building environments for both handicapped and non-handicapped individuals. The design of the present invention can also be used to minimize development costs for buildings that are situated on steeply sloped building sites by orienting the split-level ramp-well(s) so they are parallel to the slope of the ground, thereby reducing excavation and related infrastructure effort and expense. The design of the present invention can also be used to connect off-set levels of existing split-level design buildings by adding an addition containing the split-level ramp-well onto the existing building. Such additions would enable individuals with impaired mobility to continue living in their present homes without relying on mechanical devices (i.e. elevators, wheel-chair lifts, stair-climbing chairs, etc.). For some people, the availability of adding the ramp-wells of this invention to their present split level homes will mean the difference between being able to remain in their existing home rather than having to move into an assisted-care or nursing facility. The ramp wells of the present invention may also be used to provide a non-mechanical fail-safe and fire-safe means to enter and to exit buildings (both public and private), a feature that is particularly needed for individuals with impaired mobility. The present invention can also be applied to the internal lay-out and design of multi-level town-houses, apartments and condominiums to provide non-mechanically assisted access both within individual living units, and between individual living units and to spaces outside of the larger building units. Various modifications and alterations can be made by those skilled in the art to the present invention to accommodate different requirements. All such modifications which incorporate barrier-free access by ramps between half height building levels are considered to fall within the scope of this disclosure and appended claims.
Barrier-free multiple level residential housing can be constructed by employing ramps between adjacent housing levels where the housing levels are offset by one half the normal full story height found in multiple story houses. The ramps are constructed in a stacked and side-by-side manner so that the full standard height between housing levels is maintained between the ramps that are stacked one above the other.
4
This is a division of application Ser. No. 524,187 filed Aug. 17, 1983, now U.S. Pat. No. 4,578,306. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to woven sheeting material and in particular to plainwoven sheeting material for institutional use and to a method of making the same. 2. Prior Art Statement It is known in the art to provide woven sheeting material, such as, plainwoven sheeting material for institutional use wherein such institutions include hospitals, nursing homes, rest homes, and the like. However, the sheeting material proposed previously for institutional use is made in what is referred to as a balanced weave utilizing substantially the same number of warps and wefts in each unit of surface area, such as a square inch, for example, of the sheeting material. Further, the sheeting material proposed previously for institutional use employs a blend of natural material and synthetic material in both the warps and wefts thereof whereby with the usual blend of natural and synthetic material defining each warp or weft there are generally equal quantities or considerably more synthetic material than natural material in the previously proposed sheeting material whereby such previously proposed sheeting material has certain deficiencies which will now be described. The provision of sheeting material having substantial quantities of synthetic materials therein, such as a polyester, results in a material in which stains are very difficult to remove. This phenomenon is due to the fact that a synthetic material is basically oleophylic and thereby has a tendency to attract oils, such as body oils emitted from the body of a patient, for example. There is also a tendency for sheeting material having substantial quantities of synthetic materials to become dull and unattractive after about 100 institutional laundry cycles, where a laundry cycle comprises washing, drying, ironing and possibly steam sterilization of a particular sheeting material. Even though such sheeting material is usable after 100 of such cycles there is a tendancy to discard such sheeting material because of its poor appearance. Sheeting material which has been proposed previously for institutional use often is provided with a chemical no-iron surface treatment or finish. Such a treatment tends to degrade cotton fibers of the sheeting material and further tends to make the removal of stains, particularly oleophylic stains, even more difficult. SUMMARY OF THE INVENTION This invention provides an improved woven sheeting material having warps and wefts wherein such sheeting material overcomes the above-mentioned deficiencies. In accordance with one embodiment of this invention each of the warps is made of a blend of a natural material and a synthetic material and each of the wefts is made substantially entirely of the said natural material. In accordance with another embodiment of this invention a plainwoven sheeting material for institutional use is provided which has warps and wefts and is free of surface treatment to thereby require ironing thereof; and, each of the warps of such sheeting material is made of a blend of cotton and polyester and each of the wefts is made of cotton. Accordingly, it is an object of this invention to provide an improved sheeting material of the character mentioned. Another object of this invention is to provide an improved plainwoven sheeting material for institutional use of the character mentioned. Another object of this invention is to provide an improved method of making a sheeting material of the character mentioned. Other features, objects, uses, and advantages of this invention are apparent from a reading of this description which proceeds with reference to the accompanying drawing forming a part thereof. BRIEF DESCRIPTION OF THE DRAWING The accompanying drawing shows present preferred embodiments of this invention, in which FIG. 1 is an isometric view with the central portion thereof broken away illustrating one exemplary embodiment of the sheeting material of this invention, FIG. 2 is an enlarged fragmentary plan view particularly illustrating the warps and wefts of the sheeting material of FIG. 1; and FIG. 3 is a view taken essentially on the line 3--3 of FIG. 2. DETAILED DESCRIPTION Reference is now made to FIG. 1 of the drawings which illustrates one exemplary embodiment of the sheeting material of this invention which is designated generally by the reference numeral 10. The sheeting material 10 is a plainwoven material particularly adapted for institutional use and has wraps 11 extending in one direction along such sheeting material in substantially parallel relation and has wefts 12 extending in parallel relation in another direction which in this example is perpendicular to the direction of the warps and as is known in the art for a plainwoven material. The sheeting material 10 is free of surface treatment and thereby requires ironing. This requirement for ironing in institutional sheeting material is particularly desirable because it tends to reduce pilferage. Most previously proposed institutional sheeting materials are made in a so-called balanced weave, i.e., the same number of warps and wefts per square inch. However, in the sheeting material 10 the number of warps 11 in a unit area, such as a square inch thereof, is greater than the number of wefts 12 and the total number of warps and wefts in any square inch thereof is generally of the order of 190. This reference to generally of the order of 190 is intended to indicate that between 185 and 200 warps and wefts per square inch are provided. In one particular example, 192 warps and wefts per square inch were provided with 110 of this number being warps and 82 being wefts. As previously mentioned, each of the warps 11 is made of a blend of natural material and synthetic material. Preferably each of the warps 11 consists of from 40% natural material and 60% synthetic material to 60% natural material and 40% synthetic material. In one specific example of the sheeting material 10 the warps consisted of a blend of 50% natural material and 50% synthetic material. The natural material of the warps and wefts is preferably cotton and defines approximately 70% by weight of the sheeting material 10 thereby providing a light weight, high moisture absorbency, and softness in such sheeting material. In one example cotton constituted 72% by weight of the sheeting material 10. The sheeting material 10 is woven such that the cotton of the warps 11 and wefts 12 also defines approximately 80% of the surface area of such sheeting material, and it will be appreciated that with this large amount of cotton defining the surface area there is a minimum tendency for pilling by the loose or broken ends of the synthetic material. Although any suitable synthetic material may be used to define the warps 11 of the sheeting material 10, such synthetic material is preferably polyester. The preferred natural material used in the warps 11 and wefts 12 is cotton and preferably is in the form of a long staple combed cotton. In a particular example of the sheeting material each warp 11 consisted of 50% cotton and 50% polyester. Although the natural material comprising the warps and wefts in the exemplary material 10 is described as being preferably cotton, it will be appreciated that other natural materials may be utilized. For example, in applications where expense is not of paramount importance wool, silk, and the like may be utilized. Likewise synthetic materials other than polyester may be utilized provided that the selected synthetic material is easy to blend with the natural material which is being utilized and such selected synthetic material is also easy to weave as a plain weave. The sheeting material 10 has comparatively higher tensile strength in the warp direction than in the weft direction. This is due to the utilization of polyester in the warps which has a comparatively high tensile strength. It will also be appreciated that with the provision of the sheeting material 10 having approximately 70% by weight of cotton and a surface area made of approximately 80% cotton, as previously mentioned, the advantages of cotton are preeminent. In particular, cotton provides its well known luxurious feel and touch and greater comfort than sheeting material made with large amounts of synthetic material. It is also comparatively easier to remove stains from cotton. In addition, the utilization of substantial amounts of cotton in the sheeting material 10 enables the provision of such sheeting material for institutional use in colors which retain their brightness. The utilization of a natural material, such as cotton, to define generally of the order of 70% by weight of the sheeting material 10 enables such sheeting material to be subjected to numerous laundry cycles without destroying what is often referred to as the brightness and cleanliness of such sheeting material. In comparing sheeting material 10 with previously proposed sheeting materials which utilize substantial amounts of synthetic materials, such as polyester, it was found that such previously proposed sheeting materials became dull and their brightness was greatly diminished after about 100 institutional laundry cycles, as previously defined. However, the sheeting material 10 retains its bright clean appearance after 150 institutional laundry cycles and in some instances after as many as 200 such cycles. The sheeting material 10 is made with its exposed surfaces free of special treatment or finish. In this manner chemicals which tend to degrade and weaken the fibers and/or filaments defining the warps 11 and wefts 12 and which also tend to retain stains thereon are avoided. It will also be appreciated that the sheeting material 10 with substantial amounts of cotton comprising the same lends itself to the provision of colored selvages for instant identification of size and product. In this context it will be recognized that the reference to sheeting material means bed sheets, whether flat or contoured; pillowcases, so-called draw sheets, or products for hospital surgical procedures made from this sheeting. Throughout this disclosure reference has been made to warps 11 and wefts 12 of the sheeting material 10. However, it is to be understood that warps 11 means warp threads or yarns and wefts 12 means weft, i.e., fill, threads or yarns and as is known in the art. While present exemplary embodiments of this invention, and methods of practicing the same, have been illustrated and described, it will be recognized that this invention may be otherwise variously embodied and practiced within the scope of the following claims.
A woven sheeting material and method of making same are provided wherein such sheeting material has warps and wefts and each of the warps is made of a blend of a natural material and a synthetic material and each of the wefts is made substantially entirely of the natural material.
3
This is a divisional of application Ser. No. 08/569,980 filed on Dec. 8, 1995 U.S. Pat. No. 5,651,539 which is incorporated herein in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus capable of forming an image on a large-size transfer sheet. 2. Description of the Prior Art Electrophotographic copying machines are widely used which are adapted to scan a document original under light irradiation, form an electrostatic latent image on a photoreceptor by light rays reflected on the document original, develop the electrostatic latent image into a toner image, and thermally fix the toner image on a transfer sheet. Some of these copying machines are capable of copying a large-size document original such as of JIS A0 size. The copying machines for copying a large-size document original have a reading mechanism capable of reading a large-size document original and a transporting mechanism capable of transporting a transfer sheet of a large size corresponding to the size of the document original. When such a large-size transfer sheet is transported, the transfer sheet is liable to be biased, resulting in transportation failure (so-called jam) of the transfer sheet. Further, when the transfer sheet is transported from one transportation roller to the next transportation roller, there is a tendency to form a distorted copy image. The transfer sheet traveling speed relative to the circumferential speed of the photoreceptor should be constant when a toner image on the photoreceptor is transferred onto the transfer sheet. If the transfer sheet traveling speed relative to the circumferential speed of the photoreceptor is changed, the scale of an image to be copied is changed in a transfer sheet transportation direction. Where a large-size transfer sheet is transported, it is difficult to keep the transfer sheet traveling speed relative to the circumferential speed of the photoreceptor constant because of the structure of the copying machine. This is because a transportation speed at which the transfer sheet is taken into a fixing unit from the photoreceptor for fixing the toner image on the transfer sheet is generally set higher than a transportation speed at which the transfer sheet is fed into the photoreceptor. Where a larger-size transfer sheet is used, the rearward portion of the transfer sheet does not reach the photoreceptor, when the leading edge of the transfer sheet enters the fixing unit. Therefore, the scale of an image to be copied on the transfer sheet is changed during the transportation of the transfer sheet. For the foregoing reason, there is a need to prevent the scale of an image to be copied on the transfer sheet from being changed. Additionally, there is a similar problem to be solved in image forming apparatuses other than copying machines, for example, printing machines for printing an image on a larger size sheet. In view of the foregoing problem, it is one object of the present invention to provide an image forming apparatus comprising a transportation mechanism capable of properly transporting a large-size transfer sheet. It is another object of the present invention to provide an image forming apparatus which is so improved as to prevent a transfer sheet from being biasedly transported. It is still another object of the present invention to provide an image forming apparatus which is so improved as not to distort an image to be transferred onto a transfer sheet: nor change the scale of the image even if the transfer sheet transportation speed relative to the circumferential speed of the photoreceptor is changed during the transportation of the transfer sheet. SUMMARY OF THE INVENTION In accordance with the first feature of the present invention, there is provided an image forming apparatus comprising two transportation rollers, i.e., a first roller and a second roller, provided on a transportation path for guiding a transfer sheet to an image forming section. The first roller is adapted to stop the leading edge of the transfer sheet transported to the transportation path so as to align the leading edge of the transfer sheet with a line perpendicular to a transportation direction. The second roller is adapted to feed the transfer sheet to the image forming section at a predetermined transportation speed. The first roller is rotated at a circumferential speed lower by a predetermined degree than that of the second roller, thereby constantly applying a predetermined tensile force to the transfer sheet retained between the first roller and the second roller to prevent the transfer sheet from being biased during the transportation. In accordance with the aforesaid feature, the predetermined tensile force is applied to the transfer sheet transported from the first roller to the second roller. This prevents the transfer sheet from being biased with respect to the transportation direction, i.e., from being biasedly transported. In accordance with another feature of the present invention, there is provided an image forming apparatus characterized in that either a sheet obtained by cutting into a predetermined length an elongated roll sheet paid out of a roll body around which the elongated roll sheet is wound or a cut-sheet preliminarily cut into a predetermined size is used as the transfer sheet. In accordance with another feature of the present invention, there is provided an image forming apparatus wherein the first roller driving control means operates in a manner as cited in the first feature where the transfer sheet is the cut-sheet. The aforesaid feature eliminates a tendency of the cut-sheet as the transfer sheet to be biased. In accordance with another feature of the present invention, there is provided an image forming apparatus further comprising: sheet edge detection means provided upstream of the first roller along the transfer sheet transportation direction on the transportation path; wherein the first roller driving control means rotates the first roller at a circumferential speed lower by a predetermined degree than that of the second roller as cited in claim 1 in a state where the leading edge of the transfer sheet is not detected by the sheet edge detection means and, in response to the leading edge of the transfer sheet being detected by the sheet edge detection means, increases the circumferential speed of the first roller from the lower speed into a speed higher by a predetermined degree than that of the second roller to smoothly relieve a tensile force applied to the transfer sheet retained between the first roller and the second roller. In accordance with the aforesaid feature, when the tail edge of the transfer sheet departs from the first roller, the circumferential speed of the first roller is increased, so that the tensile force applied to the transfer sheet is smoothly relieved. This can eliminate a sudden fluctuation in the tensile force which may otherwise occur when the tail edge of the transfer sheet departs from the first roller. Therefore, the transfer sheet is transported to the image forming section at a predetermined speed by the second roller without suffering from a sudden fluctuation in the load to the second roller. Thus, the distortion of an image to be transferred onto the transfer sheet can be prevented. In accordance with another feature of the present invention, there is provided an image forming apparatus, wherein the first roller is a resist roller for adjusting the timing of transporting the transfer sheet to the image forming section, and the second roller is a transportation roller for feeding the transfer sheet to the image forming section at a constant speed. In accordance with another feature of the present invention, there is provided an image forming apparatus wherein the transfer sheet to be transported is a sheet having a length longer than the distance between the first roller and the second roller along the transportation path, and an image is transferred onto the sheet in the image forming section. In accordance with another feature of the present invention, there is provided an image forming apparatus wherein the image forming section electro-photographically forms an image and transfers the formed image onto a given transfer sheet. In accordance with another feature of the present invention, there is provided an image forming apparatus further comprising: an image reading section for reading an image of a document original along a reading line; document-original feeding means for changing a relative positional relation between the image reading section and the document original in a direction perpendicular to the reading line; fixing means disposed downstream of the image forming section along the transfer sheet transportation direction on the transportation path for taking in the transfer sheet transported from the image forming section and having an image transferred thereon at a transportation speed higher than that in the image forming section, then fixing the transferred image on the transfer sheet, and discharging the transfer sheet; and the image forming apparatus is characterized in that document-original feeding speed control means for controlling the document-original feeding means so as to change the relative positional relation between the image reading section and the document original at a relatively low first speed until the leading edge of the transfer sheet transported through the transportation path reaches the fixing means and, in response to the leading edge of the transfer sheet reaching the fixing means, controlling the document-original feeding means so as to change the relative positional relation at a relatively high second speed. In accordance with the aforesaid feature, the scale difference between images formed on forward and rearward portions of the transfer sheet is not produced and, therefore, an excellent image can be formed. In particular, an excellent image formation can be realized where the transfer sheet has a length longer than the distance between the image transportation position and the fixing position. In accordance with another feature of the present invention, there is provided an image forming apparatus wherein the first speed controlled by the document-original feeding speed control means is equivalent to the speed at which the image forming section feeds out the transfer sheet, and the second speed varies depending on the type of transfer sheet. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 a schematic sectional view illustrating the internal construction of a copying machine in accordance with one embodiment of the present invention; Fig. 2 is a perspective view illustrating the external construction of the copying machine in accordance with one embodiment of the present invention; Fig. 3 is a perspective view illustrating the appearance of the copying machine which is performing a copying operation in accordance with one embodiment of the present invention; Fig. 4 is a block diagram illustrating the construction of a control circuit for a transportation path of the copying machine in accordance with one embodiment of the present invention; Fig. 5 is a timing chart illustrating one example of operational timings for the transportation control shown in FIG. 4; and Fig. 6 is a timing chart illustrating another example of operational timings for the transportation control shown in FIG. 4. DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will hereinafter be described With reference to the attached drawings. FIG. 1 is a schematic sectional view illustrating the internal construction of a copying machine in accordance with one embodiment of the present invention. FIG. 2 is a perspective view illustrating the external construction of the copying machine, and FIG. 3 is a perspective view illustrating the appearance of the copying machine which is performing a copying operation. The copying machine is adapted to obtain an image of a large-size document original such as of A0 size. In the copying machine, the document original is scanned under light irradiation by a stationary optical system while being transported, and an image is formed on the basis of the optical scanning. Referring to FIG. 1, a machine body 1 has caster wheels 2 on the under side thereof for free movement. Referring to FIGS. 1 to 3, a document-original transportation section 10 for transporting a document original 9 along a document-original transportation path 41 formed on the top face of the machine body 1 is provided on the machine body 1. A discharge port 54 for discharging a sheet having a toner image transferred thereon opens in a front face la of the machine body 1. The sheet discharged from the discharge port 54 is guided by a guide member 91, dropped through a guide opening 93 with the leading edge thereof oriented downward, and accommodated in a pocket 92 defined by a front cover 5 provided along the front face la of the machine body 1, as shown in FIG. 3. On an edge portion of the top face of the machine body 1 is provided with an operation section 100 having switches, keys and the like for making various settings related to a copying operation. Referring to FIG. 1, three roll sheets 4A, 4B and 4C which are located vertically in upper, middle and lower positions and each wound into a roll shape are accommodated within a portion between the vertically middle portion and the lower portion of the machine body 1. The roll sheets 4A, 4B and 4C are rolled around feed reels 51, 52 and 53, respectively. Examples of sheets to be used as these roll sheets 4A, 4B and 4C include normal paper, film and tracing paper. In the central portion of the machine body 1 is disposed a bypass transportation path D4 for feeding a cut-sheet preliminarily cut into a predetermined length such as of A0 size to A4 size through a manually sheet feeding section 30 provided on the front face la of the machine body 1. The roll sheet 4A in the upper position is transported along a first transportation path Dl to a photoreceptor drum 20 through the feed reel 51, sheet feeding rollers 61, a first leading-edge detection switch 71 for detecting the leading edge of the transported roll sheet 4A, transportation rollers 62, a cutter mechanism 80, transportation rollers 63, a second leading-edge detection switch 72 for detecting the leading edge of the transported sheet 4A, 4B, 4C or 4D, and transportation rollers 33 in this order. The roll sheet 4B in the middle position is transported along a second transportation path D2 to the photoreceptor drum 20 through the feed reel 52, sheet feeding rollers 64, a third-leading-edge detection switch 73 for detecting the leading edge of the transported roll sheet 4B, the transportation rollers 62, the cutter mechanism 80, the transportation rollers 63, the second leading-edge detection switch 72, and the transportation rollers 33 in this order. The path down-stream of the transportation rollers 62 is common to the first transportation path Dl. The roll sheet 4C in the lower position is transported along a third transportation path D3 to the photoreceptor drum 20 through the feed reel 53, sheet feeding rollers 65, a fourth leading-edge detection switch 74 for detecting the leading edge of the transported roll sheet 4C, the transportation rollers 62, the cutter mechanism 80, the transportation rollers 63, the second leading-edge detection switch 72, and the transportation rollers 33 in this order. The path downstream of the transportation rollers 62 is common to the first transportation path Dl. The bypass transportation path D4 is a path which leads the cut-sheet 4D introduced from the manually sheet feeding section 30 to the photoreceptor drum 20 through a fifth leading-edge detection switch 75 for detecting the leading edge of the transported cut-sheet, a separation roller 32 for separating cut-sheets one from another by an abut plate (not shown) abutted against the cut-sheets, a sixth leading-edge detection switch 76 for detecting the leading edge of the transported cut-sheet, resist rollers 39, the second leading-edge detection switch 72 and the transportation rollers 33 in this order. The path downstream of the second leading-edge detection switch 72 in the bypass transportation path D4 is common to the first transportation path Dl. The cutter mechanism 80 has an elongated stationary blade 81 provided in a casing 80A and extending in a direction perpendicular to a transportation direction of the roll sheet 4A, 4B or 4C, and a rotary blade 82 cooperating with the stationary blade 81 to cut the transported roll sheet 4A, 4B or 4C therebetween. The roll sheet 4A, 4B or 4C is transported upward through the cutter mechanism 80. The document-original transportation section 10 is adapted to switch the transportation direction to either a regular direction R1 or a reverse direction R2 for the transportation of the document original 9. The image forming operation is performed when the document original is transported in the regular direction R1. When a plurality of copies are made from one document original, the document-original transportation section 10 alternates the regular transportation direction R1 and the reverse transportation direction R2 to transport the document original. The document-original transportation path 41 is provided upstream the document-original transportation section 10 with respect to the regular direction R1 on the top face of the machine body 1 and laterally projects from the top face of the machine body 1. The document-original transportation section 10 has a first document-original edge detection switch 11,, first transportation rollers 12, a second document-original edge detection switch 16, a second transportation roller 14 and third transportation rollers 15 arranged along the regular transportation direction R1 in this order. The first transportation rollers 12 are driven in response to the detection of the leading edge (on the downstream side in the regular transportation direction R1) of the document original 9 when the first document-original edge detection switch 11 is switched on. The second transportation roller 14 facing opposite to a transparent plate 13 for exposing the document original 9 to slit light serves to press the document original 9 against the transparent plate 13. The third transportation rollers 15 serve to discharge the document original 9 after the light exposure. The second document-original edge detection switch 16 is switched on when the document original 9 is transported therethrough in the regular transportation direction R1, thereby detecting the leading edge (with respect to the regular direction R1) of the document original 9. In response to the switch on of the second document-original edge detection switch 16, the transportation of the roll sheet 4A, 4B or 4C (hereinafter referred to simply as "roll sheet 4" when the term is used to explain the copying operation) is started, thereby coordinating the transportation of the roll sheet 4 with that of document original 9. The first document-original edge detection switch 11 is switched off after the document original 9 is transported therethrough in the regular transportation direction R1, thereby detecting the tail edge (with respect to the regular direction R1) of the document original 9. The cutter mechanism 80 is driven at a preset time point a predetermined time period after the detection of the tail edge of the document original 9 to cut the roll sheet 4. In this embodiment, the length of the transportation path extending from the cutter mechanism 80 to an image transfer position 20b of a corona discharge 24 for image transfer is set longer than the length of the document-original transportation path extending from the first document-original edge detection switch 11 to a document-original light-exposure position 44 by a distance between the light exposure position 20a of the photoreceptor drum 20 and the image transfer position 20b, so that the tail edge of the sheet 4 cut at the preset time point can correspond to the tail edge of the document original 9 for image formation. The second document-original edge detection switch 16 is switched off after the document original 9 is transported therethrough in the reverse transportation direction R2, thereby detecting the tail edge of the document original 9 transported in the reverse direction R2. In response to the switch off of the second document-original edge detection switch 16, the driving of the transportation rollers 12, 14 and 15 is stopped. At this time, the leading edge of the document original 9 is held between the transportation rollers 12 for the next copying operation. A reference numeral 8 denotes a reversion member for preventing the document original 9 from dropping to the rear side of the machine body 1 by reversing the transportation direction of the document original. A stationary light source 17 for irradiating the document surface of the document original 9 is disposed in a predetermined relation with respect to the transparent plate 13. The light from the light source 17 is emitted onto the document surface through the transparent plate 13. The light reflected on the surface of the document original 9 is led to the surface of the photoreceptor drum 20 disposed in a generally central portion of the machine body 1 by means of a selfoc lens 18. Before being exposed to the light from the selfoc lens 18, surface of the photoreceptor drum 20 is uniformly charged by a corona discharger 21 for electrostatic charging. After the light exposure, an electrostatic latent image corresponding to a document original image is formed on the surface of the photoreceptor drum 20. The electrostatic latent image is developed into a toner image by a developing unit 22. The toner image formed on the photoreceptor drum 20 is brought into the vicinity of the corona discharger 24 for image transfer, as the photoreceptor drum 20 is rotated in a direction indicated by the arrow 23. On the other hand, the sheet 4 led to the photoreceptor drum 20 from the transportation path D1, D2 or D3 is led into the vicinity of the corona discharger 24 for image transfer with being brought into contact with the surface of the photoreceptor drum 20. Then, the toner image formed on the surface of the photoreceptor drum 20 is transferred onto the sheet 4 by way of corona discharge by the corona discharger 24 for image transfer. The sheet 4 having the toner image transferred thereon is removed from the surface of the photoreceptor drum 20 by way of corona discharge by a corona discharger 25 for sheet removal, and then led to a fixing unit 35 through the transportation path 34. In the fixing unit 35, toner is fixed onto the surface of the sheet 4 by heat-pressing the sheet 4 between a heat roller 37 and a press roller 38. The sheet 4 on which the toner is fixed is discharged out of the machine body 1 through a discharge detection switch 55 and discharge rollers 36, guided by the guide member 91, and accommodated in the pocket 92, as described above. After the toner image is transferred, the toner remaining on the surface of the photoreceptor drum 20 is removed by a cleaning unit 26 for the next electrostatic latent image formation. Similarly, the cut-sheet 4D led to the photoreceptor drum 20 from the bypass sheet feeding path D4 is subjected to the toner image transfer and the toner fixation, and then discharged into the pocket 92. Above the guide member 91 is disposed an auxiliary guide plate 94. The auxiliary guide plate 94 is pivotally supported by a stay 95 attached to the front face la of the machine body 1. The auxiliary guide plate 94 assumes either an attitude (indicated by a dashed line in FIG. 1) for guiding the discharged sheet 4 hanging down forwardly of the guide member 91 into the pocket 92 cooperatively with the guide member 91 or an attitude (indicated by a solid line in FIG. 1) for sheet accommodation in which the auxiliary guide plate 94 is supported by the stay 95. The attitude of the auxiliary guide plate 94 can be shifted by the pivotal movement thereof. Image forming means is constituted by such members as the photoreceptor drum 20, the developing unit 22 and the corona discharger 24 for image transfer. In this embodiment, the copying machine further includes a main motor MM for driving the image forming means, a sheet feeding motor DM for driving the transportation rollers for feeding the sheet 4A, 4B, 4C and 4D, a fixation motor FM for driving the heat roller 37 and press roller 38 of the fixing unit 35, and a document-original feeding motor OM for driving the document original transportation section 10. FIG. 4 is a block diagram illustrating one exemplary construction of a control circuit of the copying machine in accordance with this embodiment. The control circuit has a motor control circuit 220. The motor control circuit 220 may be a dedicated control circuit or may be incorporated in a CPU or the like which controls the operation of the copying machine. To the motor control circuit 220 are applied signals from the fifth leading-edge detection switch 75, the sixth leading-edge detection switch 76 and the second leading-edge detection switch 72. A sheet leading-edge detection signal 241 for the fixing unit and a sheet type identification signal 242 are also applied to the motor control circuit 220. Base on these signals, the motor control circuit 220 controls the main motor MM, the sheet feeding motor DM, the fixation motor FM and the document-original feeding motor OM. The rotational speeds of the main motor MM and the fixation motor FM are controlled to be always constant. Further, the motor control circuit 22C controls the rotation and stoppage of the transportation rollers 33, the resist rollers 39 and the separation roller 32 by controlling the clutches 221, 222 and 223. Referring to FIGS. 1 and 4, one of the features of the copying machine is an improvement in which the cut-sheet transported through the bypass transportation path D4 is prevented from being biased with respect to the transportation direction of the cut-sheet or from being biasedly transported. The prevention of biasing of the cut-sheet is achieved, as will be later described, by setting the rotational circumferential speed of the resist rollers 39 (the first roller) slightly lower than that of the transportation rollers 33 (the second roller). Another feature of this embodiment is that the offset of a toner image to be transferred onto a cut-sheet is prevented which is caused by vibration of the cut-sheet due to fluctuation in the load to the transportation rollers 33. The load fluctuation is caused by a sudden removal of the tensile force which has been applied to the cut-sheet, when the tail edge of the cut-sheet transported through the bypass transportation path D4 departs from the resist rollers 39. The prevention of the image offset on the cut-sheet is also achieved by controlling the circumferential speed of the resist rollers 39. More specific explanation will be given to the rotation control of the photoreceptor drum 20, the transportation rollers 33, the resist rollers 39 and the separation roller 32 with reference to a timing chart in FIG. 5. The main motor MM is driven, and the photoreceptor drum 20 starts rotating. When a cut-sheet is inserted from the manually sheet feeding section 30 in this state, the fifth leading-edge detection switch 75 is switched on by the leading edge of the cut-sheet. In response to an ON signal of the fifth leading-edge detection switch 75, the motor control circuit 220 rotates the sheet feeding motor DM, and switches on the clutch 223 to rotate the separation roller 32. Thus, the cut-sheet inserted from the manually sheet feeding section 30 is taken in and transported to the resist rollers 39. Where a plurality of cut-sheets are inserted from the manually sheet feeding section 30, the cut-sheets are taken in on the one-by-one basis by means of the separation roller 32. When the cut-sheet is taken in by the separation roller 32, the leading edge of the cut-sheet switches on the sixth leading-edge detection switch 76. An ON signal of the sixth leading-edge detection switch 76 is applied to the motor control circuit 220. The motor control circuit 220 switches off the clutch 223 a predetermined time period after receiving the ON signal, and stops the rotation of the separation roller 32. This ensures that the cut-sheet is stopped with the leading edge thereof abutting against the resist rollers 39. More specifically, if the cut-sheet inserted from the manually sheet feeding section 30 is slightly biased with respect to the bypass transportation path D4, only a part of the leading edge of the cut-sheet abuts against the resist rollers 39. When the cut-sheet is further forced forward by the separation roller 32 in this state, the biased attitude of the cut-sheet is corrected so that the cut-sheet is aligned with the bypass transportation path D4. Thus, the entire leading edge of the cut-sheet abuts against the resist rollers 39. That is, the leading edge of the cut-sheet is aligned with a line perpendicular to the transportation direction. Thereafter, the clutch 222 is switched on at a predetermined time point, and the resist rollers 39 are rotated by the sheet feeding motor DM. The cut-sheet is transported along the bypass transportation path D4 by the rotation of the resist rollers 39, and the leading edge thereof reaches the transportation rollers 33. Just prior to the transportation rollers 33 is provided the second leading-edge detection switch 72. Therefore, when the leading edge of the cut-sheet is about to reach the transportation rollers 33, the second leading-edge detection switch 72 is switched on. The motor control circuit 220 switches off the clutch 222 and stops the resist rollers 39 in response to an ON signal of the second leading-edge detection switch 72 applied thereto. The clutches 221 and 222 are switched on at a predetermined time point in coordination with the transportation of the document original by the document transportation section 10. The transportation rollers 33 and the resist rollers 39 are rotated, thereby transporting the cut-sheet. In this case, the rotational circumferential speed of the transportation rollers 33 is set to a level different from that of the resist rollers 39. More specifically, the rotational circumferential speed of the resist rollers 39 is set lower by about 1% to 2% than that of the transportation rollers 33. Thereby, the cut-sheet is transported by the transportation rollers 33 at a higher speed and transported by the resist rollers 39 at a lower speed. Accordingly, a predetermined tensile force is constantly applied to the cut-sheet traveling from the resist rollers 39 to the transportation rollers 33. The application of the predetermined tensile force to the cut-sheet transported along the transportation path prevents the cut-sheet from being biased with respect to the transportation path or from being biasedly transported. As described above, the copying machine in accordance with this embodiment is capable of copying a large-size document original such as of A0 size. To copy a document original of A0 size, a cut-sheet to be inserted from the manually sheet feeding section 30 has to be of A0 size. When the leading edge of such a large-size cut-sheet transported through the transportation rollers 33 reaches the photoreceptor drum 20, the rearward portion thereof hangs down from the entrance of the manually sheet feeding section 30. As the cut-sheet is further transported, the tail edge of the cut-sheet passes through the fifth leading-edge detection switch 75. When the tail edge of the cut-sheet passes through the fifth leading-edge detection switch 75, the fifth leading-edge detection switch 75 is switched off. In response to an OFF signal of the fifth leading-edge detection switch 75, the motor control circuit 220 increases the rotational speed of the sheet feeding motor DM. The rotational circumferential speed of the resist rollers 39 is increased by the increase in the rotational speed of the sheet feeding motor DM. More specifically, the rotational circumferential speed of the resist rollers 39 is increased, for example, by about 5% to 7%. Since the increase in the rotational circumferential speed of the resist rollers 39 is achieved by increasing the rotational speed of the sheet feeding motor DM, not by shifting a clutch, the circumferential speed can be smoothly increased. Therefore, the tensile force applied to the cut-sheet traveling from the resist rollers 39 to the transportation rollers 33 is smoothly relieved without giving a shock to the cut-sheet transported by the transportation rollers 33 and the resist rollers 39. Thereafter, the tail edge of the cut-sheet passes through the sixth leading-edge detection switch 76, which is thereby switched off, and then departs from the resist rollers 39. When the tail edge of the cut-sheet departs from the resist rollers 39, the tensile force applied to the cut-sheet transported from the resist rollers 39 to the transportation rollers 33 is relieved as described above. Therefore, the transportation rollers 33 suffer from no load fluctuation and apply no vibration to the cut-sheet at the moment the tail edge of the cut-sheet departs from the resist rollers 39. The clutch 222 is switched off a predetermined time period (e.g., about one second) after the sixth leading-edge detection switch 76 is switched off, thereby stopping the resist rollers 39. Thereafter, the tail edge of the cut-sheet passes through the second leading-edge detection switch 72, thereby switching off the second leading-edge detection switch 72. Then, the tail edge of the cut-sheet is transported from the transportation rollers 33 to the photoreceptor drum 20. The clutch 221 is switched off a predetermined time period after the tail edge of the cut-sheet departs from the transportation rollers, i.e., after the second detection switch 72 is switched off, thereby stopping the transportation rollers 33. In this embodiment, the resist rollers 39 provided on the bypass transportation path D4 allow the leading-edge of the cut-sheet inserted into the bypass transportation path D4 to be aligned with a line perpendicular to the transportation direction, as described above. In such a state, the transportation of the cut-sheet is started, and a predetermined tensile force is constantly applied to the cut-sheet transported from the resist rollers 39 to the transportation rollers 33. This prevents the cut-sheet transported along the transportation path from being biased with respect to the transportation path. However, at the moment the tail edge of the cut-sheet transported from the resist rollers 39 to the transportation rollers 33 with the tensile force constantly applied thereto departs from the resist rollers 39, the tensile force is suddenly removed from the cut-sheet. This may cause load fluctuation to the transportation rollers 33 and give vibration to the cut-sheet. In this embodiment, when the tail edge of the transported cut-sheet is brought into the vicinity of the resist rollers 39, the rotational circumferential speed of the resist rollers 39 is increased to smoothly relieve the tensile force applied to the cut-sheet transported from the resist rollers 39 to the transportation rollers 33. Thus, the biased transportation and image offset can be prevented which tend to occur when a large-size cut-sheet is transported along the bypass transportation path D4. Though the copying machine in accordance with this embodiment is adapted to use a roll sheet as the transfer sheet on a regular basis and, when using a cut-sheet as the transfer sheet, manually feed thereto the cut-sheet from the manually sheet feeding section 30, the construction of the present invention is applicable to a copying machine which is adapted to use a cut-sheet as the transfer sheet on a regular basis and automatically feed thereto the cut-sheet. In the aforesaid embodiment, the explanation has been given to the method for controlling the cut-sheet transportation which is employed when a cut-sheet is used as the transfer sheet. This method can be applied to the sheet transportation control where a roll sheet is used as a transfer sheet. To be more specifically described with reference to FIG. 1, the transportation rollers 63 and 33 are used where the roll sheet 4A, 4B or 4C is transported to the photoreceptor dram 20. The method for controlling the rotation of the resist rollers 39 previously described with reference to FIG. 5 is applied to the rotation control of the transportation rollers 63. Thus, a tensile force can be applied to the roll sheet transported from the transportation rollers 63 to the transportation rollers 33, thereby preventing the roll sheet from being biasedly transported. When the tail edge of the roll sheet departs from the transportation rollers 63, the rotational speed of the transportation rollers 63 is increased, thereby preventing the roll sheet from being subjected to vibration. With the aforesaid arrangement, the transfer sheet can be transported to the image forming section without being biased with respect to the transportation direction. Therefore, the copying machine rarely causes jam of a transfer sheet. In particular, where a large-size cut-sheet is used as the transfer sheet, the occurrence of jam of the cut-sheet can be significantly reduced. As described above, the proper transportation of a transfer sheet can be ensured by giving consideration to the method for controlling the transportation of the transfer sheet. In the present invention, distortion of an image to be transferred onto a transfer sheet can be prevented not only by controlling the transportation of a transfer sheet but also by changing the transportation speed of a document original. The method for controlling the transportation speed of a document original will hereinafter be described more specifically. In case of an electrophotographic copying machine, the sheet transportation speed in a fixing unit is generally set a little higher than the circumferential speed of a photoreceptor. This is because a consideration is given to prevent the slacking of the transfer sheet which may occur when the transfer sheet having a toner image transferred thereto from the photoreceptor drum is transported to the fixing unit. Where a fairly long-size transfer sheet is used, the transfer sheet traveling speed relative to the circumferential speed of the photoreceptor drum varies. More specifically, where the leading edge of a transfer sheet has not yet reached the fixing unit and the toner image is transferred onto a forward portion of the transfer sheet, the transfer sheet traveling speed relative to the circumferential speed of the. photoreceptor drum is low. On the other hand, where the leading edge of the transfer sheet has reached the fixing unit and the toner image is transferred onto a rearward portion of the transfer sheet from the photoreceptor drum, the rearward portion of the transfer sheet travels at a speed higher than the circumferential speed of the photoreceptor drum. That is, the forward portion of the long-size transfer sheet is transported at a relatively low speed with respect to the circumferential speed of the photoreceptor drum, while the rearward portion of the long-size transfer sheet is transported at a relatively high speed. Therefore, the scale of an image slightly varies along the transportation direction, i.e., the forward portion and rearward portion of the transfer sheet have slightly different image scales. In this embodiment, the transportation speed of the document original is changed in accordance with the change in the transportation speed of the transfer sheet for correction of the image scale. Where the transfer sheet traveling speed relative to the circumferential speed of the photoreceptor drum is relatively low, i.e., where the image is transferred onto the forward portion of the transfer sheet, the document original is transported at a relatively low regular speed (generally at the same speed as the circumferential speed of the photoreceptor drum). On the other hand, when the leading edge of the transfer sheet reaches the fixing unit which starts transporting the transfer sheet at a relatively high speed, the document original is transported at a relatively high speed in harmonization therewith. As a result, the document original image to be formed on the photoreceptor drum is slightly shrunk as the transportation speed of the document original becomes relatively high, and the shrunk image is slightly expanded to be transferred on the transfer sheet as the transportation speed of the transfer sheet becomes relatively high. Thus, the document original image is transferred onto the transfer sheet without changing the scale thereof. More specifically, the rotational speed of the document-original feeding motor OM is changed in accordance with the change in the transportation speed of the transfer sheet under the control by the motor control circuit 220. When the speed of the document-original feeding motor OM is changed, the rotational circumferential speeds of the first transportation rollers 12, the second transportation roller 14 and the third transportation rollers 15 in the document-original transportation section 10 (shown in FIG. 1) driven by the motor OM are changed. Thus, the transportation speed of the document original is changed. The motor control circuit 220 changes the rotational speed of the document-original feeding motor OM in response to a transfer-sheet leading-edge detection signal 241 for the fixing unit applied thereto. The transfer-sheet leading-edge detection signal 241 for the fixing unit indicates a time point at which the heat roller 37 and press roller 38 start transporting the transfer sheet at a transportation speed higher than the former transportation speed when the leading edge of the transfer sheet transported along the transportation path 34 (see FIG. 1) reaches the fixing unit 35. For example, the transfer-sheet leading-edge detection signal 241 for the fixing unit is output a predetermined time period after the transportation rollers 33 start transporting the transfer sheet toward the photoreceptor drum 20. That is, the transfer sheet is once stopped at the transportation rollers 33, and then the transportation of the transfer sheet by the transportation rollers 33 is started in synchronization with the start of the image formation at the photoreceptor drum 20. The transportation rollers 33 are driven by the main motor MM, which constantly transports the transfer sheet at a constant speed. Accordingly, the leading edge of the transfer sheet transported through the transportation path 34 reaches the fixing unit 35 the predetermined time period after the transportation rollers 33 start transporting the transfer sheet. Therefore, the transfer-sheet leading-edge detection signal 241 for the fixing unit is output the predetermined time period after the start of the driving of the transportation rollers 33. In another arrangement of the present invention, a leading-edge detection switch is disposed prior to the fixing unit 35 or in a given position on the transportation path 34., and the transfer-sheet leading-edge detection signal 241 for the fixing unit is output a predetermined time period after an ON signal is output when the leading-edge detection switch is switched on by the passage of the leading edge of the transfer sheet transported along the transportation path 34. Thus, the transfer-sheet leading-edge detection signal 241 for the fixing unit indicates a time point at which the fixing unit 35 starts transporting the transfer sheet at a transportation speed higher than the former transportation speed when the leading edge of the transfer sheet transported along the transportation path 34 reaches the fixing unit 35. As shown in FIG. 6, the motor control circuit 220 increases the rotational speed of the document-original feeding motor OM in response to the transfer-sheet leading-edge detection signal 241, thereby increasing the transportation speed of the document original. Accordingly, the document original image to be formed on the photoreceptor drum is slightly shrunk in the rotational direction of the photoreceptor drum by the increase in the document-original transportation speed. However, since the transfer sheet is transported to the photoreceptor drum at a higher speed, the shrunk image is slightly expanded in the transportation direction of the transfer sheet to be transferred on the transfer sheet. Thus, the scale of the document original image can be kept unchanged despite the change in the transportation speed of the transfer sheet. Referring back to FIG. 4, the motor control circuit 220 also receives a transfer-sheet type identification signal 242. The copying machine uses as the transfer sheet the roll sheet 4A, 4B or 4C or the cut-sheet transported through the bypass transportation path D4. The transfer-sheet type identification signal 242 indicates the type of the transfer sheet to be used. The motor control circuit 220 corrects a change in the speed of the document-original feeding motor OM in accordance with the type of the transfer sheet to be used. This is because different types of transfer sheets have different stretchabilities. More specifically, a film sheet, normal paper and tracing paper have greater stretchabilities in this order. The difference in the stretchability between transfer sheets influences the change in the scale of an image which is to occur when the transportation speed relative to the circumferential speed of the photoreceptor drum 20 is changed. In this embodiment, the rate of change in the rotational speed of the document-original feeding motor OM is, therefore, suitably corrected depending on the type of transfer sheet to change the rate of change in the document-original feeding speed. As a result, the scale of an image to be formed can be corrected to be equivalent to that of the document original image, regardless of the type of transfer sheet to be used. Where a copy is to be made from a large-size document original on a transfer sheet of a large size corresponding to the size of the document original, the copying machine with the construction of this embodiment prevents the change in the scale of an image to be copied along the transportation direction, thereby providing an excellent copy image. In accordance with the aforesaid embodiment, an improved copying machine capable of forming an excellent copy image is provided, which does not produce a scale difference between images formed on forward and rearward portions of a transfer sheet where the transfer sheet has a length longer than the distance between an image transfer position and an image fixing position. The copying machine is particularly suitable for copying an image on a large-size transfer sheet such as of A0 size. Though a copying machine is taken as an example of the image forming apparatus in the foregoing description, the present invention is applicable to any other image forming apparatuses such as printing machine, which are adapted to form an image on a particularly large-size transfer sheet.
An image forming apparatus that includes an image reading section, a transportation path, a photoreceptor, transferring area, a fixing area, and a feeding speed controller. The feeding speed controller selects the speed at which an original document passes through the image reading section between two speeds. A first speed is used when the transfer sheet is normal sized and for a period of time prior to a large sized sheet entering the fixing area. Once a large sized sheet enters the fixing area, the feeding speed controller changes the speed of the original document from the first speed to the second speed to provide proper scaling of the reproduced image on the transferred sheet. The second speed may be adjusted depending on the type of transfer sheet being used to take into account the amount of stretching of the material used to make the transfer sheet.
6
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT This invention was made with Government support under contract No. DE-AC05-960R22464 awarded by the United States Department of Energy to Lockheed Martin Energy Research Corporation, and the Government has certain rights in this invention. BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates generally to the field of accelerator mass spectrometry. More particularly, the invention relates to accelerator mass spectrometers employing a multicharged ion source. 2. Discussion of the Related Art The main difficulty in single atom detection of C-14 arises from the isobaric interferences due to N-14 atomic ions and 12 CH 2 and 13 CH molecular ions. In conventional accelerator mass spectrometry (AMS) the approach consists of using a negative ion source to eliminate the 14 N contamination, since it does not support a stable negative ion, accelerating the negative ion beam in a tandem accelerator to high energy (few MeV), and then dissociating molecular ions isobaric with 14 C − also present in the ion beam either in a foil or gas target. Subsequent stages of electrostatic and magnetic analysis are then used to isolate the 14 C ions prior to their detection. Conventional AMS requires large, nuclear physics scale facilities, with correspondingly high cost, which are usually not dedicated to a single task, and entails time consuming sample preparation prior to the actual measurements, and so is not suited to quasi-real time monitoring Of C-14 levels. SUMMARY OF THE INVENTION The invention includes an apparatus and method for the detection of carbon-14 and other rare isotopes where molecular ion isobaric interferences are a problem, and where interfering atomic isobars do not form stable negative ions. In this invention, large nuclear physics scale facilities such as used in conventional accelerator mass spectrometry (AMS), for example, are not needed. These, and other, goals and embodiments of the invention will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following description, while indicating preferred embodiments of the invention and numerous specific details thereof, is given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the invention without departing from the spirit thereof, and the invention includes all such modifications. BRIEF DESCRIPTION OF THE DRAWINGS A clear conception of the advantages and features constituting the invention, and of the components and operation of model systems provided with the invention, will become more readily apparent by referring to the exemplary, and therefore nonlimiting, embodiment illustrated in the drawing accompanying and forming a part of this specification. FIG. 1 a illustrates a high level schematic view of an accelerator mass spectrometry apparatus, representing an embodiment of the invention. FIG. 1 b illustrates a high level schemative view of another accelerator mass spectrometry apparatus, representing an embodiment of the invention. DESCRIPTION OF PREFERRED EMBODIMENTS The invention and the various features and advantageous details thereof are explained more fully with reference to the nonlimiting embodiments that are illustrated in the accompanying drawings and detailed in the following description of preferred embodiments. Descriptions of well known components and processing techniques are omitted so as not to unnecessarily obscure the invention in detail. Within this application several publications are referenced by Arabic numerals within parentheses. Full citations for these, and other, publications may be found at the end of the specification immediately preceding the claims after the section heading References. The disclosures of all these publications in their entireties are hereby expressly incorporated by reference into the present application for the purpose of indicating the background of the invention and illustrating the state of the art. The below-referenced U.S. Patents disclose embodiments that were satisfactory for the purposes for which they were intended. The entire contents of U.S. Pat. Nos. 4,489,237; 5,661,299; 5,621,209; and 4,830,010 are hereby expressly incorporated by reference into the present application as if fully set forth herein. FIG. 1 a illustrates an embodiment of an apparatus 10 according to the invention. The apparatus 10 includes multicharged ion source 12 for the production of a multicharged ion beam 14 . Suitable multicharged ion sources include, but are not limited to, an electron cyclotron resonance (ECR) ion source. An ECR ion source 12 contains a high-temperature electron plasma which is very efficient in removing electrons from source atoms to form multiply charged positive ions. If mass-14 ions are extracted from the ECR plasma in sufficiently high charge states, one is assured that there will be no molecular species in the extracted multicharged ion beam 14 , since the loosely bound electrons forming the relevant chemical bonds of the molecule will have been removed, leading to immediate breakup of the molecule into smaller mass fragments. During operation of the apparatus 10 , the ECR preferably produces a multicharged ion beam 14 with a charge state which is high enough to eliminate molecular isobar interference. The charge state is preferably at least +2, and more preferably at least +3. In addition to facilitating removal of one of the isobaric interferences, a further advantage of using an multicharged ion source such as an ECR source 12 is very high ionization efficiency. Stable C beams with ionization efficiencies as high as 24% are achievable for formation of +4 ions. For low abundance isotopic species, this value is reduced about a factor of two due to adsorption on the source chamber wall. However, the use of a hot liner can reduce wall adsorption, and result in values very close to that obtained for the corresponding stable isotope. After the multicharged ion beam 14 is extracted from the multicharged ion source 12 and accelerated to energies in the keV range, the beam 14 passes to an analyzing magnet 15 where the ions are separated into different regions according to their mass-14 charge state. The ions in different regions can be processed independently of one another. For instance, the ions in one region can be received by a detector 16 for monitoring the C-12 intensity for reference purposes and the ions in another region can be selected for further processing by the apparatus. The charge state for the selected ions is preferably at least +2, more preferably +3, and most preferably +4 to maximize ionization efficiency. The beam 14 from the analyzing magnet 15 will be completely free of any interfering molecular isobars, but will still contain a strongly dominant 14 N component of the same charge state. The beam 14 from the analyzing magnet 15 enters a UHV chamber 17 where the beam 14 is incident upon a target surface 18 at a grazing angle of incidence for the formation of negative ions. The angle of incidence is preferably at most approximately 5° (e.g. from approximately 1° to approximately 5.0°), but depends on the energy of the multicharged ion beam. Suitable target surfaces 18 include, but are not limited to, a metal or insulator high quality single crystal. With a LiF (100) target, very high efficiency for converting incident multicharged O and F projectiles into scattered negative ions can be obtained, that is essentially independent of incident charge state. Maximum efficiencies for converting incident C 4+ to C − are estimated to be in the 50% range. Operating the insulator target surface at high temperature where the ionic conductivity will be sufficiently high will ameliorate sample-charging effects due to impact of the high intensity ion beam 14 . Alternatively a single crystal metal target can be used, with a concomitant decrease of negative ion yield of about an order of magnitude, but having the same feature of the negative ion yield being independent of incident charge state. This feature is a key one, in that it permits the choice of charge state to be determined solely on the basis of maximum ionization efficiency. Since specular reflection conditions apply, the scattered beam 14 will still have low divergence, small size, and very close to its original energy. The scattered beam 14 passes from the target 18 to a first (primary) electrostatic analyzer 20 to disperse the different scattered charge states. The different scattered charge states can be dispersed into different regions 21 . The different regions 21 can be discrete or can overlap. Suitable first electrostatic analyzers 20 include, but are not limited to, low resolution electrostatic analyzers and low resolution deflection plates. The ions in the zone 21 receiving the charge state of interest pass to a second (secondary) electrostatic analyzer 22 which further spatially separates the desired 14 C − ions from other scattered charge states. The secondary analyzer can provide high resolution. For instance, the negative ion component of the beam 14 can be further separated from the other scattered charge states to further reduce background and discriminate against other negative ions of different energy (e.g. 28 Si − from 28 Si 8+ having the same mass to charge ratio as the 14 C 4+ ions extracted from the ECR source 12 ). The negative ion component of the beam 14 will not exhibit interference from 14 N due to the instability of 14 N as a negative ion. The second electrostatic analyzer 22 preferably has a higher resolution than the first electrostatic analyzer 20 . Suitable second electrostatic analyzers 22 include, but are not limited to cylindrical or hemispherical analyzers. The beam 14 from the second electrostatic analyzer 22 is received by a particle detector 24 such as a channel electron multiplier or multichannel plate, which may be position sensitive. FIG. 1 b illustrates an alternative embodiment of the apparatus 10 according to the invention. This embodiment of the apparatus adds an electrostatic analysis apparatus 13 prior to the surface scattering stage to remove possible contamination due to charge exchange of the extracted beams with residual gas prior to magnetic analysis. As depicted, the electrostatic analysis apparatus involves turning an additional turn of the beam 14 . In place of the beam/solid target negative ion formation process, a gas cell could be introduced in which multiple electron capture could occur to form the fast neutrals, followed by a second gas cell for negative ion formation. If a suitable gas could be found, the two steps could be performed in a single gas cell. Any approach involving gas phase collisions for the neutralization of the multicharged ions and negative ion formation will have much lower efficiency than the ion-target surface interaction process. In place of the ECR ion source 12 , other ion sources of low energy multicharged ions could, in principle, be employed. But at present only the ECR source 12 combines the high ionization efficiency and beam intensity characteristics required for this apparatus 10 . This invention can in principle be used for detection of other rare isotopes where molecular ion isobaric interferences are a problem, and where interfering atomic isobars do not form stable negative ions, provided the specie of interest can be formed in a charge state sufficiently high that the interfering molecular ion is no longer stable. The apparatus 10 has value within the technological arts. As medical diagnostic, for measurements of in vivo 14 C uptake related to detection of cancer or other pathologies, for biomedical research into oral availability of drugs or transport across cell membranes, for radiocarbon dating applications in the areas of paleoclimatology and archaeology, for tracer studies of atmospheric chemistry and transport, ocean mixing, erosional processes and glacial recession, diffusion through soils, as diagnostic in studies of diesel exhaust pollution, lubricant consumption and degradation, wear analyses of graphite composite materials, and of various petroleum industry problems (see Ref. 10). There are virtually innumerable uses for the invention, all of which need not be detailed here. The ion-target surface interaction process described above (see also Ref. 8 and 9) essentially combines two steps: neutralization of the multicharged C ions and negative ion formation. This results in simplicity, compactness of design and low cost. Additionally, the apparatus 10 requires voltages in the range 5-20 kV in contrast to the conventional approaches (Ref. 1 and 3) which can require at least a factor of 100 higher voltages. The reduced voltage requirements can also translate into increased simplicity, compactness and reduced cost. Additionally, the compact ECR source 12 (Ref. 7) combined with the highly efficient process for converting multicharged positive ions to negative ions (Ref. 7 and 8) provides an increased efficiency and throughput than those obtained with existing approaches. The difficulty of sample preparation is substantially reduced in the invention as compared to conventional accelerator mass spectrometry (AMS) hardware. In previous approaches the samples had to be converted off line to solid pellets (Ref. 1) that could be inserted into a negative ion sputter source. The present scheme can use samples in gaseous (see Ref. 5) form directly (Ref. 6 and 7). Together with the highly efficient compact ECR source 12 and method for converting multicharged positive ions to negative ions, this makes possible much faster processing times, and opens the possibility of quasi real-time monitoring. The apparatus 10 can also provide an increased sensitivity above what can be achieved with conventional biomedical tracer measurement methods. This increased sensitivity permits usage of lower radioactive tracer levels, with corresponding positive environmental, health and safety, and financial impacts. Because of the above advantages, this apparatus 10 should find great utility in quasi-real time monitoring of C-14 based chemical tracer uptake in biological systems for the purposes of atmospheric pollution studies, cancer research, medical diagnostics, or other biomedical studies. The term “approximately”, as used herein, is defined as at least close to a given value (e.g., preferably within 10% of, more preferably within 1% of, and most preferably within 0.1% of). The term “substantially”, as used herein, is defined as at least approaching a given state (e.g., preferably witin 10%, more preferably within 1% of, and most preferably within 0.1% of). The term “coupled”, as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically. All the disclosed embodiments of the invention described herein can be realized and practiced without undue experimentation. Although the best mode of carrying out the invention contemplated by the inventors is disclosed above, practice of the invention is not limited thereto. Accordingly, it will be appreciated by those skilled in the art that the invention may be practiced otherwise than as specifically described herein. For example, the individual components need not be formed in the disclosed shapes, or assembled in the disclosed configuration, but could be provided in virtually any shape, and assembled in virtually any configuration. Further, the individual components need not be fabricated from the disclosed materials, but could be fabricated from virtually any suitable materials. Further, although the components of the apparatus described herein can be constructed from physically separate modules, it will be manifest that any two or more of the components may be integrated into a single modules. Furthermore, all the disclosed elements and features of each disclosed embodiment can be combined with, or substituted for, the disclosed elements and features of every other disclosed embodiment except where such elements or features are mutually exclusive. It will be manifest that various additions, modifications and rearrangements of the features of the invention may be made without deviating from the spirit and scope of the underlying inventive concept. It is intended that the scope of the invention as defined by the appended claims and their equivalents cover all such additions, modifications, and rearrangements. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means-for.” Expedient embodiments of the invention are differentiated by the appended subclaims. REFERENCES 1. D. Elmore and F. M. Phillips, Science 236, 543 (1987). 2. U.S. Pat. No. 4,489,237: Method of broad band mass spectrometry and apparatus therefor. 3. U.S. Pat. No. 5,661,299: Miniature AMS detector for ultrasensitive detection of individual carbon-14 and tritium atoms. 4. U.S. Pat. No. 5,621,209: Attomole detector. 5. U.S. Pat. No. 4,830,010: Methods for the diagnosis of gastrointestinal disorders. 6. R. Geller and B. Jacquot, Physica Scripta T3 (1983); R. Geller, IEEE Trans. Nucl. Sci. NS-26, 2120 (1979). 7. L. Maunoury et al., Proc. 13th Int. Workshop on ECR Ion Sources, D. May, ed., Texas A&M, 26-28 February 1997. 8. L. Folkerts, S. Schippers, D. M. Zehner, and F. W. Meyer, Phys. Rev. Lett. 74, 2204 (1995). FIG. 3 . 9. F. W. Meyer, Q. Yan, P. Zeijlmans van Emmichoven, I. G. Hughes, and G. Spierings, NIMB 125, 138 (1997). FIG. 12 . 10. J. C. Davis, NIMB 92, 1 (1994).
A method for performing accelerator mass spectrometry, includes producing a beam of positive ions having different multiple charges from a multicharged ion source; selecting positive ions having a charge state of from +2 to +4 to define a portion of the beam of positive ions; and scattering at least a portion of the portion of the beam of positive ions off a surface of a target to directly convert a portion of the positive ions in the portion of the beam of positive ions to negative ions.
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