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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This divisional application claims the priority benefits of U.S. Non-Provisional application Ser. No. 14/463,627, filed Aug. 19, 2014, titled “Systems and methods of enabling integrated activity scheduling, sharing and real-time social connectivity through an event-sharing platform”, and U.S. Provisional Application Ser. No. 61/867,494, filed Aug. 19, 2013, titled “A Real Time Calendar Feed and Event-Scheduling Platform”, the disclosures of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The embodiments herein relate to social media sharing platforms, particularly those that enable activity scheduling and interactive sharing during said activities, between users as peer consumers as well as interactive sharing between users as consumers and users as activity providers.
BACKGROUND
[0003] Rapid technological advancements in telecommunications nowadays make it possible to instantly access the Internet, obtain information, find and consume services, attend or join activities and share nearly anything with anyone, such as activities, images, videos, opinions, thoughts and bookmarks using any web-ready mobile device such as tablets, digital cameras, digital recorders, body gear, consoles, terminals, drones, PDAs, laptops, computers or phones. Social media platforms are based on media created and disseminated by users through social interaction, which may be blogging, photo sharing, video sharing, product reviewing, and so forth. Social media and social network platforms and their applications make this real-time interaction easier by providing a central location of tools that make this happen, allowing various inter-relationships between users. Existing social network platforms connect users based on one or more specific types of interdependencies, such as friendship, family, interest, sexual orientation, social status, business relationships, and so on. Social networks however, are not generally based on connecting consumers and activities, and more importantly not connecting users with activities around the corner or in an unfamiliar town. With regard to events and activities, social media platforms may do better in not only influencing the way consumers behave, but how they interact as well. Using the feedback and information that these social media platforms manage to obtain on the activities they do collect, they affect user behaviors; so with the system and methods herein, users may select from a much larger, more enriched population of things to do of interest, stay connected with the activities that they might be enjoying regularly or might want to enjoy in the future, and interact with activity providers and other consumers.
[0004] A huge problem facing social consumers, entertainment enthusiasts, visiting tourists and bored consumers alike, is that a comprehensive source and simple process of locating upcoming activities, large or small, impromptu or one-time gatherings in a given area remains a challenge to this day. Whether it be a local movie night, a sale at a store, a farmer's market, a book club meeting, a grand opening at a restaurant, a rummage sale or local concert in the park, trying to discover something to do of interest can be frustrating. There are activity and event systems and publications available online and in print, but no single source is centralized and comprehensive. Existing sources are limited with sparse, “spammy”, stale, cherry-picked, or paid-only listings. As a result, in order to find out about activities happening in an area, one must stumble on them in newspaper listings, magazine sections, travel brochures, random flyers, TV advertising, radio advertising, word of mouth, local bulletin boards, online blogs, sparse media sources, or overhear it during casual conversation. The seemingly impossible task oftentimes results in an activity with no attendees, or worse yet, the discovery of an incredible event AFTER the date has passed, and the activity missed. FIG. 24A , Table 1 displays common event data sources currently used that may be replaced or supplemented by an event-scheduling platform.
[0005] With the growing popularity of social media interaction, consumers will continue to enjoy collecting images, amassing bookmarks, sharing discussions, creating music and video libraries, showing off an activity or location, and so forth, and there are many platforms to do this. There is no method, however that enables the collection of these items collectively as an activity or event “unit” or “entity” with cross interaction, for example, an instance where a blogger may be chatting with another user attending a seminar in another state, in real-time, discussing a slide show that a third user may be streaming from another room during a keynote speech, at the same seminar. The blogger may archive the entire interaction with all users including blogs, chats, slideshows, and speech transcript. FIG. 24B , Table 2 displays common sharing and archival methods currently used that may be replaced or supplemented by an event-scheduling platform.
[0006] Additionally, there are few, if any, mechanisms available for consumers to a) keep abreast and stay connected with all activities happening nearby, b) interact directly with activity providers, other users and even other attendees in real-time, through online tools in a way that fosters a new, unique shareable experience and c) instantly announce an activity for immediate consumption with global reach. An event-scheduling platform containing a social media suite may finally address these needs. Part of the reason for a disconnect occurring between users and unknown activities may be attributed to a limited and narrowed reach of activity promotion sources. Comprehensive activity listings are difficult to manage and obtain, due to a fragmented and selective collection process; so listings are cherry-picked, sparsely populated or reserved for higher ad payers and users see only a small portion of what is happening around them. Lack of new interactive experiences online can be attributed to existing social media platform tools and interfaces (Facebook®, Twitter®, LinkedIn®, Craigslist®, Yelp®, StumbleUpon®, Meetup®, Groupon®, GooglePlus®, Instagram®, Vine®, Tumblr®, Youtube®, Pinterest®, et al) being narrowed in scope and having limited, if any activity or event targeted functionality. None encourage users to get out of a residence to act. With regard to an ease of announcing and hosting an activity, none provide a simple or cost-effective, aggressive entry into an activity or event marketing and promotion space; and certainly none do it with a suite of tools, data object stores, image galleries, video libraries and live services that an event-scheduling platform provides. An event-scheduling platform paired with a social media suite may fill these voids if built with a core functionality that attaches each activity to a critical date parameter, to a location parameter, to user parameters, to data objects, to users and friends, forming permanent links between activities and users, creating “event entities” or “event units” that may have activity objects attached to them creating a massive activity-sharing network.
SUMMARY OF THE INVENTION
[0007] The embodiments herein provide for an effective social network comprising a graphical user interface of an event-scheduling platform and social sharing system comprising methods, interactive tools and services that may incite a user or activity provider to act; attend or join an activity, post an activity, host an activity, share an activity or interact with someone who is—with each action enhancing an ever growing, dynamic and robust, activity related data store, data gathering, and social communication engine creating a new level of interpersonal relationships and new ways to experience life.
[0008] The invention is an interactive activity scheduling and sharing Web site—a social media system also serving a robust event-scheduling platform with up-to-the-minute activity listings tailored for a user. This dual purpose may enable actual participation in activities of which one would otherwise not be aware and enable interaction with other users at an activity or even those not in attendance, simultaneously. The event-scheduling platform may collect and disseminate activity data based on user-specific criteria such as location, interests or preferences. Based on said criteria, the platform may instantly search the database, alert, announce and display all tailored activities within a user specified radius, including in-process ones, anywhere at any time and engage a user to act. It may also bring the activity to other users via powerful elements of images, voice, live streaming video and video upload, key documents and schedules, maps and a myriad of sharing options to enhance an experience. The invention may disseminate live, current activity data to users for immediate consumption. Activities may be online activities or offline events. They may comprise a deep discount sale at store, a live concert in the park, a grand opening of a restaurant, the birth of a baby, a graduation party, a weather alert, a sports event, a farmer's market, a keynote speech at a convention, a chat session with a celebrity, a live stream of a show; it could be anything. Immediate access may allow for immediate reaction, response and may satisfy today's human need for instant gratification. This coupled with the ability to share content with groups of individuals across the globe with live video streams, images, comments, voice, as if they were actually attending or joining an activity, may serve as a powerful tool in marketing and mobilizing people for a common purpose. Individuals may become their own actors, bloggers, reporters, photographers, videographers, broadcasters and newscasters. The platform may facilitate adding an activity to a user's stored schedule, or export to other calendaring software systems off-platform. Finally, users may post their own special event or activity and record it in history as an activity collection with intimate perspectives—with video recordings and uploads, shared objects and files, real-time comments and interactions with other attendees documented, all of which may far exceed a collection of images in a picture book.
[0009] Activities are added for immediate consumption, live updating and live sharing continually. The collection of data may occur automatically by computer or by manual means,—collected automatically from public and authorized Internet sources or entered by a user or activity provider using import tools and forms on the platform for adding an activity. By tapping into an always growing, global activity database of real-time, constantly evolving data, users may access relevant activities that suit their needs at any hour of the day. Given that a user or activity provider may list their activities in a simple way, regardless of their entity size, the database may accumulate large budgeted or heavily advertised activities along with small, local ones and ensure a most comprehensive activity data set. Activity providers, large and small, may promote their up-to-the-minute activity to a global audience equally. Furthermore, an event-scheduling platform may provide a medium for review and feedback that could foster improvements in marketing and promotion to ensure future activity successes and in turn encourage more activities. The activity database may realize unlimited growth and have unlimited growth potential.
[0010] Technologies of a scheduling system and a social media platform may exist separately on popular Web platforms, but nothing exists that joins the two platforms to form a powerful activity-sharing suite. This invention may bridge that gap by bringing all activities to a user, displaying them in data point clusters around said user's chosen location on a map, including those that would have otherwise been unknown and engaging a user to act. Given this, users may plan their schedules more effectively, even in an unfamiliar city. The platform may allow activity goers and users to review, discuss an activity and simultaneously broadcast their experience, creating a new experience and in doing so provide invaluable input to the activity provider. The platform may show the overall effectiveness of a marketing campaign to activity providers, give valuable feedback of user consumption and help improve future activity or activity success. Few online media systems exist that can generate, as this platform may, significant amounts of foot traffic for small brick and mortar businesses to compete with larger businesses or online shops on a level playing field. An event-scheduling platform, with a social media suite of services may allow individuals, businesses and communities to market themselves through their activities, incite users to act, get users out of their homes and into their doors, bringing in much needed, foot-traffic and revenue. The invention may memorialize entire activities by providing a record of all objects, comments, images, video, chats and streams in ways that before didn't exist. The usefulness of the invention will vary from user to user and user as activity provider. The event-scheduling platform herein may relieve users of boredom, encourage users to be active, be social, travel, browse, shop, dine, live and share experiences. As activity providers, any individual, group or business that looks to increase foot traffic to their event may see it as a valuable marketing tool. Corporations and enterprises that require organizing and mobilizing groups around a time sensitive deadline to achieve a desired result or project deliverable (i.e., event promoters, travel coordinators, party planners, contractors) may find value in the invention.
[0011] The embodiments herein relate to a system and a method for efficiently mining, collecting, organizing, managing, storing activity data to a comprehensive database and disseminating said data within a framework that enables users to act, interact and transact; looking for activities in which to participate now or schedule to participate in later, or as activity providers looking for a means to promote, manage and store objects related to an activity for retrieval by other users. The system may include software designed for collecting and disseminating this information on various media devices, i.e. mobile phones, digital cameras, digital recorders, laptops, personal computers, body gear, ocular viewers, consoles, terminals, tablets, drones and any Internet-ready device. The system may make it easier for users to overcome the “fear” of missing out of an activity by having all activity happenings displayed on these devices on-the-fly. Moreover, the system may streamline procedural bottlenecks in the coordination and organization of these individual activity related tasks by having them accessible for updating in real-time by users, promoters and activity providers, thus keeping the activity data current, shortening time periods and maximizing attendance. The invention may also allow for the immediate sharing of itineraries, calendars and schedules through social media sources, links, interest boards, personal walls, tags, image photo streams, video galleries, interactive conversations, comments, posts and reviews.
[0012] The event-scheduling platform is comprised a graphical user interface designed specifically for viewing on mobile and non-mobile computing devices, i.e., mobile phones, laptops, personal computers, body gear, ocular viewers, drones, PDAs, consoles, terminals and tablets. It may also include a full, and always updating, commercial relational database engine for the storage of content and user inputted information and user-defined custom preferences and locations.
[0013] The event-scheduling platform may include annotation and indexing mechanisms which may simplify the collection, storage and management of critical activity data elements and uploaded objects, bring these user-defined items into the same searchable context as those that are inherently systemic and structured so that they may be indexed and matched for tracking, analyzing and disseminating results in a useful way—through mapping, calendaring, notifying, viewing, reporting, archiving and sharing.
[0014] The event-scheduling platform may include a mapping feature that may use stored data and display categorized activity data points or pins relative to a user's location, entered address and stored user-defined preferences or selected categories and filters.
[0015] The event-scheduling platform may use a notification system to alert the user or activity provider to upcoming activities, system emergencies, pending activities or approaching task deadlines, based on user-defined criteria via voice and text alerts, text messages, emails or notifications to an inbox. The system may also use a notification system to send activity reminders and follow-ups to users registered to receive them. The system may allow the user or activity provider to send invitations, annotations, tags, and comments to other users via the notification system.
[0016] The event-scheduling platform may include a software architecture comprising an event-scheduling platform that is further comprised three environments: a 1) social media presentation tier comprising a social media suite, an 2) advertising, content, device and management tier, a 3) relational database tier.
[0017] The event-scheduling platform may include additional tools for activity tracking and presentation, report generation, data analytics, trend analysis, statistical routines, security patches and installation packages.
[0018] The event-scheduling platform may have a universal browser-based presentation structure that may be scaled and deployed across various hardware resources and networks without a need to retool. It may be implemented on phones, laptops, tablets, optical viewers, body gear, drones, PDAs, consoles, terminals and personal computers by rendering the software at the non-mobile or mobile computing device level.
[0019] The event-scheduling platform may utilize widgets and plug-ins—blocks of programming code containing Web site functionality comprising Web services, Web API, SOAP, REST, JSON and XML real-time activity feeds—to collect, disseminate and share activity data. Widgets and plug-ins may be designed for embedding into off-site Web pages, emails and messages seamlessly to collect data, display schedules, calendars and maps and showcase featured activities.
BRIEF DESCRIPTION OF THE ILLUSTRATIONS AND DRAWINGS
[0020] Other objects and advantages of this invention will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments, when read in light of the accompanying drawings wherein:
[0021] FIG. 1 illustrates a network incorporating an Event-Scheduling Platform (ESP), according to embodiments as disclosed herein;
[0022] FIG. 2 shows an ESP, according to embodiments as disclosed herein;
[0023] FIG. 3 shows communication links between the ESP interface and the user, according to embodiments as disclosed herein;
[0024] FIG. 4 illustrates an example user profile, according to embodiments as disclosed herein;
[0025] FIG. 5 illustrates an example login gateway, according to embodiments as disclosed herein;
[0026] FIG. 6A illustrates an example user initial access page before login, according to embodiments as disclosed herein;
[0027] FIG. 6B illustrates an example user initial access page after login, according to embodiments as disclosed herein;
[0028] FIG. 7A and FIG. 7B illustrate an example user initial access page in two scenarios, before login FIG. 7A and after login FIG. 7B , as viewed on a mobile device, according to embodiments as disclosed herein;
[0029] FIG. 8 illustrates an example search module and options, according to embodiments as disclosed herein;
[0030] FIG. 9 illustrates an import functionality between global and personal scheduling feeds, according to embodiments as disclosed herein;
[0031] FIG. 10 illustrates an example activity content page, according to embodiments as disclosed herein;
[0032] FIG. 11A and FIG. 11B illustrate an example activity content page, as viewed on a mobile device, according to embodiments as disclosed herein;
[0033] FIG. 12 illustrates an example activity-scheduling page in an activity management module, according to embodiments as disclosed herein;
[0034] FIG. 13 shows user-object relationships, according to embodiments as disclosed herein;
[0035] FIG. 14 shows a notification flow, according to embodiments as disclosed herein;
[0036] FIG. 15 shows an example RSVP system page, in an activity management module, according to embodiments as disclosed herein;
[0037] FIG. 16 shows an example notification system page, in an activity management module, according to embodiments as disclosed herein;
[0038] FIG. 17 illustrates an Initial Access, according to embodiments as disclosed herein;
[0039] FIG. 18 illustrates an Access As User Flowchart, according to embodiments as disclosed herein;
[0040] FIG. 19 illustrates an Access As Activity Provider Flowchart, according to embodiments as disclosed herein;
[0041] FIG. 20 illustrates a Content Module Flowchart, according to embodiments as disclosed herein;
[0042] FIG. 21 illustrates a Search Module Flowchart, according to embodiments as disclosed herein;
[0043] FIG. 22 illustrates an Add/Edit Activity Flowchart, according to embodiments as disclosed herein;
[0044] FIG. 23 illustrates a table comprising sample database, indices, and primary key assignments, according to embodiments as disclosed herein; and
[0045] FIG. 24A and FIG. 24B display replaced or supplemented, common sources table ( FIG. 24A ) and replaced or supplemented common archiving mediums table ( FIG. 24B ), according to embodiments as disclosed herein.
DEFINITIONS
[0046] user—For the purposes of this specification and the associated claims, the term “user” is used to reference the Event-Scheduling Platform (ESP) account owner, such as an individual, consumer, group, closed user group, user-agent, automated agent, corporate or a commercial entity.
[0047] activity, event, activity database records—For the purposes of this specification and the associated claims, the term “activity”, “event” and “activity database records” are used interchangeably to reference a happening and the related data records that are associated with it, such as an offline or online activity, streaming activity, non-streaming activity or recorded activity; which may consist of a performance, alert, broadcast, announcement, commercial event, sale event, open house, recorded audio, recorded video, fund-raiser, conference, political event, discussion, interview, auction, book-signing, lecture, lesson, natural disaster, emergency, flash mob, accident, prank, sports activity, family gathering, get-together, party, celebration, memorial, assembly, protest, meeting, to-do item, task, contract deadline, reservation or appointment. The activity may also be categorized into multiple different categories, such as entertainment or ceremonies and subcategories assigned thereof such as concert or wedding. Activities, events and activity database records may also refer to a collection of sub-activities, sub-events and sub-activity records, that make up an overall activity, event or activity database record. For example, a corporate conversion from one operating system to another operating system may comprise a collection of project phases (i.e., data mapping, testing) that too, are comprised smaller activities, each of which needs to be completed before the overall conversion activity is completed.
[0048] activity provider—For the purposes of this specification and the associated claims, the term “activity provider” is used to reference a user operating in a “point-person” capacity such as a moderator, team leader, host, manager, dispatcher, director, organizer, planner, promoter, coordinator, facilitator, instructor or point of contact for an activity.
[0049] place or venue—For the purposes of this specification and the associated claims, the terms “place” and “venue” are used interchangeably to reference physical locations, such as restaurants, theaters, stadiums, office, ballroom, conference room, or places of business, among others. A place or venue will have various attributes or features, such as a physical location, category and hours of operation, among others. The place or venue may also be categorized into multiple different categories, such as restaurant or Italian restaurant.
[0050] location—For the purposes of this specification and the associated claims, the term “location” is used to refer to a geographic location, such as a longitude/latitude combination, zip code or a street address.
[0051] real-time—For the purposes of this specification and the associated claims, the term “real-time” is used to refer to calculations or operations performed on-the-fly as activities occur or input is received by the operable system. However, the use of the term “real-time” is not intended to preclude operations that cause some latency between input and response, so long as the latency is an unintended consequence induced by the performance characteristics of the machine.
[0052] on-the-fly or ad-hoc—For the purposes of this specification and the associated claims, the term “on-the-fly” and “ad-hoc” are used interchangeably to refer to an action that is performed at a moments notice, on demand, with little planning or forethought, for example a last second search for “chef appearances” for a special surprise night out, or a report to generate how sudden weather changes are affecting a crowd gathering.
[0053] off-platform or off-site—For the purposes of this specification and the associated claims, the term “off-platform” and “off-site” are used interchangeably to refer to instances, occurrences or objects that are not within the framework and environment of the Event-Scheduling Platform (ESP) as outlined herein.
[0054] on-platform or on-site—For the purposes of this specification and the associated claims, the term “on-platform” and “on-site” are used interchangeably to refer to instances, occurrences or objects that are within the framework and environment of the Event-Scheduling Platform (ESP) as outlined herein.
[0055] widget or plug-in—For the purposes of this specification and the associated claims, the term “widget” and “plug-in” refers to a snippet or block of software code that may be copied and embedded, or “plugged”, into other Web pages, media, emails, interfaces or applications easily, and may utilize a Web API (i.e., XML, JSON, REST, SOAP) or Web services structure to enable a live connection that may refresh on its own, or each time a page or screen is accessed or refreshed. For example, a calendar widget may be embedded into an email so that current activities happening around a reader are displayed whenever the email is read.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0056] The embodiments herein and the various features and advantageous details thereof are explained more fully with reference to the non-limiting embodiments that are illustrated in the accompanying drawings and detailed in the following description. Some descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein, for example a “log out” button which may always be accessible from any page of the Web site, may not be disclosed in every embodiment or drawing. Similarly, because users may also be activity providers, access to management modules may be accessible from every page of the Web site, even though it may not be illustrated or apparent in some of the embodiments or herein. The examples used herein are intended merely to facilitate an understanding of ways in which said embodiments might be practiced and to further enable those skilled in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
[0057] The embodiments herein disclose a system for permitting Internet and mobile Internet users to access Internet resources, social media services and activity schedules and calendars more efficiently. Regarding the drawings, and more specifically to FIGS. 1 through 16 , where similar reference characters denote corresponding features consistently throughout the figures, there are shown embodiments. Further regarding the drawings and embodiments herein, and more specifically to FIG. 4 , FIG. 6A , FIG. 6B , FIG. 7A , FIG. 7B , FIG. 8 , FIG. 9 , FIGS. 12-16 , a list of items may be depicted as a collection or summation Σ of N activities where N begins at 0 and is incremented by 1 for each item until all items have been counted and a final item is reached with the Nth item being the last item. For example, item 1, item 2, item 3, item 4, . . . item N. In these embodiments, each item within a set of N items, may stand mutually exclusive from the others, or may together comprise a relationship set of N items, or a subset of relationship items from N population of items with other mutually exclusive items therein. For example, a list may comprise N related activities, with all activities together comprising one complete activity set that comprises N activities.
System Embodiments
[0058] FIG. 1 depicts a network incorporating an event-scheduling platform according to embodiments as disclosed herein. It shows an overview between the Event-Scheduling Platform (ESP) 101 and activity providers and users. The network comprises an ESP 101 at the center of a network bridging users in a user domain 102 & 103 and an activity provider domain 104 & 105 . A user domain and an activity provider domain may be connected to the ESP 101 using Web services, Web API or any other suitable communication means such as a mobile network. The network may be accessed using non-mobile or mobile computing devices, protocols and services to facilitate interaction and access to it through static and dynamic Web pages via browsers, software clients, mobile applications and so forth. User and activity provider domains may be one in the same, since a user may also act as an activity provider. Users may be any individual, sole proprietor, vendor, group or business entity such as a restaurant, corporation, music band, theater, salon, contractor, service provider, neighborhood store, and so on. An activity provider may reside entirely in an enterprise domain as a listing retrieved from a public or authorized Web site through a Web search or manual data collected entry process 106 . A user or activity provider domain further comprises an access means such as a mobile device 102 & 104 or a Web browser based console 103 & 105 . Domains may access the ESP 101 using a mobile device 102 & 104 using any equipped Internet connection means, such as 3G, 4G, LTE, GPRS, EDGE or any available Internet access means. Users and activity providers may also access the ESP 101 using a Web console 103 & 105 from a browser and computer, handheld device, tablet, etc. Web consoles 103 & 105 may connect to the ESP 101 using any available Internet connection means such as a wireless network, a wired network, LAN, VPN, a dial-up connection and so forth.
[0059] The ESP 101 provides a graphical user Web interface comprised a Social Media Suite (SMS) 213 , which allows mobile and Internet users or groups to access platform services and utilize them as deemed appropriate. The SMS 213 may enable users and activity providers to register, log in, find and post activities and events. The system may house information provided in a database, index records based on parameters, categorize them and display results according to consumer specific variables. Parameters may be static, like interest categories, address, size, or other such configurable parameters, or dynamic such as GPS location, capacity levels, wait times, or the weather. These parameters combined with user input, keyword search parameters allow for optimally matched results to be provided instantly. The ESP 101 may also use unique individual identifiers, or keyword entries, such as a popular name of the activity, or user or activity provider name (to locate a particular host, for example), that a user provides to help with a primary search in accordance with stored search parameters deemed appropriate for ease of quick decision making, such as locations nearby or activities happening now, and make those search options available for use in said user's profile permanently, by importing them into their schedules and stored in said user's preferences.
[0060] The ESP 101 via the SMS 213 may emulate existing features of similar social media applications, an ability to discuss, review, comment, share and upload media files, images and video with an added utility to stream live data with any non-mobile or mobile computing device. The ESP 101 however, may allow users and activity providers to link media of their choice, such as images, drawings, graphics, sound clips, music, video, live streams, documents, products lists, menu items, and so on, to an activity, so that they may be instantly viewed by a consumer and shared across the ESP 101 for promoting an identity, image, product, activity or event. The user or activity provider may share activity information data items on a per item basis and select or configure particular users or groups whom to target, giving certain users access permissions to view, comment, share or download. A user or activity provider may upload said activity data objects through the ESP 101 with smart tags, keywords, categories, location information so that users may access, view, interact and act on immediately.
[0061] FIG. 2 illustrates an event-scheduling platform according to the embodiments as disclosed herein and illustrates the enterprise environment that makes up the invention. The ESP 101 comprises a user or activity provider database 201 , a content database 202 , an activity database 203 , an advertising engine 210 , a mobility management engine 211 , a mobile device management engine 212 , and an SMS 213 comprising a front-end 204 and a management back-end 205 . The front-end of the SMS 213 comprises modules described later in the user embodiments section, further comprising user preferences, parameters and profiles, global scheduling feeds, user scheduling feeds, file and media sharing modules and search engine and search profiles. The back-end of the SMS 213 comprises a user or activity provider management module 206 , an activity management module 207 , a content management module 208 , and a file management module 209 . Example main tables, indices and primary keys are shown in FIG. 23 .
[0062] The ESP 101 is a combination of powerful software interfaces, scheduling feeds and an SMS 213 , to create a robust scheduling and activity-sharing system. It may provide users with immediate access to activities happening in an area, given data stored preferences their profiles. Upon setting up an account, a user may enter vital pieces of information, such as age or favorite hobby, which may be used as parameters for returning relevant data to said user. Because this happens continuously at the ESP 101 through a continuous connection between users and the SMS 213 , a user or activity provider may access activity information instantly via a non-mobile or mobile computing device and find an activity happening at anytime, anywhere. Not only may a user attend or join an activity, which may be a live concert, a sale at a store, a streamed event, or something happening around the corner, it may allow for immediate sharing with others, even other attendees, with plug-in capabilities to interact with one another at the SMS 213 via a chat box, peer to peer messaging systems, SMS messaging, on-platform software clients or with other third party Web tools. The platform may also be a powerful marketing tool for activity providers so that they may make announcements instantly to users, of activities to attend or join, warnings to heed, or services to consume.
[0063] The Domains
[0064] A user or activity provider domain may comprise Web enabled and computing devices further comprising computers, laptops, terminals, consoles, body gear, ocular viewers, digital cameras, digital recorders, drones, PDAs, tablets or mobile devices via an application interface. Communication between the ESP 101 and a user or activity provider may occur on a browser console or computer by means such as a wireless network, a wired network, LAN, VPN, a dial-up connection and so forth, a mobile device via any equipped Internet connection means, such as 3G, 4G, LTE, GPRS, EDGE or any available Internet access means, and with continued connectivity through various protocols comprising Web services, Web API, feed protocols, on demand by user or on-the-fly, real-time with location services so that said user is continually updated.
[0065] The Databases
[0066] Data is continually collected and may be stored in 3 main databases, a user or activity provider database 201 , a content database 202 and an activity database 203 . A user or activity provider database 201 may house basic profile information of a user, special interests, preferences, privacy settings, etc. A content database 202 may contain comments, files, media, blogs, ads, etc. An activity database 203 may contain activity data collected, dates, times, duration, etc. The databases are the primary sources of data, items and objects presented on the platform.
[0067] The ESP 101 may store information about a user or activity provider in a user or activity provider database 201 , comprised a user name, nickname, business name, residential address, business address, occupation, hobbies and interests. A user or activity provider database 201 may contain both static and dynamic data, interest and search parameters and may be a repository capable of persistent storage and long term archiving. A user or activity provider database 201 may contain a user location, friends and group affiliations, setting of privacy and preferences, a record of activities attended, location profiles, search profiles, interest profiles, activity profiles and histories of activities involved. A user or activity provider database 201 may also have an ability to store commerce related data, such as services consumed or provided, occupancies, capacities, products purchased or offered, menus, maps, marketing materials and activities attended. A content database 202 may store content related to users, posts, reviews, conversations, documentation, media files, as well as advertisements, promotions and announcements related to businesses and their offerings. An activity database 203 may contain information pertaining to activities themselves such as dates, times, attendance, invitations, notifications sent/received, and admission costs, invitation lists, product lists, reviews and ranking data, along with other static and dynamic data such as location, capacity levels, rain-dates, duration, etc. Activity data may be collected by various methods comprising a user inputting activity data manually, automated bots mining public or authorized Internet sources, a user importing activities from off platform sources, third party services allowing such discovery using Web services or Web API (i.e., SOAP, JSON, REST, XML) or on-platform widgets installed on third-party sources collecting and forwarding activity data back to the platform.
[0068] The SMS Front-End Interface & Feeds
[0069] The SMS 213 front-end 204 , global scheduling feeds and user scheduling feeds may access activity data records stored in databases to present relevant activity data to a user through a graphical user interface, collection of tools and on-platform resources, allowing users to customize browsing experiences, interact with others, transact with activity providers and assemble groups for gathering, all in real-time. A featured component of the front-end Web-interface SMS 204 may be a global scheduling feed and a user scheduling feed, which may announce activities happening in an area. A global scheduling feed may be a presentation of activities without any filters, except for that of location, so that every activity in an area is listed. A user's location and radius may be changed at any time to show different results. A user scheduling feed may be a customized subset of a global schedule of activities, accessed and filtered upon signing into the SMS 213 , filtered by user-defined parameters, interests and various other criteria. Included flowcharts illustrate sample uses of the front-end Web interface SMS 204 . FIG. 17 shows an initial access to the platform prior to a user logging in or accessed after logging in, where a user may simply browse activities in the global scheduling feed and decide if anything happening at that moment is worth attending or joining, or do a search as illustrated in FIG. 21 . If there is any activity of interest, a user may view details, attend an event and choose to import an activity into a user schedule along with storing preferences that exists for that activity in a user profile, so that similar activities may be incorporated into future scheduling feeds. If there is none of interest, then a user may log in to the platform and see if there are any personalized activities worth attending or joining. While at an activity, a user may interact, stream an activity live, upload images, post comments, review an activity, and so forth, as illustrated in FIG. 20 .
[0070] Logging into the Web site, a user may sign in as a user as shown in FIG. 18 , or activity provider as shown in FIG. 19 —with a different sequence of pages presented during a browsing experience. Access site pages for a user may be geared toward finding an activity to consume or interact with others online, whereas access site pages for an activity provider may be geared toward adding or managing an activity. FIG. 18 may show a flow as a user after logging in and accessing a main user profile page on a Web console or a condensed access page on a mobile device—where a user may view activities in a user scheduling feed, toggle to and from a global scheduling feed, import activities respectively, comment on activities, interact with primary friends and groups, extended friends and groups and associates, check mail, upload files, stream an activity live, modify account information as shown in FIG. 20 or search for activities as shown in FIG. 21 . On a mobile device, due to screen size, content may be split and a mobile toggle may exist to flip from scheduling feeds to posts and back again. There may be another toggle to flip between a global scheduling feed and a user scheduling feed; both toggles are detailed later in the user embodiments section. Importing activity details from a global scheduling feed or user scheduling feed into a user's schedule may allow copying preferences, keywords, categories and so forth, to a user search profile, so that similar activities would be displayed in a user scheduling feed going forward. At any point during or after an activity, users may rate an activity, venue, activity provider, entertainment, etc. which may be useful to other users in evaluating future activities of said activity or said activity provider.
[0071] A user signing in as activity provider as shown in FIG. 19 may be presented with an activity management system 207 and be able to view current activities that are set up, add, modify, delete an activity as shown in FIG. 22 , upload items for an activity such as an agenda, menu, product list, directions, coupons, etc. and/or send notices to invitees. A user may access an RSVP system to review existing notices on a per activity basis, invites, correspondence that have been sent, such as RSVP's, reservations and headcounts, and an ability to suppress or resume notices, for example if an event is nearing capacity. A user may access a notification system which collects responses in a mailbox utility, compose or resend letters, decide on how messages are to be sent, i.e., by email, fax, text, voice, letter, and so forth, and then may assign friends, groups or associates lists as recipients.
[0072] The SMS 213 front-end 204 may present real-time scheduling feeds, facilitate in-line collaboration, manage and share user data and objects. The SMS 213 front-end 204 is responsible for user management, activity management, group collaboration, activity search and other functions performed by the ESP 101 . The SMS 213 front-end 204 may also track user movement and update said user's location in a user database 201 in real time. It may also allow a user to create closed user groups or create custom groups for sharing and interacting. A closed user group or custom group may be people with a commonality, for example, with similar interests, business associates, same school, or related in a familial way. The SMS 213 front-end 204 may also provide privacy tools for users to control access to certain areas of said user account and content.
[0073] At any moment, a user may perform detailed searches, querying the databases accordingly. A search engine may enable a user to search for a user, activity or activity provider based on several parameters for an immediate call to action. Parameters used to search for a service may comprise an activity category, location of a user, location of an activity, date and time of an activity, a particular activity provider, activity reviews, popularity of activity providers, services, or activities. A search module depicted in FIG. 21 shows options that a user may use to find activities around which to plan, attend or join. A search may also enable a user to locate online activities as well as offline activities, such as a webcast, webinar, live feeds, online sales, and so on, to attend or import to a user schedule. A powerful ability to customize searches by saving preferences, keywords, categories to a user search profile, so that similar activities would be displayed going forward in a user scheduling feed, may enable a user to store multiple search profiles to further enhance a browsing experience.
[0074] The SMS Back-End & Management
[0075] The SMS back-end 205 and management engines 210 - 212 contain management utilities 206 - 209 of the enterprise so that current, relevant content and services may be offered to users. It may contain administration functions, repositories and dedicated modules to make this happen by controlling content, providing notification tasks, sending auto-responders, maintaining activity data records, providing mailing functions, executing security modules, storing recovery tools, testing environments, documenting policies and procedures, performing behavioral and trend analytics and serving advertisements relating to activity providers.
[0076] The advertising engine 210 may intuitively stream context based or paid advertisements to a user based on preferences entered during registration, interests in said user's profile, current search context, search history and other criteria to display targeted advertisements. A content management module 208 may interface with an advertising engine 210 to retrieve data from a content database 202 to make this happen.
[0077] The mobility management module 211 may manage the mobility of individual users, plurality of users as groups, location of static as well as mobile activities. A mobility management module 211 may provide location related algorithms in order to compute a location of an activity with reference to a group of users or a single user, or users relative to each other.
[0078] The mobile device management module 212 provides device management capabilities to render and support adaptive content to a plethora of mobile device types, models, platforms, protocols, and so forth, used by a user or activity provider to access the ESP 101 . Such devices may be any non-mobile or mobile computing device comprising tablets, smart phones, laptops, ocular viewers, consoles, terminals, drones, PDAs, video recorders, mobile cameras and body gear.
[0079] The activity management module 207 allows users, and users as activity providers to perform activity coordination, scheduling and management within a single user or a multiple set of users connected logically or at least registered with the SMS 213 . An activity management module 207 may provide an ability to synchronize global scheduling feeds and user scheduling feeds within a mobile device or console to update activities that were created or modified by users. An activity management module may allow users to create, modify, delete activities, find other users with whom to interact, stream and share objects. The ESP 101 may disseminate activity information over the Internet via the SMS 213 to other users for immediate consumption and engage interaction. For example, live document sharing may be used in an office meeting, one-to-one video may be used for interviews, a one-to-many video activity may be set up for a lecture or class or a many-to-many video may be set up for a teleconference.
[0080] The content management module 208 provides a management engine that may house and retrieve user content comprising consumer reviews, media files, press releases, images, documentation, promotional materials and advertisements related to activity providers 104 , 105 in a content database 202 . A content management module may provide software for recording, storing and retrieving activity data and access repositories with protocols for sharing and streaming media, such as SIP, RTP, RTMP with video encoding capabilities for standard definition, high definition, and for voice over IP and video control signaling.
[0081] FIG. 3 depicts a communication implementation between the ESP 101 and a client (a non-mobile or mobile computing device or a console) according to embodiments disclosed herein. It shows communication protocol layers that may exist between the ESP 101 interface and a user. A communication implementation between a client and ESP 101 may be based on activity-driven, or notification-based interaction patterns, which are commonly used patterns for inter-object communication and syndication. Examples exist in many domains, for example in publish/subscribe systems provided by message oriented middleware vendors, or in system and device management domains. This notification pattern is increasingly being used in a Web services context as well. WS-Notification is a family of related white papers and specifications that define a standard Web services approach to notification using a topic-based publish/subscribe pattern. It includes standard message exchanges to be implemented by service providers that wish to participate in point to point notifications, standard message exchanges for a notification broker service provider (allowing publication of messages from entities that are not themselves service providers, i.e. third party feeder systems, third party marketers), operational requirements expected of service providers and requestors that participate in notifications, and maybe be of an XML (i.e., RSS) or JSON model that describes topics of subscription. In an example environment, a client and ESP 101 may provide JSON and XML engines and implement existing standard Web service specifications for inter-communication and syndication. For the purposes of the embodiments disclosed herein, a syndicated service may be an “always on” or “always available” streaming communication between the ESP 101 and a user or activity provider through the SMS 213 via global scheduling feeds 601 and user scheduling feeds 401 comprising activity feeds, calendar feeds and mapping feeds, so a user may stay abreast of what is happening in an area.
User Embodiments
[0082] FIG. 4 shows a typical user profile, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to the embodiments as disclosed herein. It illustrates an example user profile page for updating interests, preferences, characteristics, and so on. A user or activity provider profile comprises a collection of user information, contacts and preferences where a user may customize their browsing experience. A user or activity provider profile comprises a User ID 400 , a USF 401 , user information 402 , privacy settings 403 , special interests and preferences 404 , user location 405 , with location being either dynamic (GPS) or user entered, an interests and preferences profile 406 , a UAF 407 , activity history and archive 408 , a file, media, content container 409 , a subscriptions and following area 410 , a stream activity live module 411 , an add an activity module 1202 , an edit an activity module 1204 , saved searches and saved locations 413 , a friends and associates social pools module 419 , comprising primary (i.e., close or familial) friends and groups (PUG) 414 , secondary (i.e., casual or extended) friends and groups (SUG) 415 and tertiary (i.e., professional) associates and groups (TUG) 416 , a UMF 417 , a UCF 418 , a user's schedule 420 , and a message and email receptacle 603 .
[0083] The user ID 400 is assigned at a time of registration and is used to access the ESP 101 and is a primary index for joining data across databases and tables along with an activity ID.
[0084] The USF 401 comprises three elements: 1) a list of tailored upcoming activities UAF 407 , 2) a corresponding plotted interactive map UMF 417 and 3) a corresponding calendar UCF 418 , and may highlight all activities surrounding a user, so that an immediate decision to interact, attend or join an activity may be made. On an interactive map UMF 417 , a user may click a plotted activity on said map to view activity details. Similarly, on a calendar UCF 418 , a user may click to view activities by day for easier scheduling and click on an activity in a list UAF 407 for details and calls to action, with links to view date(s), time(s), duration, related documents, details, category, rating, reviews of an activity and/or activity provider along with links to other activity specific information. A user may also import 407 an activity to a user schedule 420 in their profile. A USF 401 may use information stored in a user profile as its main source for parameters used to dynamically generate customized activity lists. A USF 401 is comprised activities present in a database that are auto-filtered based on user-defined preferences. A list of activities may be of anything, sales, ceremonies, speeches, announcements, meetings, parties or group activities. Any changes made by a user to a profile, interest, location, etc. on-the-fly may be instantly reflected in an activity list generated by a USF 401 . Activity information in a USF 401 is also stored as a part of a user profile and indexed with an activity ID. Since activities may be common to multiple users, activity related information may be stored separately in a cache, a cookie, or in an archive and history, but references to them may be made available to a user profile, objects or sessions. Exchange of information between the ESP 101 and GSF/USF scheduling feeds and a user may happen using a Web services or Web API notification architecture.
[0085] The user information 402 comprises information of a user, such as a real name of a user, nickname, age, gender, marital status, phone number, etc. Some elements of user information 402 may be optional for a user. Privacy preferences 403 may enable a user to indicate how much personal details should be publicly visible. A user may also set how another user or activity provider may contact said user. For example, a user may want to hide a real name and address, but want to keep age and gender public. A user may utilize special interests and preferences 404 to narrow interests or store interest stacks, for example a user may be interested in watching movies, eating out and shopping all as a “set” of activities done in one day. Advertisements to a user may be tailored according to interests as indicated by said user. Location and radius 405 may be a dynamic field and may be updated with a location of a user and stored in terms of mapping coordinates (latitude and longitude). A location 405 may also be stored as a physical address, in terms of a street and area, manually entered. A location may also be stored with respect to a plurality of cellular base stations. A location 405 may be an element and via a location ID assigned per user, used to generate data feeds to a USF 401 continuously by area as well as integral in returning search location based search results. It is a key index to saving location search information on a per area basis in a user saved search/saved locations profile 413 discussed a bit later in this figure.
[0086] The history and archive 408 is a module that may track and store history of attendance, interactions, chats, posts, bookmarks and archive online navigation trails for retrieval later. A user history and archive 408 may store previous attendance and associated interactions of a user that occurred that day surrounding an activity. This field may be configurable by a user. For example, a user may want to store their history for the past two weeks or past twenty days only, or save portions of an activity, such as a video feed only, or posts only and decide which to share and which to keep private. In history and archive 408 , a user may access activities created by said user or activities that a user attended even when created by others, along with any interactions that happened, conversation, chats, messages, video, etc. A user may also delete items from a repository if desired. A user content bin 409 is a storage area, where a user may store media indefinitely. Media may be videos, pictures, text, blogs, documents, marketing materials or any other media, and may be linked and indexed by activity ID and may be shared with others within a social network. A user may also configure settings so that media from an activity is shared with only a specific individual, group or those in a subscriptions/following area. This may happen on a per activity basis via unique activity IDs. A user may also assign permissions for sharing on a per item basis. A subscriptions/following area 410 may comprise other users, activities, topics, and so on, in which a user has found some interest, subscribed to and/or follows to keep abreast of their activity. A stream activity live 411 module may enable users to stream video live through the ESP 101 . A user may add an activity 1202 and in doing so assigning an activity ID to said activity. An add activity function is shown in FIG. 22 and may be performed in an activity management module.
[0087] A user may have multiple locations and search profiles and save them for easy retrieval later. For example, a user may save key search parameters, one of them being by location and radius, so if a user was in Honolulu, a user could have a wide default search parameter set to locate activities, and a smaller one set for bustling New York City. Similarly, a user may have several location profiles 413 , for default location references during login. For example, a user visiting Paris could have the ESP 101 respond in every aspect with that location at its zero point, friend lists reshuffled, search profiles reshuffled, and so forth.
[0088] A friend and associates pools module 419 offers a user quick access to user groups associated with said user account, so that peer interaction may take place, i.e., sharing files, chat sessions, one to one video, one to many video, emailing, messaging, SMS texting, chatting, and so forth, using third party software tools or tools available on the ESP 101 . A friend and associates pools module 419 comprises primary (i.e., close or familial) friends and groups (PUG) 414 , secondary (i.e., casual or extended) friends and groups (SUG) 415 and tertiary (i.e., professional) associates and groups (TUG) 416 . A user may create custom groups, which may have a common factor, for example, a group may comprise friends of a user who went to college, while another may comprise associates from work and yet another may be a members of a user's family. Primary (i.e., close or familial) friends and groups (PUG) 414 , extended (i.e., casual or extended) friends and groups (SUG) 415 , tertiary (i.e., professional) associates and groups (TUG) 416 and subscriptions/following area 410 may make up a user's interactive social pools 419 .
[0089] At any time in a browsing experience, a user may add an activity 1202 , delete an activity 1203 or edit an activity 1204 . A user schedule 420 may display activities that a user has added or imported into their schedule, listed in an orderly date and time format. It may comprise activities imported from a GSF 601 , imported from a USF 401 , imported from search results 502 , imported from off-platform calendars or manually added by a user 1202 . A user may export an activity from their schedule to an off-platform schedule, calendar or device, for example to a Google calendar or mobile phone calendar.
[0090] FIG. 5 displays a registration/login page, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to the embodiments as disclosed herein. It illustrates an example login gateway where users may opt to sign in as user or activity provider, and load saved profiles. During a user or activity provider registration/login 501 , a quick view of any system messages, alerts, miscellaneous platform specific news and announcements may be displayed in a system messages area 502 . Users may create an account 503 . New or existing users may modify an existing password 504 and following reset steps therein. Existing users may log in to the ESP 101 with a user ID 505 set up during a registration process and corresponding password 506 . A user may opt to access an account as a user or activity provider by ticking an appropriate box 507 . A user may also log in with a prior, user saved location profile using a location profiles dropdown box 508 pre-loaded with user saved profiles or by clicking an option in a detailed saved location profiles 509 section. If logged in as a user, said user may land at a user screen depicted in FIG. 6 , if logged in by a Web console or web-ready computer, or if by a web-ready mobile device, a condensed screen as in FIG. 7 . If logged in as activity provider, another sequence of pages may be presented—beginning with an activities maintenance area in a management console FIGS. 12 , 15 and 16 . Regardless of whether a user is logged in as an activity provider or as a user, throughout an entire browsing experience, same screens may be accessible and permissions are mirrored, however a sequence of navigation may differ. Same permissions may be given to both user and activity provider, so anyone may view an activity and anyone may post an event. Same data structures may exist for individuals as it does for businesses, contractors, artists, or anyone with a need to organize an activity. Enhancements for custom commercial, activity planning features and other sample uses are noted in the Alternative Embodiments section below to outline specific interface access permissions on a per user or group basis.
[0091] A key functionality of a login page is an ability for a user or activity provider to sign in with a saved location profile by selecting a profile in a location profiles dropdown list 508 or by selecting one from a list of saved location profiles 509 . A user may have several location profiles saved for default location points of reference during a login. For example, if a user was in Paris, said user could have the platform respond in every aspect with that location at its zero point, friend lists reshuffled, search profiles reshuffled, etc. Any auto-assigned location setting may be overridden by a selected location. A new set of browsing parameters may be viewed and loaded because of assigned location IDs stored within the database from prior searches and visits.
[0092] FIG. 6A and FIG. 6B are of two access homepages with a toggle between them, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to the embodiments as disclosed herein. It illustrates an initial access Web page before and after login, highlighting a functioning toggle button that may allow users to switch between a global scheduling interface and a user scheduling interface. FIG. 6A and FIG. 6B are of a GSF 601 and USF 401 together, showing that a user may click between the interfaces seamlessly with a GSF/USF toggle 669 , and how activity data in a GSF 601 , USF 401 and respective posting areas 608 are affected appropriately as described below.
[0093] FIG. 6A depicts an initial access page, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to various embodiments herein. It illustrates an initial access Web page of the platform prior to a user logging in, which may include an activity feed list, appropriately date highlighted calendar, and appropriately plotted map of all activities within a central, device generated GPS location. An initial access page may be seen when the platform is accessed with every new session prior to logging in or seen when a user logs out. Its main focus is on a live, at-a-glance view of activities available, with a global scheduling feed (GSF) 601 which comprises 3 elements: 1) a list of upcoming activities in a global activity feed (GAF) 607 , 2) a corresponding plotted, interactive global map feed (GMF) 617 and 3) a corresponding global calendar feed (GCF) 618 to highlight all activities surrounding a user, so that said user may make an immediate decision to log in 600 attend an activity, interact, or join an activity. On an interactive map GMF 617 , a user may click on a plotted point to view activity details. On an activity calendar GCF 618 , a user may view activities by day, week, or month for easier scheduling, and an activity list GAF 607 . Clicking a live activity link anywhere on a GSF 601 may present activity details and calls for action as in the list 1000 , with options to view date(s), time(s), duration, related documents, details, category, rating, reviews of an activity and activity provider along with links to other activity specific information, and offer options of reviewing, discussing, sharing, rating said activity and an activity provider. A user may also have an option of importing 1007 an activity to a schedule 420 in their profile along with activity parameters, discussed a bit later in this description.
[0094] The activities displayed may be presented based on a central location and a radius parameter, which may be edited dynamically using a user location and radius link 405 . A central point may be an automatic triangulated GPS location of a user's mobile device, or a manually entered location by a user as an address, zip code, latitude/longitude coordinates, a stored profile favorite location or a location from a prior session visit. A radius search parameter may be selected from among varying radii (e.g., 1 mile, 5 mile, 10 mile), or a stored profile radius preference from a prior session visit. A user may also allow access permissions to said user's location, giving access to the public, to a closed user group(s), or to specific users.
[0095] Revisiting an import feature, a key functionality of an activity listing may be an ability to import 1007 any activity displayed from a GAF 607 into a user's schedule 420 or update preferences in their profile accordingly. After selecting an activity 1000 , a user may specify if basic information comprising—name, date, time, location—are to be imported or if all its search parameters are to be saved to a user's profile, so that similar activities are added to a USF 401 ongoing, i.e., a search radius, a specific category or categories, a specific activity provider, and so on.
[0096] Along with aforementioned features, a keyword search 602 and a display of latest live posts and comments 608 relating to upcoming activities increase the invention's functionality. At any time, a user may search for specific activities 602 based on search criteria offered by a search module FIG. 8 , such as location and radius, category, activity provider, etc. as illustrated in FIG. 21 on-the-fly and import activity results from a search result list presented. A scrolling chat box of posts 608 from users in an area discussing activities reflected in a GSF 601 , offer a user an arena for discussing related activities. A chat box of posts 608 may include a steady flow of comments pertaining to activities displayed in a GSF 601 , either by a default settings database call, or an on-the-fly search that a user has performed using static and dynamic parameters comprising said user's search parameters, and reflects in real-time, whatever posts are occurring for whatever activities are shown in a GSF 601 .
[0097] If a user is logged in, a friend and associates pools module 419 may display offering a user quick access to contacts and user groups associated with said user account, so that peer interaction can take place, i.e., sharing files, chat sessions, one to one video, one to many video, messaging, SMS texting, chatting, and so forth, using third party software tools or tools available on the ESP 101 . A user may also check messages and emails 603 . A friend and associates pools module 419 comprises primary (i.e., close or familial) friends and groups list (PUG) 414 , secondary (i.e., casual or extended) friends and groups list (SUG) 415 and tertiary (i.e., professional) associates and groups list (TUG) 416 .
[0098] A user may use a toggle feature 669 to flip between a global access page FIG. 6A and a user access page FIG. 6B .
[0099] FIG. 6B depicts an initial access page, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to various embodiments herein. It illustrates an initial access Web page of the platform after a user logs in, which may include a customized activity feed list, appropriately date highlighted calendar, and appropriately plotted map of all activities within a central user-defined location. A user initial access page is a first page seen after a user logs into the platform and contains all activity related content and options with respect to said user's preferences. Its main focus is on a live, at-a-glance view of activities available, with a user scheduling feed (USF) 401 which comprises 3 elements: 1) a list of upcoming activities in a user activity feed (UAF) 407 , 2) a corresponding plotted, interactive user map feed (UMF) 417 and 3) a corresponding user calendar feed (UCF) 418 to highlight all activities surrounding a user, so that said user may make an immediate decision to log in 600 attend an activity, interact, or join an activity. On an interactive map UMF 417 , a user may click on a plotted point to view activity details. On an activity calendar UCF 418 , a user may view activities by day, week, or month for easier scheduling, and an activity list UAF 407 . Clicking a live activity link anywhere on a USF 401 may present activity details and calls for action as in the list 1000 , with options to view date(s), time(s), duration, related documents, details, category, rating, reviews of an activity and activity provider along with links to other activity specific information, and offer options of reviewing, discussing, sharing, rating said activity and an activity provider. A user may also have an option of importing 1007 an activity to a schedule 420 in their profile along with activity parameters, discussed a bit later in this description.
[0100] The activities displayed may be presented based on a central location and a radius parameter, which may be edited dynamically using a user location and radius link 405 and various parameters unique to each user, i.e., interests, history, etc., which too may be edited dynamically using a preferences and interests profile 406 . A central point may be an automatic triangulated GPS location of a user's mobile device, or a manually entered location by a user as an address, zip code, latitude/longitude coordinates, a stored profile favorite location or a location from a prior session visit. A radius search parameter may be selected from among varying radii (e.g., 1 mile, 5 mile, 10 mile), or a stored profile radius preference from a prior session visit. A user may also allow access permissions to said user's location, giving access to the public, to a closed user group(s), or to specific users.
[0101] Revisiting an import feature, a key functionality of an activity listing may be an ability to import 1007 any activity displayed from a UAF 407 into a user's schedule 420 or update preferences in their profile accordingly. After selecting an activity 1000 , a user may specify if basic information comprising—name, date, time, location—are to be imported or if all its search parameters are to be saved to a user's profile, so that similar activities are added to a USF 401 ongoing, i.e., a search radius, a specific category or categories, a specific activity provider, and so on.
[0102] Along with aforementioned features, a keyword search 602 and a display of latest live posts and comments 408 relating to upcoming activities increase the invention's functionality. At any time, a user may search for specific activities 602 based on search criteria offered by the search module FIG. 8 , such as location and radius, category, activity provider, etc. as illustrated in FIG. 21 on-the-fly and import activity results from a search result list presented. A scrolling chat box of posts 608 from users in an area discussing activities reflected in a USF 401 , offer a user an arena for discussing related activities. A chat box of posts 608 may include a steady flow of comments pertaining to activities displayed in a USF 401 , either by a default settings database call, or an on-the-fly search that a user has performed using static and dynamic parameters comprising said user's search parameters, and reflects in real-time, whatever posts are occurring for whatever activities are shown in a USF 401 . A user may add 1202 or edit an activity 1204 , upload files, documents, videos and images to a repository 409 and stream live content 411 for sharing.
[0103] A friend and associates pools module 419 offers a user quick access to user contacts and groups associated with said user account, so that peer interaction may take place, i.e., sharing files, chat sessions, one to one video, one to many video, messaging, SMS texting, chatting, and so forth, using third party software tools or tools available on the ESP 101 . A user may also check messages and emails 603 . A friend and associates pools module 419 comprises primary (i.e., close or familial) friends and groups list (PUG) 414 , secondary (i.e., casual or extended) friends and groups list (SUG) 415 and tertiary (i.e., professional) associates and groups list (TUG) 416 .
[0104] The user may use a toggle feature 669 to flip between a global access page FIG. 6A and a user access page FIG. 6B .
[0105] FIG. 7A and FIG. 7B are of two access page views as may be rendered on a mobile device, with two toggle tabs, as may be rendered for viewing on a non-mobile or mobile computing device, according to the embodiments as disclosed herein. FIG. 7A and FIG. 7B illustrate a GSF/USF toggle 669 and a mobile/widget toggle 701 as described. A user may flip between a user scheduling feed 401 and a global scheduling feed 601 interface seamlessly with a GSF/USF toggle 669 , and respective components comprising activity feeds 407 / 607 , map feeds 417 / 617 , calendar feeds 418 / 618 , posting areas 608 are affected and displayed appropriately.
[0106] FIG. 7A is an access page viewed after logging into the ESP 101 as may be rendered for viewing on a non-mobile or mobile computing device, and may be a condensed version of a Web site access pages, FIG. 6A and FIG. 6B . To accommodate a smaller screen, a second mobile/widget toggle 701 may allow a user to flip to a second screen, FIG. 7B and back again to FIG. 7A . FIG. 7A comprises a scheduling feed among other options and FIG. 7B comprises corresponding user posts relating to said scheduling feed in FIG. 7A , among other options. An initial access mobile/widget view may be of either a USF 401 or GSF 601 and may have the same functionality and content as a Web browser access pages, FIG. 6A and FIG. 6B . A user may view activity details 1000 and import items 1007 to a personal schedule 420 , search with parameters, location, radius, etc. 602 or load a prior location or search profile 413 , and import 1007 to a personal schedule 420 from those results. A scrolling chat box 608 as in FIG. 7B may show latest, real-time posts and comments displayed relating to a results set of activities provided by scheduling feeds, filtered by user-defined settings, activity preferences and other user-defined parameters. A user may add 1202 or edit an activity 1204 , upload files, documents, videos and images to a repository 409 and stream live content 411 for sharing.
[0107] A friend and associates pools module 419 offers a user quick access to user contacts and groups associated with said user account, so that peer interaction may take place, i.e., sharing files, chat sessions, one to one video, one to many video, messaging, SMS texting, chatting, and so forth, using third party software tools or tools available on the ESP 101 . A user may also check messages and emails 603 . A friend and associates pools module 419 comprises primary (i.e., close or familial) friends and groups list (PUG) 414 , secondary (i.e., casual or extended) friends and groups list (SUG) 415 and tertiary (i.e., professional) associates and groups list (TUG) 416 .
[0108] The user may use a toggle feature 669 to flip between a global access page FIG. 7A and a user access page FIG. 7B .
[0109] FIG. 8 is a search module, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, given various embodiments herein. It illustrates an example search module and search options, and an option to save a search. FIG. 21 illustrates a search module flowchart. A user may search for activities collected and input manually, retrieved from automated bots mining public Internet sources, a user importing from off platform sources, from third party services that allow such disclosure using Web services or Web API (i.e., SOAP, JSON, REST, XML) or retrieved by on-platform widgets installed on off-platform sources or embedded in off-platform content, emails or listings. A user may control activities being searched in various ways, such as limiting results to local activities or those centered within a specific area by radius, address or zip code 802 . A user may also restrict activities to a particular category by choosing category or tags 803 , by a keyword search in a text box 800 , or by date or date ranges 801 . A user may also choose to search by a user name or activity provider name 807 or narrow a search by online activities or offline activities 804 , just search activities 805 or just search services 806 . After selecting options, submitting a form may yield activity results 808 comprising an activity name, date, time of an activity along with a rate or review option and an ability to import an item into a user's schedule 420 , along with saving its preferences to a user profile, if desired, to customize future search results. A user may save search 809 parameters and store search term combinations that have been used for future searches. If, for example a search yielded particularly good results, a user may wish to save it for ease of access later. Any combination of selections may be used and saved in a search profile for future access and saved search results 810 may be loaded, if desired. This may particularly be useful for different cities, to enable custom profiles to feed useful information on a per area basis. In various embodiments, a search database at the ESP 101 may be indexed with registered information by various search providers as well as index data made available by several third party business listings, reviews, blogs, activity listings or phone directories through Web services, Web API feed type services. For example, search data may be indexed by activity name, activity category, activity location, price and rating along with discussions imported from Twitter®, among other key search terms aforementioned.
[0110] FIG. 9 illustrates the dynamic nature of a push/pull feature according to embodiments as disclosed herein. It illustrates sample interactive relationships between global schedules, user schedules and personal schedules. A push/pull functionality between a GAF 607 /UAF 407 and a user schedule 420 may offer an ability to import and merge selections from scheduling feeds to an individual schedule 420 along with parameters assigned to it, providing a personalized browsing experience as a tailored activity information resource. When clicking an import tab 1007 , a user may be presented with options to select one or more parameters tied to that activity to be imported with it to be saved in a user profile. For example, if a live music concert a block away in the neighborhood park is listed with free admission, a user may import said event into their schedule and parameters associated with said event. So, any offline, live music event, within a one-mile radius of said user, with free admission, may be appended to an already existing, stored search profile for that user if desired. A user may also export 1008 an activity or the entire set of activities 901 to an off-platform or off-line calendar.
[0111] FIG. 10 illustrates an example activity content page in a content module, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to the embodiments as disclosed herein. Activity content 1000 illustrates how a user may interact with other users or the ESP 101 after selecting an activity from a source comprising a personal schedule, GSF 601 , USF 401 , GMF 617 , UMF 417 , GAF 607 , UAF 407 , GCF 618 , UCF 418 , a search result or an activity discovered while sharing or browsing the ESP 101 . A user may attend an activity in person and may interact through the ESP 101 with actions comprising sharing an activity 1001 with other users, reviewing an activity 1002 , discussing 1003 or blogging 1004 about an activity with others live, following an activity 1005 or activity provider 1006 for future news and schedules, importing an activity 1007 to a personal schedule 420 or exporting an activity 1008 to a scheduling system on an off-platform device. A user may also use software tools on the ESP 101 to stream an activity 1009 , record an activity 1010 or upload files, photos or videos 1011 to a gallery.
[0112] FIG. 11A and FIG. 11B illustrate an example activity content page in a content module, as may be rendered for viewing on a non-mobile or mobile computing device, with a toggle, according to the embodiments as disclosed herein. A toggle 1101 may be used to toggle between activity content 1000 in FIG. 11A among other options, and related activity posts 608 in FIG. 11B . A mobile view may reflect a consolidated version of a non-mobile view as in FIG. 10 with identical functionalities.
Activity Provider Embodiments
[0113] FIG. 12 displays an example activity provider access page in an activity management module, as may be viewed on a client like a Web browser on a non-mobile or mobile computing device, according to the embodiments disclosed herein. For the purpose of illustrating an example implementation, the activity provider embodiments comprise an example wedding with a fragrance garden theme, hosted by SOS Fragrance Store, along with other store activities. A user, as activity provider, may access an activity management console, in this case SOS Fragrance Store, with an ordered list of their activities in queue 1201 . FIG. 19 illustrates a flowchart of management options a user, as an activity provider, may face when accessing the platform. Using information from a user or activity provider registration and an activity management module, the ESP 101 may access information for an activity provider and assign an activity ID during an add activity process 1202 as illustrated in FIG. 22 . An activity provider (host, vendor, individual, group, corporation, etc.) may then modify 1204 or delete 1203 activity information. Apart from providing basic information, like activity name, dates, times, location, duration, and categories, a user may compile invitation lists 1205 , friend lists 1208 , associates lists 1209 or groups lists 1210 . An activity provider may also share activity specific information and activity data objects, such as a point of contact person, details of a business, such as service offerings, marketing materials, brand collateral, pricing or product lists, menus, itineraries, agendas, video, direction maps and so on, from a media bin 1206 . Activity data objects may be uploaded and maintained on an individual activity basis, because items are indexed, and stored in a database with a media ID and may be linked to an activity ID and said activity data objects shared via email, voice messaging, SMS messaging, in-box messaging 1207 or shared on other social media platforms via a widget plug-in. In a notification area 1207 , documents are indexed with a notification ID and an activity provider may select from a collection of pre-made or canned emails, messages, notices, upload their own templates for use in initial email blasts or compose an entirely new one. When sending notices, activity providers may make friends 1208 , groups 1210 or associates 1209 administrative assignments, block users from an invite list 1205 and choose to publicize or make private invite lists. As a part of a group assignment process, an activity provider may assign permissions to groups or individuals, such as an ability to edit event times, upload media, send notices, delete activities, etc. This may be helpful, in our wedding example, when an extended family member is given the authority to change the time of the reception. A user may utilize an indexing capability of linking an activity ID and a location ID, which are assigned during an add activity process shown in FIG. 22 to make this happen. This may be useful in instances where multiple locations of an activity are occurring. Additionally, through an activity management module, a user may consolidate groups of activities as part of a larger activity or task by assigning a parent ID to an event and assign sub-activities within an umbrella of a parent activity using a link activity tab 1211 . For example, if SOS Fragrance Store has more than one wedding occurring in different cities, a administrative coordinator may be set up as with editing permissions and each wedding comprising subordinate entities that may be assigned to umbrella activities, linked as a group. This may also help in instances where activities are dependent on other activities (i.e., sub-tasks or sub-activities), or for tracking milestones in a project. In our wedding example, the conclusion of the photography session may trigger the reception activity. Under an enhanced model (see Alternative Embodiments below) of participation in the ESP 101 , activity providers may have a capability to present customized Web page content for each branch, franchise, outlet and show content, pages, permissions, letter templates specific to their respective business. The ESP 101 has a Web server engine and content management system that allows Web page content to be adapted to specific needs of a business location.
[0114] FIG. 13 shows a relationship of a user or activity provider ID as a primary index tying all other data records together, according to the embodiments as disclosed herein. An activity provider ID may tie all objects together across databases with other primary key IDs and subordinating indices as illustrated in FIG. 23 . A user or activity provider ID is creating during account creation 503 . Using a dynamic GPS locator or mobile location services, or user entered location by address and/or zip code, or geo-positioning data on-the-fly, a user may have multiple location IDs, identifying location profiles 413 to customize data feeds, content flow and narrow interaction to a specific area so that only relative customized user activity information is presented. This may be useful when visiting another city, or planning a visit ahead of time. In our wedding example, out of town visitors may log into their account on the ESP 101 and locate activities to attend after the wedding. In a user or activity provider profile page FIG. 4 , a user may save current locations or create new location parameters 413 .
[0115] Using information from inputs of a user or activity provider in FIG. 12 , FIG. 15 , FIG. 16 , the ESP 101 may build activity profiles as shown comprising an activity set 1201 that may be linked together because of a commonality or an interrelationship, to affect one another or occur simultaneously. An activity provider may have N activities listed, each with an activity ID. This may be useful when a project or activity requires a multitude of sub-tasks to happen before for an overall project or activity is considered completed, in our example wedding, coordinating of a band, minister, caterer, invitations, photography, fragrance bar, gifts and flowers may all need individual tasks and even sub-tasks within them, to make sure the wedding is a success with some activities relying on other activities being completed before commencing and others occurring simultaneously. All information relating to an activity, including sub-activities may be associated with a corresponding parent activity ID. Some details may be static such as address, contact information, etc., and some may be dynamic, such as duration or attendance levels. Sub-activities are linked to activity IDs to comprise activity sets. All activities hosted by an activity provider may be associated with a single user or activity provider ID, thus each activity may have a unique activity ID associated with a user ID. All parameters being tracked and indexed for an activity provider may be related to a corresponding activity. Therefore, each parameter may be linked to a unique user ID, through a relationship between an activity ID and a user or activity provider ID. A relationship may allow a search parameter, or group of parameters, to be linked to a search profile for each user 413 . Search IDs may be attached to a user or activity provider ID and therefore search IDs may be linked to activity IDs. Also shown is a relationship between media, documents and files to a user ID. A user or activity provider may attach files, media, documents to an account profile, such as menus, marketing documents, business files, or agendas 409 , stream live video 411 from a personal profile page or from an activity management module 1206 , and assign document IDs or object IDs. Document IDs or object IDs may be directly attached to user IDs and may be linked to activity IDs, and depending on a nature of a file, document or object, a user or activity provider may then define access permissions on a per item basis. Relating to this ability is an assignment of group IDs during an affiliation set up process. A user or activity provider may define a social pool comprising a friend and associates pools module 419 further comprising primary (i.e., close or familial) friends and groups list (PUG) 414 , secondary (i.e., casual or extended) friends and groups list (SUG) 415 and tertiary (i.e., professional) associates and groups list (TUG) 416 ; and by doing so assign them group IDs with varying administrative access permissions to portions of a user or activity provider accounts, friend admin security 1208 , group admin security 1210 and associates admin security 1209 . Similar to other IDs, a group ID may be associated with an activity ID through a relationship with a user or activity provider ID. In our wedding example, a user or activity provider may grant extended friends a “viewing only” access to view an seating chart, rather than update or sharing permissions.
[0116] FIG. 13 illustrates an activity notification flow between a user domain and an activity provider domain according to the embodiments disclosed herein. Through the ESP 101 , both domains are essentially the same in that data may be collected and stored in a user or activity provider database 201 , content database 202 and activity database 203 . Communication may pass through the ESP 101 for routing, tracking and archiving, and it is through the platform that alerting and mailing is most effective. An activity provider may send mass alerts, SMS messages and mass mailings to the public, individual groups, or associates, etc., suppress notification on a user-by-user basis; track RSVPs, headcounts, and reservation counts for each event. A user or activity provider may also receive responses accordingly and view them in an organized environment on a per activity basis. A user (as activity provider) may also pre-schedule or send out reminder notices anytime in advance, or if needed at a moments notice, when last minute changes are made and require immediate dispatch. Also, with the ESP 101 interface, an activity provider may attach information data objects from a media bin to a mailing. For our wedding example, it may be a useful follow up tool for thank you notices from the family or event surveys and feedback for future SOS Fragrance Store improvements.
[0117] FIG. 15 depicts an example RSVP page in an activity management module, according to the embodiments disclosed herein. A user, as activity provider, may access an RSVP module, in this case SOS Fragrance Store, with an ordered list of their activities in queue 1501 . Displayed in the main content area is an inbox or response list 1501 pertaining to individual activities and notification options relating to each. Once an activity has been set up, a user may attach notification options to it for an initial mailing. For each activity, an activity provider may decide if there are criteria that need to be met in order to attend or join an event. For example, for our wedding, the activity provider may require an RSVP in order to attend or join an event, due to capacity restrictions. An activity provider may simply require a headcount, so a “yes” or “no” type response may be needed to know how many individuals for whom a food caterer must prepare. Some tables closer to the married couple may require RSVPs. After deciding a response type, an activity provider may send or resend invites, instructions, agendas, and other pertinent activity specific information data objects, i.e. directions, instructions, maps, gift registry lists, and so on, from their media bin 1206 via email, voice or SMS text or instant message 1207 . If desired, in a notification area 1207 , an activity provider may select from a collection of pre-made, canned response requested emails, messages, notices, upload their own templates for use in initial email blasts or compose an entirely new one. An RSVP page may track counts per type of notification received and activity providers may quickly decide to suppress or resend notifications, i.e., for event rescheduling or if at a full capacity status. Also here, is an ability to add 1202 , delete 1203 , or modify 1204 activities for convenience. An activity provider may create custom lists or access their mailing lists on a per activity basis for a recipient list. For example, by ticking a select box for an activity in an activity list 1501 and then clicking a send notices 1207 tab section along with an associate's list 1209 , an activity provider may send or resend a particular invite type to that group. An activity provider may similarly access a list of groups, manage guests, send notices and make invite lists public or private.
[0118] FIG. 16 illustrates an example notification system in an activity management module, according to the embodiments as disclosed herein. A notification system is similar to an RSVP system, in that a queue of activities and related notification attributes 1601 may occupy a main content area. However, notification options may relate to non-RSVP mailings, such as a frequency, duration, and timing of activities. An activity provider may send out non-RSVP ad-hoc notices and status updates comprising canned emails and messages 1207 for ease of sending mass mailings across the network. An activity provider may create custom lists or access mailing lists on a per activity basis for a recipient list. For example, by ticking a select box for an activity in an activity list 1601 and then clicking a send notice 1207 tab along with an associates list 1209 , an activity provider may send or resend a particular email or message to a group or compose a new message. An activity provider may similarly access a list of groups, manage guests, send notices and make invitation lists public or private.
[0119] To summarize, unique features that make this platform differ from other systems may be an up-to-the-minute, real-time access to activities that would otherwise be unknown through a GSF 601 and a USF 401 . Also key, may be an ability to import 407 activities from a GSF 601 and a USF 401 into a user's personal schedule 420 as a tool for immediate planning Because it is activity centered, the platform may allow sharing of actual activities, highlighting the dynamic nature of experiencing moments first hand and sharing moments with others as they happen, with live video streaming, live one on one, one to many chatting 411 or with live discussion 608 . Other systems allow for schedule and calendar sharing or a sharing of information data objects and snapshots of life, but this platform may dynamically share an activity as it unfolds. A scrolling chat box 608 on a per identity basis (based on user stored or on-the-fly defined parameters) may dynamically show what others with similar interest are talking about at that moment, alongside activities happening at that moment. This platform may offer a key ability to create various identities and save various profiles, based on interest stacks, activity sets 404 , customized search options or favorite locations 413 , so that the most relevant data may be served to a user regardless of location or time of day. The platform also may put the power of instantly mobilizing people in the hands of a user unlike ever before. Streaming activities live 411 and archiving activity collections of uploaded files, data, video, posts, images and conversations 409 , may powerfully memorialize activities for associates, a family or group. Finally, marketing aspects of the platform across many industries may offer concrete monetizing possibilities that in many ways be more solid than other social media platforms.
Alternative Embodiments
[0120] The invention as described above has within its design, intent and scope, scalability and flexibility for deployment online or offline. The invention with the embodiments herein, is targeted towards everyone. However, just as depicted activity management modules FIG. 12 , FIG. 15 , FIG. 16 , may do for activities, simply adding additional modules, utilizing or not using database records, document templates and specialized data entry interfaces, the ESP 101 and SMS 213 may be tailored to specific businesses on any LAN/WAN. Any enterprise that requires organizing and mobilizing groups around a time sensitive deadline to achieve a desired result or project deliverable, i.e., event planning, travel business, party planners, and contractors, may realize value in the invention. With the embodiments herein, the ESP 101 is a foundation that within its composition has an ability to define, assign and track “activity units” or “activity entities” automatically and generate reminders and status updates at critical dates, thus guaranteeing completion—for example, a scheduling and completing of individual tasks to make a store liquidation sale a success or pull off a wedding without a hitch. Sub-tasks would in themselves be “child” activities that may be monitored and tracked via activity ID's and assigned parent ID's. A workflow set up this way may minimize paper and shorten activity durations—aiding businesses large and small in areas such as agenda coordination, meeting scheduling, training classes, project planning, convention organizing and so forth. Corporate businesses may use the platform to formulate project plans, assign deliverable dates and steps within, to complete a project, all while being able to upload files, forms, videos, live streams, presentations for others in a group to view, and collaborate online while preserving a history of meeting minutes. Travel businesses may use the platform to plan itineraries for visitor tours and vacations.
[0121] Possible embodiments of the invention may be as outlined here: 1) as an activity coordinator, the invention functions like an event announcer of a three-ring circus, but with unlimited rings all over the world, in every city. As an announcer, the ESP 101 may keep users abreast through its automatic scheduling feeds GSF 601 and USF 401 , of activities happening continuously in their area, so that at any moment a decision could be made whether to attend or join an activity, alone or with friends, online or offline, and interact with other users while there if desired 608 . To add to the dynamic nature, a user may pop on over to another locale, neighborhood or country and find out what is happening there in a snap. 2) The invention may operate as a day planner or organizer. Through its user settings 402 , search profiles 413 , location profiles 413 , identities may be stored for retrieval later and used to access activity data and present user specific activity information. Notifications 1207 may be set to remind a user of upcoming activities so that a day may be planned to the minute, making the most of every day. 3) The invention may also function as a diary-like repository 409 archiving shared activities online indefinitely, so a graduation party or birth of a baby, for example, may be shared in real-time or as a recorded activity, with documents, files, discussions, etc. archived forever. 4) The invention may also be an all-in-one marketing tool. The platform may allow anyone to post an activity regardless of their size or budget reach and exposure is the same for large or small entities and individuals alike. A media storage 1206 , on a per activity provider profile level may allow for a promotion of a business image, through menus, product lists, press items, sample portfolios, etc. and media storage on a per activity basis may build powerful brand recognition. By making activity announcements worldwide, business may increase their attendance. Higher foot traffic means more eyeballs, more exposure, more sales and more fun. 5) The platform may be a motivator by showing a user what they could be missing in a format that is simple and relatable, exciting people to act, encouraging users to get out and enjoy life wherever they are, and engaging users in dynamic real-time interaction both online and offline.
[0122] The embodiments disclosed herein can be implemented through at least one software program running on at least one hardware device and performing network management functions to control the network elements. The network elements shown in FIG. 3 may be at least one of a hardware device, or a combination of hardware device and software modules. It is understood that in the art that any of the aforementioned usage of interfaces, widgets and form controls may be enacted by various other similar programming means and on other operating platforms and devices.
[0123] In accordance with the provisions of the patent statutes, the principle and mode of operation of this invention have been explained and illustrated in its preferred embodiment. Although an embodiment has been described with reference to specific example embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader spirit and scope of the invention. The examples used in the description of this invention are intended to facilitate an understanding of ways in which the embodiments herein function. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, to inform and help visualize the processes. The accompanying drawings that form a part hereof show by way of illustration, and not of limitation, specific embodiments in which the subject matter may be practiced. The embodiments illustrated are described in sufficient detail to enable those skilled in the art to practice the teachings disclosed herein. Other embodiments may be used and derived there from, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Furthermore, it is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. This detailed description, therefore, is not to be taken in a limiting sense, and the scope of various embodiments is defined only by the appended claims, along with the full range of equivalents to which such claims are entitled.
[0124] Such embodiments of the inventive subject matter may be referred to herein, individually and/or collectively, by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept if more than one is in fact disclosed. Thus, although specific embodiments have been illustrated and described herein, it should be appreciated that any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.
[0125] In this document, the terms “a” or “an” are used, as is common in patent documents, to include one or more than one, independent of any other instances or usages of “at least one” or “one or more.” In this document, the term “or” is used to refer to a nonexclusive or, such that “A or B” includes “A but not B,” “B but not A,” and “A and B,” unless otherwise indicated. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the respective terms “comprising” and “wherein.” Also, in the following claims, the terms “including” and “comprising” are open-ended; that is, a system, device, article, or process that includes elements in addition to those listed after such a term in a claim are still deemed to fall within the scope of that claim. Moreover, in the following claims, ordinal lists if used, are used merely as labels and are not intended to impose numerical requirements on their objects.
[0126] The abstract of the disclosure is provided to comply with 37 C.F.R. §1.72(b), requiring an abstract that will allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing detailed description, it may be seen that various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed embodiment. Thus the following claims are hereby incorporated into the detailed description, with each claim standing on its own as a separate embodiment.
[0000]
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on a mobile device | Embodiments herein provide for an interactive event-scheduling platform (ESP), wherein locating activities via location data, notifying and alerting of them via real-time feeds and encouraging interaction through a full-service social media suite (SMS), enhanced with live streaming and “always-on” connectivity, could provide a fresh experience for users and hosts. A real-time data procuring system and method may solve problems with stale or incomplete activity data within a geographic area, bridge gaps between users and hosts by shortening time periods—from activity announcement, to discovery, to launch, to action—create buzz, maximize venue attendance, boost sales and ensure promotional success. Software crawlers may mine public Web sites for thorough activity data coverage. Stored activities, profiles and collected user interaction data may produce behavioral reports to increase ROMI. Security packages, installations and access controls may incite users to safely register themselves in the SMS to engage, interact and transact. | 6 |
[0001] This is a divisional application of U.S. patent application Ser. No. 10/818,577, filed on Apr. 6, 2004, which is herein incorporated by reference in its entirety, and assigned to a common assignee.
FIELD OF THE INVENTION
[0002] The invention relates to the general field of magnetic disk systems With particular reference to perpendicular write poles and controlling flux therefrom.
BACKGROUND OF THE INVENTION
[0003] One of the key advantages of single-pole (SP) head/media, with a magnetically soft underlayer (SUL) and perpendicular recording system, is the capability of providing a larger write field (than that of a ring head) to enable writing into the relatively thick media with high anisotropy constant. The latter quality leads one to assume better thermal stability associated with perpendicular recording. However, this advantage is diminished as the dimension of the pole tip is reduced to increase the areal recording density [1]. So, the tradeoff between head writing field and thermal stability may still limit the achievable areal density for perpendicular recording.
[0004] FIG. 1 is a schematic representation of a typical single pole vertical recording system of the prior art. Seen there is single write pole 13 whose ABS (air bearing surface) moves parallel, and close to, the surface of recording medium 16 . The latter comprises an upper, high coercivity, layer (not shown) on a magnetically soft underlayer. Coils 12 generate magnetic flux in yoke 14 which passes through main pole 14 into tip 13 and then into media 16 (where a bit is written). The magnetic circuit is completed by flux that passes through the soft under layer and then back into return pole 15 . The space enclosed by the yoke and poles is normally filled with insulating material 17 .
[0005] FIG. 2 is a front view of the structure shown in FIG. 1 when viewed along direction 18 .
[0006] An enlarged view of the write and return poles is shown in FIG. 3 . In this prior art design, the main pole 13 is about 0.1 to 0.4 microns thick at the ABS 19. The main pole is made of a high moment material, such as CoFe having a saturation magnetization, Bs, of about 2.4 T, but, in practice, this main pole does not saturate, except at the pole tip region. Thus the maximum write field in the media is mainly determined by the saturation level of the pole tip and the solid angle opened by the ABS of the pole tip.
[0007] To increase the write field, large W and t and small NH are preferred (as defined in FIGS. 1 and 2 ). However, for ultra-high density recording, track width W is limited by the track density requirement. To have good control of track width W, NH cannot be reduced to the extent desired due to the rounding effect of the photo mask used to pattern it. A small neck height also increases the side-fringing field and causes adjacent track erasure (ATE) [2].
[0008] A large pole width t will result in head skew problems [3]. Thus better methods for compensating field loss at ultra-high recording densities are essential. The present invention discloses a novel structure for a perpendicular write head that overcomes these problems.
References:
[0009] (1) Z. Bai, and J.-G. Zhu, “Micromagnetics of Perpendicular Write Heads with Small Pole-Tip Dimensions”, J. Appl. Phys, vol. 91, 6833 (2001).
(2) J. Schare, L. Guan, J. G. Zhu, and M. Kryder, “Design Considerations for Single-Pole Type Write Heads”, IEEE Tran. Magn., May, 2003
(3) R. Wood, T. Sonobe, Z. Jin, and B. Wilson, “Perpendicular recording: the promise and the problems”, J. Magn. Magn. Mater., vol 235, 1 (2001)
[0010] A routine search of the prior art was performed with the following references of interest being found:
[0011] U.S. Pat. No. 5,600,519 (Heim et al) discloses a tapered main pole as does U.S. Pat. No. 5,173,821 (Maloney).
SUMMARY OF THE INVENTION
[0012] It has been an object of at least one embodiment of the present invention to provide a single pole vertical write head having both a large head field as well as good spatial resolution.
[0013] Another object of at least one embodiment of the present invention has been to provide a process for manufacturing said vertical writer.
[0014] A further object of at least one embodiment of the present invention has been that said process introduce little or no changes to current processes for manufacturing vertical writers.
[0015] These objects have been achieved by means of a vertical main pole whose thickness has its conventional value a short distance from the tip but that tapers down to a significantly reduced value as it approaches the tip. Typically, the distance over which this tapering takes place is about 0.1 to 4 microns. In order to manufacture this structure, a trench is etched, using ion milling, partly into the yoke region and partly into the insulated coil well. Said trench has sides whose slope is carefully controlled through adjustment of the angle of incidence of the ion beam, this slope determining the afore-mentioned taper. After the trench has been just filled with a high moment layer, a second high moment layer is deposited to complete formation of the pole tip. After an appropriate lapping step to define the ABS, the process is complete.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows a single vertical pole magnetic writer of the prior art.
[0017] FIG. 2 is a head-on view of the structure of FIG. 1 .
[0018] FIG. 3 is a closer view of the pole tip portion of a vertical writer
[0019] FIG. 4 shows the starting point for the process of the present invention.
[0020] FIGS. 5 and 6 illustrate formation and filling of a trench with a high moment material.
[0021] FIG. 7 shows deposition of a second layer of high moment material over the afore-mentioned first layer.
[0022] FIG. 8 shows the final structure.
[0023] FIG. 9 compares the magnitude and spatial distribution of the head field in a device made according to the present invention with two prior art devices.
[0024] FIG. 10 is a cross-section of the write head, including an ABS level shield.
[0025] FIG. 11 is an ABS view of FIG. 10 for a single trailing edge shield.
[0026] FIG. 12 is said ABS view for a shield that surrounds the main pole on three sides.
[0027] FIG. 13 is an example of a tapered main pole at a trailing edge combined with a trailing shield
[0028] FIGS. 14-20 illustrate the process for making the structure shown in FIG. 13 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] We will disclose the present invention through a description of a process for its manufacture. This description will also serve to make clear the structure of the present invention.
[0030] Referring now to FIG. 4 , the process of the present invention begins with the formation of return pole layer 15 on a substrate (not shown). Layer 15 is any of Ni, Fe, or Co, or their alloys and it is deposited to a thickness between about 0.5 and 5 microns. This is followed by the formation of magnetic yoke 14 that includes a well within which is coil 12 embedded in layer of insulation 17 . Yoke 14 is a material such as Ni, Fe, Co, or their alloys.
[0031] Now follows a key novel feature, namely the formation of trench 51 , as shown in FIG. 5 . Ion beam milling is most commonly used to form said trench whose depth is typically between about 0.1 and 2 microns, this depth being controlled through adjustment of the ion beam's dose and duration. Walls 52 of trench 51 have sloping sides as shown in the figure. The sides of the trench slope at an angle between about 15 and 65 degrees from vertical, slope angle being controlled through adjustment of the ion beam's angle of incidence.
[0032] Trench 52 is then overfilled with layer 61 of a material capable of a magnetic moment of at least 1.8 T and is then planarized until insulation layer 17 is just exposed, as illustrated in FIG. 6 . Layer 61 should have high Bs and is any of Ni, Fe, or Co, or their alloys.
[0033] Next, as seen in FIG. 7 , layer 71 of a material capable of a magnetic moment of at least 2 T, is deposited. Layer 71 is any of Ni, Fe, or Co, or their alloys. This essentially completes formation of the magnetic write head which, as can be seen, now includes a tapered single vertical pole. All that remains to be done is to form air bearing surface 19 through planarizing in a plane normal to the upper surface of layer 71 . The final structure is seen in FIG. 8 .
[0034] FIG. 9 compares calculated plots of the head field (in Tesla) as a function its downtrack position (in microns) for three cases: Curve 91 is a conventional straight pole design having t=0.2 microns. Curve 92 is a straight main pole having t=0.4 microns, while curve 93 is for a tapered main pole (present invention) (t 1 =t 2 =0.2 microns, and NH=0). These data make it clear that the head field can be increased by providing a thicker main pole (curve 92 ) but this comes with an accompanying problem that the head field could erase data on adjacent tracks when the head is skewed. On the other hand, a main pole designed according to the teachings of the present invention (curve 93 ) achieves a head field even larger than that of the thicker, but conventional, pole with less erasure problems for the same head skew angle because of smaller pole thickness at the ABS.
[0035] The concept of a tapered main pole is not limited to only single pole perpendicular writers, but is also applicable to a shielded pole type perpendicular write head, a cross-section of which is shown in FIG. 10 with the shield being designated as element 25 . Shield designs may vary. For example, in FIG. 11 we show an ABS view of shield 26 which is located on only one side (the trailing edge), while in FIG. 12 we show shield 27 that surrounds the main pole on three sides (trailing edge and two sides in the cross-track).
[0036] In addition to the previously described tapered main pole structure at a leading edge, a tapered main pole at a trailing edge, combined with trailing shield 135 , is disclosed here, as shown in FIG. 13 . Note that the trailing shield is tapered to the same angle as the main pole, thereby maintaining a constant horizontal distance 131 therefrom.
[0037] The major process steps to make this trailing-edge-tapered main pole with trailing shield are illustrated in FIGS. 14-20 . FIG. 14 shows the starting point for manufacturing the writer once the reader structure has been completed. First, isolation 41 layer (usually Al 2 O 3 , between about 1 and 3 um thick) is deposited on the top reader shield 42 , followed by layer 43 of high Bs materials (Co, Fe and their alloys, Bs˜2.4 T, thickness about 0.2 to 2 um), which will eventually form the main pole. In FIG. 15 , an etching process similar to that shown in FIG. 5 , is applied to form trench 151 , whose slope angle defines the taper angle of the main pole. Subsequently, the process to define main pole track width is applied so the front geometry of the main pole (as in FIG. 2 ) is formed. In FIG. 16 non-magnetic layer 141 (usually Al 2 O 3 , 0.03 to 0.2 um thick) is deposited to serve as the gap between the trailing shield and main pole. In FIG. 17 , trailing shield 135 (alloys of Co, Fe, Ni, Bs around 1.0-2.0 T) is deposited on top of gap layer 141 . In FIG. 18 , coils 12 are made. Then the whole structure is filled with Al 2 O 3 and polished to expose the top surface of the trailing shield. In FIG. 19 , the return pole (alloys of Co, Fe, Ni, Bs around 1.0-2.0 T, thickness=0.5-5.0 um) is deposited and connected with the trailing shield. Finally, in FIG. 20 , lapping is applied to define the ABS of the head. | Prior art designs of single pole writers have been limited by premature saturation at the tip. This limits the head field that can be achieved without simultaneously widening the write profile. This problem has bee solved by means of a vertical main pole whose thickness has its conventional value a short distance from the tip but that tapers down to a significantly reduced value as it approaches the tip. A process for manufacturing this tapered tip design is also presented. | 8 |
FIELD OF INVENTION
[0001] The invention refers to a steam turbine with a relief groove on the rotor for relieving thermal stresses.
BACKGROUND
[0002] In rotors of steam turbines, local thermal stresses arise during running up and running down of the turbines, which are caused by the rapid change of the hot gas flows. Such stresses arise particularly in the region of the steam inlet of the high-pressure and intermediate-pressure steam turbines and often lead to crack developments in the region of the blade grooves, especially of the first blade rows. These can limit the operational service life of the rotor and particularly the number of risk-free running up operations of the turbine.
[0003] DE 2423036 discloses a turbine rotor disk with grooves which extend radially inwards between adjacent blades. The grooves serve for avoiding circumferential stresses on the edges of the rotor disks, which can arise on account of the thermal expansion of the rotor. On the base of each groove, a drilled hole is located in each case, into which a rivet is inserted.
[0004] EP 1724437 discloses a steam turbine with a fastening region for the rotor blades on the turbine rotor, the radial distance of which fastening region from the rotor axis reduces in the direction of the axial rotor blade thrust. Between the fastening region of the rotor blades and the equalizing piston, the rotor has a continuous recess ( 28 ) over the rotor periphery, which ensures an entry of steam from the inflow chamber in the inner casing to the equalizing piston and at the same time acts as a relief notch for the initial rotor blade thrust.
SUMMARY
[0005] An object of the invention is to create a steam turbine, especially a high-pressure or intermediate-pressure steam turbine, the turbine rotor of which has a device for relieving thermal stresses.
[0006] A steam turbine for operating with high-pressure or intermediate-pressure steam has a rotor, stator and an inlet passage for live steam which, downstream of the inlet passage, in a downstream direction of the operating steam flow, flows through the bladed flow path of the turbine. The turbine furthermore has a piston seal between rotor and stator and an equalizing piston. According to the invention, the steam turbine has a relief groove on its rotor for the purpose of relieving thermal stresses. The relief groove is arranged in the region of the equalizing piston of the rotor and extends in the circumferential direction of the rotor. The relief groove is therefore located at a point which is at a distance from the live steam inlet passage and, moreover, with regard to the inlet passage, in an axial direction which is opposite to the direction of the operating steam flow through the bladed flow path.
[0007] The relief groove, with regard to the first blade row in the bladed flow path, is arranged in a region in which the greatest thermal stresses would typically arise in the turbine rotor, especially during running up and running down of the turbine or during load changes. Moreover, the relief groove is arranged on the turbine rotor outside a region in which the steam flow enters the bladed flow path of the turbine via the inlet passage. This arrangement of the groove effectively reduces the thermal stresses, wherein at the same time the steam inlet flow is not impaired and therefore the performance of the machine is maintained.
[0008] A steam turbine with a relief groove on the rotor according to the invention brings about an extended operational service life in comparison to steam turbines of the prior art. The relief groove specifically allows an increased number of risk-free running up and running down operations of the steam turbine without detriment to the turbine performance. Moreover, the positioning of the relief groove according to the invention enables cooling of the groove with little cooling mass flow. Finally, the steam turbine according to the invention also allows easier inspection of the rotor by an inspection for crack development in the relief groove alone also giving reliable information about the state of the groove of the first blade row. In particular, the heat transfer in the region of the groove is reduced and therefore brings about a lower thermal load.
[0009] The relief groove preferably extends in the same shape over the entire periphery of the rotor. Its cross-sectional shape in this case can be of either symmetrical or asymmetrical design. In the asymmetrical design, the groove extends with increasing radial depth towards the live steam inlet passage.
[0010] In one embodiment, the relief groove is arranged in the region of the piston seal.
[0011] In a further embodiment of the invention, the relief groove has a cover in its opening. This has the effect of vortex flows inside the groove, which can arise from leakage flows in the piston seal, being reduced or even completely avoided. The arrangement of the relief groove in the region of the piston seal, together with the cover of the groove opening, in a further embodiment of the invention allows the arrangement of additional sealing strips on the cover which in the case of a relief groove without a cover would not be possible. As a result of this measure, an optimized sealing effect is made possible, despite the relief groove.
[0012] A cover of the relief groove can be realized either as an integral part of the stator or can be produced as a separate part and fastened on the stator, for example by hooks.
[0013] In a further embodiment of the invention, the relief groove additionally has a device for reducing the heat transfer and for controlling rotor vibrations. Since the relief groove is located in the vicinity of the hot live steam inflow, this can lead to the rotor heating up on the inside to an undesirable level as a result of high heat transfer. Furthermore, excitations of rotor vibrations can take place in the region of the relief groove. In order to avoid or at least to reduce these problems, the cover of the relief groove has a passage which extends axially at the level of the rotor surface. This ensures that a hot leakage flow from the piston seal can flow through this passage instead of finding its way into the relief groove.
[0014] In a further embodiment of the invention, the steam turbine has a cooling flow passage in the stator which, in the direction of the leakage flow, upstream of the relief groove, leads into the region of the piston seal. The relief groove has a cover with a passage level with the rotor surface.
[0015] In a further embodiment of the invention, the steam turbine has a cooling flow passage through the stator, which leads to a relief groove without a cover. The part of the stator which forms the wall of the live steam inlet passage extends radially inwards into the region of the bend of the inlet passage, where the passage leads into the bladed flow path of the turbine. A gap between stator and rotor extends from the inlet passage, partially radially, partially axially, as far as the relief groove. Cooling steam, which finds its way into the groove via the cooling flow passage, flows from the relief groove through the passage between stator and rotor into the live steam inlet passage. These cooling measures enable a reduction or even avoidance of excessive heating of the rotor.
[0016] In a further embodiment of the invention, the rotor is, in particular, a welded rotor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In the drawing FIG. 1 shows a steam turbine in a cross-sectional view along the rotor axis with a relief groove according to the invention in an arrangement in the region of the equalizing piston and the piston seal,
[0018] FIG. 2 shows a more detailed view according to the detail II in FIG. 1 of the relief groove according to the invention,
[0019] FIG. 2 a shows a detailed view of the invention with a relief groove with a cover in its arrangement in the piston seal,
[0020] FIG. 3 shows a further embodiment of the invention with a relief groove with a cover in the design of a blade root,
[0021] FIG. 4 shows a further embodiment of the invention with a relief groove with a passage for the leakage flow,
[0022] FIG. 5 shows a further embodiment of the invention with a relief groove and an additional cooling device in the stator of the steam turbine,
[0023] FIG. 6 shows a further embodiment of the invention with cooling of the relief groove from an additional cooling passage,
[0024] FIG. 7 shows a further embodiment of a relief groove with asymmetrical cross-sectional shape and a radially delimited cover,
[0025] FIG. 7 a shows a further embodiment of an asymmetrical relief groove with a radially extended cover,
[0026] FIG. 7 b shows a view of a cross section along the rotor axis of the relief groove with a cover according to FIGS. 7 and 7 a along the line VIIb-VIIb, particularly of the cross-sectional shape of the inner region of the passage for the leakage flow through the cover.
[0027] Like designations in the different figures represent the same components in each case.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] FIG. 1 shows in a meridional cross section a steam turbine 1 , for example a high-pressure steam turbine, the rotor 2 of which, with rotor axis 3 and stator or inner casing 4 , form a bladed flow path 1 ′, wherein rotor blades and stator blades 3 ′, 4 ′ are fastened on the rotor or on the stator. The steam turbine 1 is enclosed by an outer casing 1 ″. An inlet passage 5 for the operating steam leads from an inlet scroll 9 into the axially extending bladed flow path 1 ′, wherein the inlet passage 5 is defined by the stator 4 and a equalizing piston 6 . The operating steam flows in the axial downstream direction from the end of the inlet passage through the bladed flow path, where it is expanded. In the axial upstream direction from the inlet passage 5 , i.e. in the direction opposite from the downstream direction, a piston seal 7 extends between stator 4 and rotor 2 . Also, an encompassing relief groove 8 is arranged in the rotor 2 , at a distance from the inlet passage in the axial upstream direction and in the piston seal 7 .
[0029] FIG. 2 shows in detail the inlet scroll 9 from which flows a live steam flow 11 , via a guide vane row 10 , through the inlet passage 5 and from there impinges upon the first rotor blade row 12 . A leakage flow 14 finds its way from the live steam flow 11 through the piston seal 7 with sealing strips 13 . The relief groove 8 is arranged axially at a distance from the inlet passage 5 and in the region of the equalizing piston 6 . In this region, the relief groove can be arranged as close as possible to the first rotor blade row 12 which is affected most of all by thermal stresses and at the same time at a distance from the hot inlet steam flow 11 . As a result, the inlet flow and operating flow can flow as far as possible without hinderance through the relief groove and without loss into the bladed flow path 1 ′.
[0030] The groove 8 extends over the entire periphery of the rotor 2 and extends from its opening on the rotor surface essentially radially inwards. The groove extends, for example, radially into the region of the depth of the blade grooves of the rotor blades 12 . On its radially inner end, the relief groove is widened in comparison to its opening on the rotor surface. The widening on the radially inner end serves essentially for a notch effect being reduced as far as possible. The relatively narrow opening on the rotor surface is aimed at preventing hot steam, as far as possible, from being able to find its way from the leakage flow 14 into the groove 8 and therefore preventing vortex flows, as far as possible, from being able to arise there, which otherwise would lead to a local heating of the rotor.
[0031] FIG. 2 a shows an embodiment of the relief groove 8 according to the invention, wherein this has a cover 15 on its opening in order to further reduce vortex flows. The cover is connected on one side of the groove 8 to the rotor 2 by means of a welded seam. For example, the groove 8 in the region of its opening has a shoulder 17 , on which the cover is arranged. The cover extends over a greater part of the groove opening, wherein an open clearance 16 remains between the cover 15 and the edge of the opening which allows free thermal expansions.
[0032] The cover 15 , moreover, enables sealing strips 13 , which are fastened on the inner casing 4 , being able to extend up to the cover 15 in order to thus optimize the sealing effect of the piston seal 7 . Moreover, further sealing strips 13 can be fastened on the cover 15 in order to further perfect the sealing effect. The cover, especially with regard to its radial and axial dimensions, is formed so that it can withstand potential vibrations. For example, the cover can have a radial depth which is up to three-quarters of the entire radial depth of the relief groove. In particular, the radial depth of the cover can be between a half and three-quarters of the entire radial depth of the relief groove.
[0033] In a further embodiment of the invention according to FIG. 3 , the relief groove 8 , at least in the region of the rotor surface, is realized in the form of a blade groove 17 with a radially inwards widened region. In addition, an associated cover 18 of the relief groove 8 is realized in the form of a blade root which fits into the groove. In this case, the cover 18 is designed slightly smaller than the groove, so that movements which are induced by thermal expansions are freely permitted.
[0034] The blade root-form cover 18 , moreover, in this embodiment can have one or more sealing strips 19 which extend towards the inner casing 4 .
[0035] In an embodiment of the invention according to FIG. 4 , the steam turbine again has a relief groove 8 and also a cover of the groove opening level with the rotor surface. The cover in this case is realized by means of a part 20 of the inner casing 4 which extends radially inwards into the groove. Level with the rotor surface, this part 20 has a passage 21 which serves for guiding the leakage flow 14 through the cover and or for preventing the hot flow from finding its way into the groove.
[0036] In a particular embodiment, the passage 21 has a first widening 22 at the flow inlet of the bore. As an option, the passage 21 can also have a second widening 23 at the flow outlet in order to further benefit the flow through the passage. The passage 21 can be realized for example by means of a bore with round cross section. Alternatively, the passage can also be realized by milling out, wherein other flow-dynamically more advantageous cross sections can also be realized. Moreover, such passages can also be produced more cost-effectively in this way.
[0037] In the embodiment according to FIG. 4 , the cover is shown as an integral part of the stator. Alternatively to this realization, the cover as a separately produced part is also conceivable, which can be fastened in a groove on the stator by means of hooks or inserting a closed ring, which for production engineering reasons is simpler and more cost-effective.
[0038] FIG. 5 shows a steam turbine with a relief groove 8 with a cover 20 of the type as shown in FIG. 4 . In addition, the steam turbine has a cooling flow passage 25 which, for example, leads from a superheater, which is not shown, through the inner casing 4 into a chamber in the region of the piston seal and upstream of the cover 20 . A leakage flow 14 flows through the piston seal and through the passage 21 of the cover 20 . A cooling flow from the passage 25 can find its way into the relief groove and flow around the cover, as a result of which it is cooled.
[0039] FIG. 6 shows a further embodiment of a steam turbine with a relief groove 8 and a device for active cooling of the groove. The relief groove 8 , however, is of the type as shown in FIG. 1 , wherein the groove has no cover. In particular, the steam turbine has a piston seal 13 which extends only after the relief groove 8 and in the axial direction opposite to the direction of the steam flow through the bladed flow path 1 ′ of the turbine. There is no piston seal between the live steam inflow passage and the relief groove 8 . Instead, the stator extends in an extension 28 radially inwards up to the region of the bend of the inlet passage 5 . A cooling flow passage 26 extends from a suitable cooling steam source through the inner casing 4 to the opening of the relief groove on the rotor surface. The cooling flow finds its way from the relief groove into the live steam inlet passage 5 , wherein it flows through a gap 27 between the equalizing piston 6 and the part 28 of the stator into the inlet passage 5 . The cooling steam flow expediently has a steam pressure which is higher than that of the steam flow 11 in the inlet passage.
[0040] FIG. 7 shows an example of a relief groove 8 ′ which is formed asymmetrically in its cross-sectional contour. In particular, the relief groove extends with increasing depth in the direction towards the rotor axis also towards the inlet passage 5 . This contour is advantageous by it having curvature radii on one side, which result in lower stresses. In addition, as a result of this shape of the relief groove the distance between relief groove and the first rotor blade row is smaller, which additionally improves the relief. The relief groove 8 ′ can be designed with or without a cover. A cover 15 ′ extends for example radially only over a part of the radial depth of the relief groove.
[0041] FIG. 7 a shows a variant of this asymmetrical relief groove with a cover 15 ″ which extends over a greater part of the groove. The radial and axial dimension of the cover influences the heat transfer and also the mass flow resistance in the relief groove in each case.
[0042] Moreover, the cover 15 ′ or 15 ″ from FIGS. 7 and 7 a has a passage 21 ′ with a cross-sectional shape according to FIG. 7 b . The convex contours of the inner walls of the passage 21 ′ on the one hand can be produced cost-effectively by milling out and, moreover, have the effect of the rotor dynamics and the heat transfer in the relief groove being advantageously influenced.
LIST OF DESIGNATIONS
[0000]
1 Steam turbine
1 ′ Bladed flow path
1 ″ Outer casing
2 Rotor
2 ′ Rotor blades
3 Rotor axis
4 Stator, inner casing
4 ′ Stator blades
5 Inlet passage
6 Equalizing piston
7 Piston seal
8 Relief groove, symmetrical
8 ′ Relief groove, asymmetrical
9 Inlet scroll
10 Guide vane row
11 Steam flow in the inlet passage
12 First rotor blade
13 Sealing strips
14 Leakage flow
15 Cover
15 ′ “Short” cover
15 ″ “Long” cover
16 Clearance
17 Groove in the form of a blade groove
18 Blade root-form cover
19 Sealing strips
20 Part of the inner casing
21 Milled out leakage flow passage
21 ′ Milled out leakage flow passage
22 First widening
23 Second widening
24 Sealing strip
25 Cooling flow passage
26 Cooling flow passage
27 Gap between rotor and stator
28 Stator part, extending radially inwards | A steam turbine is provided having a relief groove which is arranged in the region of the equalizing piston and extends in the circumferential direction of the rotor. The relief groove, with regard to an inlet passage, is arranged in the axial upstream direction so that it is arranged on the rotor outside a region in which the steam flow enters the bladed flow path via the inlet passage. The relief groove, with regard to the first blade row, is arranged in a region in which the greatest thermal stresses can arise in the rotor. As an option, the relief groove has a cover for reducing vortex flows, and also devices for reducing heating of the groove or devices for active cooling. The steam turbine allows an increased number of risk-free running up and running down operations of the steam turbine with minimum detriment to the turbine performance. | 5 |
The present invention relates to polymeric materials and to sizing compositions containing such materials for synthetic yarns. More particularly, the present invention relates to polymeric materials and sizing compositions useful for sizing synthetic yarns to be used in water jet weaving operations.
A warp size is a chemical applied to a yarn comprising a warp for the purposes of protecting the yarn during subsequent handling and weaving. In these operations the yarns running in the warp direction are subjected to considerable abrasion from guide surfaces, drop wires, heddles, reed, shuttle and adjacent yarns. On a staple fiber yarn such as cotton, the size coats the yarn, protects it against abrasion and covers up such warp defects as knots, crossed ends, slubs and weak spots which occur in the normal variation of textile production. This is accomplished because the size glues down the protruding fibers, and provides an abrasion resistant coating for the fibers. On a filament yarn, the size coats the yarn and cements the filaments together to form essentially a monofilament yarn, thereby preventing chafing between filaments and between the yarn and guide surfaces.
Sizes such as corn starch, gelatin, carboxy methyl cellulose, polyvinyl alcohol, polyacrylic acid and styrene/maleic anhydride copolymers and alkali metal salts of ethylene/acrylic acid copolymers are conventionally employed as warp sizes for weaving on conventional fly shuttle looms as well as the more modern shuttleless rapier and projectile looms. However, due to the sensitivity of the conventional sizes to moisture, the weaver must carefully control weave room humidity to optimum levels for the size being used. This water sensitivity of conventional sizes renders such sizes totally unacceptable as sizes for warps to be woven on modern water jet looms.
In a water jet loom, a high pressure jet of water is used to carry the weft yarn through the loom shed, thereby forming the pick. During this operation, the warp yarn becomes saturated with water. If the warp yarn has been sized with conventional, water sensitive sizings, the size soon becomes water swollen and gummy, causing yarn-to-yarn entanglement and size buildup at the heddle eyes and reed. Under such conditions, spun warp yarns break and filament yarns entangle, either of which necessitate stopping the loom, often also causing defects in the fabric. In view of the difficulties resulting from the use of conventional sizes on the water jet loom, weavers wishing to utilize the water jet loom must either use a relatively high twist unsized filament yarn or a low twist filament yarn sized with a water-insensitive composition. Use of a high twist yarn is feasible only in the manufacture of a few types of cloth, thus limiting the versatility of the water jet loom. Unfortunately, the water-insensitive sizes now being employed in the manufacture of fabrics employing low twist filament yarns are not totally water-insensitive and do not adhere well to the yarn. Such sizes may also, of course, be difficult to remove in subsequent desizing operations.
In view of these difficulties existing in the weaving of textile fibers by water-jet looms, it would be highly desirable to provide improved polymers, sizing compositions and processes for sizing textile fibers for use in weaving with water-jet looms and, subsequently, to desize the woven material.
Advantages achieved by means of the subject matter of the present invention include excellent adhesion of the sizing composition to the textile yarns during the sizing and weaving processes. The sizing compositions of the present invention, furthermore, may withstand the high humidity of water-jet weaving locations without causing sized yarn to block in the beam as a result of high pressure winding. The sizing compositions of the present invention may also be easily removed by conventional scouring techniques using alkaline conditions after weaving so that the fabric may be further processed. The sizing compositions of the present invention exhibit excellent adhesion to a wide variety of synthetic fibers including polyester, nylon, aramide, acetate, and other fibers; they exhibit no blocking under high humidity and pressure conditions and can be easily removed under mildly alkaline conditions and moderate temperatures encountered in normal desizing operations.
According to the invention a polymeric material useful in a sizing composition for sizing textile fibers to be employed in weaving with water-jet looms is provided which comprises monomer units as follows:
a.) from about 23 to about 32 parts by weight butyl acrylate;
b.) from about 16 to about 22 parts by weight of a lower alkyl methacrylate;
c.) from about 28 to about 40 parts by weight of a monomer selected from vinyl acetate and styrene; and
d.) from about 14 to about 20 parts by weight of an acidic monomer selected from acrylic acid and methacrylic acid;
said polymer being further characterized as having an intrinsic viscosity of from about 0.16 to about 0.30 deciliter per gram as measured by a Cannon-Fenske Kinematic viscometer.
According to an embodiment of the invention, a sizing composition is provided for sizing textile fibers to be employed in weaving with water-jet looms which comprises an aqueous dispersion of from about 5 to about 40 parts by weight of a polymer as defined above, said composition having been adjusted to a pH of from about 6 to about 8 and a low molecular weight alcohol present in an amount to provide a bulk viscosity of less than 2000 centipoise as measured by a Brookfield LTV viscometer.
According to yet a further embodiment of the present invention, a process for sizing textile fibers to be employed in weaving with water-jet looms is provided which comprises applying to the fibers to be employed in the water-jet weaving operation a sizing composition as described above so as to deposit from about 1 to about 15 parts by weight of the polymer based upon the weight of the yarn, weaving said material on a water-jet loom and thereafter removing said sizing composition by conventional desizing operations employing mildly alkaline conditions and moderate temperatures.
DETAILED DESCRIPTION OF THE INVENTION
The polymeric materials of the present invention may be made by conventional free radical emulsion polymerization techniques which will be readily familiar to those skilled in this particular art. As used herein, the term polymer is intended to include homopolymers and copolymers made from two or more monomeric materials.
Butyl acrylate units are provided in the polymeric material to impart film forming characteristics to the polymer which is essential to achieving the desired continuous coverage of the yarn substrate. The proportion of butyl acrylate monomer units in the polymer may range from about 23 to 32 parts by weight based upon the weight of the polymer, preferably from about 24 to about 31 parts by weight, most preferably from about 25 to about 30 parts by weight.
Lower alkyl methacrylate monomer units are present in the polymeric material to reduce the tack of the polymer thus eliminating the tendency of the polymer to "block." The amount of lower alkyl methacrylate may be from about 16 to about 22 parts by weight based upon the weight of the polymeric material, preferably from about 17 to about 21 parts by weight, most preferably from about 18 to about 20 parts by weight. Typical lower alkyl methacrylate units which may be employed include isobutyl methacrylate, which is preferred, as well as butyl methacrylate and n-propyl methacrylate. Other lower alkyl methacrylates having high glass transition temperatures (herein Tg) may also be used. As used herein, the term "lower alkyl" is intended to include alkyl units having from 1 to about 6 carbon atoms.
The vinyl acetate and/or styrene monomer units are present in the polymeric material to promote adhesion to the fiber substrates, in particular, polyester and acetate substrates and also to reduce the tack of the polymer. These monomer units may be present in the polymeric material in an amount of from about 28 to 40 parts by weight based upon the weight of the polymer, preferably from about 29 to about 38 parts by weight, and most preferably, from about 30 to about 36 parts by weight. Styrene and/or vinyl acetate monomer units may be used as this monomeric component although vinyl acetate is preferred.
An acidic monomer is also employed, preferably acrylic acid or methacrylic acid and these monomers are used to promote adhesion to, for instance, nylon substrates. Such monomer units are also present in order to impart alkaline scourability to the polymeric material which, obviously, is necessary in order to remove the sizing composition during conventional alkaline scouring processing. The amount of such monomer units present in the polymer may be from about 14 to about 20 parts by weight, preferably from about 15 to about 19 parts by weight, most preferably from about 16 to about 18 parts by weight based upon the weight of the polymeric material.
The polymeric material of the present invention is prepared, as mentioned above, by conventional free radical polymerization techniques using a technique known in the art as delayed pre-emulsion addition. Such technique typically involves charging of water to a reactor which is then heated with nitrogen purge to about 60°-65° C. A pre-emulsion is prepared using water, a suitable surfactant, and the desired monomers. A chain transfer agent may then be added to control the molecular weight. Polymerization is initiated by a redox system such as potassium or ammonium persulfate, sodium bisulfite, sodium metabisulfite or sodium formaldehydesulfoxalate. The reaction temperature is then held typically at about 75° C. while the pre-emulsion and redox initiators are fed continuously into the reactor.
When the reaction is complete the polymeric materials generally have a pH in the range of from about 2 to about 4. In order to prevent corrosion of pipelines and equipment, ammonia may be added to neutralize the emulsion polymer to a pH of from about 6 to about 8. The bulk viscosity of the latex increases dramatically upon neutralization and may be controlled by the addition of, for instance, from about 1 to about 5 percent by weight based upon the weight of the composition of a low molecular weight alcohol such as methanol or isopropanol, or a water miscible solvent such as acetone or ethyl acetate.
The sizing composition of the present invention may be applied to the yarn by either conventional or single end sizing techniques. The amount of polymeric material applied to the yarn may range from about 1 to about 15 percent by weight based upon the weight of the yarn depending on the nature of the yarn, the denier, the amount of twist, the degree of texturizing, etc. After the sizing composition has been applied to the yarn drying may be accomplished by simply heating the yarn in air and/or drying cans. Oven drying may also be employed at temperatures ranging from about 70° to about 135° C. When using drying cans, a temperature profile of from about 80° to about 110° C. may typically be employed.
The invention may be further understood by reference to the following examples which are not to be construed as limiting the subject matter of the present invention as claimed in the claims appended hereto. Unless otherwise indicated all parts and percentages are by weight. In the examples and tables the following abbreviations have been used:
______________________________________AA = acrylic acid MAA = methacrylic acidACN = acrylonitrile MMA = methyl methacrylateBA = butyl acrylate ST = styreneiBMA = isobutyl methacrylate______________________________________
SIZE EVALUATION PROCEDURE
A. Size dots are generated by dropping three percent active size solutions onto polyester, nylon or acetate films. The dots are placed about one inch apart. The dots are air dried and then cured in a 115° C. oven for 15 minutes. The film and dots are then conditioned at ambient atmosphere for at least one hour prior to testing.
1. Adhesion test
Five dots are scored by a razor blade in a crisscross fashion without cutting through the substrate film. A piece of adhesive scotch tape is pressed onto the dots and then lifted from the dots quickly. The adhesion is defined as the percentage of the dot sectors which remain on the film.
2. Water sensitivity test
A section of the film with size dots is immersed in 25° to 30° C. water for 15 minutes. The dots are evaluated for clarity, toughness and adhesion. The water sensitivity rating of one to five is judged as follows:
1--totally unaffected, no change in appearance and toughness
2--slightly attacked (cloudy) but does not soften
3--softened, can be scraped off by spatula
4--softened, can be wiped off by finger
5--totally dissolved, dot disappeared
For the polymer to be an effective water-jet size, the water sensitivity rating has to be one or two, preferably one.
3. Face-to-face blocking
Films are placed together with the size dots facing each other and a 140 gram weight is placed on top of each pair of dots. The assembly is then placed in a closed chamber at room temperature (25° C.) with 100% relative humidity maintained by a dish of water. After 16 hours the films are peeled apart. The degree of sticking is noted and the amount of the dots transferred to the other film is visually judged:
0% blocking=dots peeled apart easily with no transfer
100% blocking=one dot totally transferred to the other dot, or the dots are stuck together and cannot be peeled apart
For a size to resist blocking in a water-jet weaving location even at high add-on, less than 10% blocking in this test is desired.
B. Size Removal Test
Size films are prepared by depositing the size compound containing 0.1 gram active solids onto the substrate film over an area of 4.5 cm 2 . The size films were air dried and then cured in a 115° C. oven for 15 minutes and then conditioned at ambient atmosphere for at least one hour.
1. Desizing Procedure
A desizing bath containing one liter of tap water, 2.5 g of soda ash and one gram of a nonylphenol ethoxylate nonionic surfactant is heated to 50° or 70° C. The substrate film supporting the size film is immersed in the desizing bath and stirred occasionally. The time required for the entire size film to dissolve is recorded.
From plant experience, a size with desizing times of ten minutes at 50° C. and six minutes at 70° C. by this test performs adequately in an actual desizing operation. In contrast, a size with desizing times of 35 minutes at 50° C. and 30 minutes at 70° C. by this test cannot be totally removed under normal plant scouring procedures.
It is noted that the time required to dissolve the size film is independent of the nature of the substrate within the realm of experimental error.
EXAMPLE 1
BA/VAc/iBMA/MAA 30/35/18/17
A one liter glass reactor is equipped with an agitator and addition funnel, thermometer, and nitrogen inlet tube. 191 grams of water is charged and heated to 65° C. with nitrogen purge. A pre-emulsion is made by adding 43 grams of butyl acrylate, 26 grams of isobutyl methacrylate, 50 grams of vinyl acetate, and 25 grams of methacrylic acid and 0.45 grams of n-dodecylmercaptan to a solution of 89 grams of water and 14 grams of a surfactant of a sodium salt of sulfosuccinic acid half ester, the pre-emulsion is then placed in the addition funnel.
An initiator solution is prepared by dissolving 0.9 grams potassium persulfate in 47 grams water. A catalyst solution is prepared by dissolving 0.27 grams sodium bisulfite in 13 grams water. The reaction is initiated by adding 15% of the pre-emulsion to the reactor followed by all the initiator solution and 20% of the catalyst solution. A gradual temperature rise to 70°-75° C. will occur. Maintain the reactor temperature at this range and add the remaining pre-emulsion and catalyst solution to the reactor over 90 to 100 minutes.
When the reaction is complete add a solution of 8.2g aqueous ammonia, 22 grams isopropanol, and 242 grams water to the reactor. When mixing is complete cool and discharge.
This composition contains 20% polymer solids, has lower than 100 centipoise viscosity, a pH at 7.2, and an intrinsic viscosity of 0.18 dl/g. Molecular weight determined by gel permeation chromatography is 1.4 million.
EXAMPLE 2
BA/VAc/iBMA/MAA 25/40/21/14
The same procedure in Example 1 is carried out using 36 g of butyl acrylate, 30.2 g of isobutyl methacrylate, 57.5 g of vinyl acetate, and 20.1 g of methacrylic acid.
EXAMPLE 3
BA/St/MAA 51/37/12
The same procedure is carried out using 76.5 g of butyl acrylate, 55.5 g of styrene and 18 g of methacrylic acid. 0.3 g of n-dodecylmercaptan was used and the neutralization step was not carried out due to the high viscosity of the final product.
EXAMPLE 4
A size with the copolymer composition of BA/VAc/iBMA/MAA 30/35/18/17 was applied to textured polyester using conventional sizing method. Size add-on was 8% by weight of the fiber. The warp was woven on a Nissan W51 water-jet machine. We obtained a warp stop level of 0.0088/mpx and a mechanical stop level of 0.0023/mpx. Six thousand yards were run over three weeks and no wash-off was noted during slashing or weaving. On the weaving machine, the drop-wires, the heddles and reeds were free from wash-off. The loom beams exhibited no blocking and no blistering; whereas beams using Permaloid 172, an acrylic copolymer manufactured by North Chemical Company, run concurrently with our test beams showed some blocking.
TABLE I__________________________________________________________________________SIZE EVALUATION - ON POLYESTER SUBSTRATE [η] (dl/g) DESIZABILITY INTRINSIC % WATER % (MIN)POLYMER COMPOSITION VISCOSITY ADHESION SENSITIVITY BLOCKING 50 C. 70__________________________________________________________________________ C.BA/VAc/iBMA/MAA 30/35/18/17 0.30 85 1 0 21 11 0.24 95 1 0 12 10Example 1 0.22 95 1 0 12 10 0.18 90 1 10 12 10 0.14 25 1 0 23 12 34/35/14/17 0.29 25 1 40 9 6 0.27 30 1 40 9 6 37/35/11/17 0.30 50 1 70 28 25 39/30/14/17 0.16 75 1 50 11 6 42/35/6/17 90 1 50 35 20 27/38/20/15 0.20 85 1 0 24 19 34/29/22/15 0.19 85 1 90 14 11 30/26/24/20 0.27 0 1 5 8 6Example 2 25/40/21/14 0.18 50 1 0 10 7BA/iBMA/MAA 45/38/17 0.20 80 1 40 45 40BA/VAc/ACN/MAA 45/32/8/15 95 2 80 28 22BA/VAc/St/MAA 44/29/10/17 75 1 80 19 11BA/VAc/MAA 48/35/17 75 1 60 34 30 48/38/14 95 2 90 37 29 45/38/17 55 1 50 32 30BA/VAc/MMA/MAA 46/32/5/17 95 1 70 20 11BA/EA/VAc/MAA 24/24/35/17 75 1 70 37 33BA/VAc/ACN/AA 48/25/10/17 50 3 90 9 7 52/25/6/17 35 4 70BA/VAc/MMA/ACN/ 43/29/5/6/17 30 2 90 29 25BA/St/AA 51/37/12 100 1 50 >60 >60BA/St/MAA 51/37/12 95 1 0 >60 >60Example 3BA/MMA/AA 51/37/12 85 2 80 >60 41BA/MMA/MAA 51/37/12 25 2 80 >60 33__________________________________________________________________________
TABLE II__________________________________________________________________________PERFORMANCE COMPARISON WITH OTHER PRODUCTS ON POLYESTER ON NYLON % WATER % % WATER % DESIZING (MIN)PRODUCT ADHESION SENS. BLOCK ADHESION SENS. BLOCK 50° C. 70° C.__________________________________________________________________________Example 1 95 1 0 100 2 0 12 10Abco FZ-47 30 2 0 90 3 0 34 31Permaloid 172 30 2 5 100 3 10 7 5Abco BY-4 0 1 0 50 2 0 10 6BA/St/AA 51/37/12 100 1 50 100 1 50 >60 >60BA/St/MAA 51/37/12 95 1 0 95 1 0 >60 >60BA/MMA/AA 51/37/12 85 2 80 100 2 70 >60 41BA/MMA/MAA 51/37/12 25 2 80 60 2 80 >60 33__________________________________________________________________________ | A polymeric material is provided which comprises the following monomer units: from about 23 to about 32 parts by weight butyl acrylate; from about 16 to about 22 parts by weight of a lower alkyl methacrylate; from about 28 to about 40 parts by weight of a monomer selected from vinyl acetate and styrene; and from about 14 to about 20 parts by weight of an acidic monomer selected from acrylic acid and methacrylic acid; said polymer being further characterized as having an intrinsic viscosity of from about 0.16 to about 0.30 deciliter per gram as measured by a Cannon-Fenske Kinematic viscometer. | 3 |
BACKGROUND OF INVENTION
The invention relates to a method, system and apparatus for treating water including a treatment mode comprising the steps of drawing said water from a pressurized water source through a controlling device to a treating vessel, the water inlet of said treating vessel being substantially at the top of a treating vessel, contacting said water with pressurized air present at the top of said treating vessel to release substantially all hydrogen sulfide and offensive odors present in the water and to dissolve oxygen in the water which reacts with soluble iron in the water to form ferric oxides, flowing the water through a filter bed of calcite mineral to remove substantially all sediment present in the water and to neutralize the ph of the water and to remove substantially all the ferric oxides from the water, the ferric oxides fastening to the calcite minerals and to already fastened ferric oxides, flowing the water to a final media means and to the outlet of the treating vessel and through the controlling device to a potable water plumbing system connected thereto.
BRIEF SUMMARY OF THE INVEVTION
It is therefor an object of this invention to provide a water treatment method, system and apparatus to effectively and efficiently remove substantially all offensive and malodorous contaminants and gases contained in ground water for use in a potable water system.
It is yet another object of this invention to provide a water treatment method, system and apparatus to effectively and efficiently remove substantially all ferrous bicarbonate, ferric hydroxide, hydrogen sulfide, odors, sediment, acidity and small amounts of manganese from ground water using a single combination aeration treatment vessel.
The prior art is replete with all types of water treatment systems, methods apparatus that are susceptible to clogging caused primarily by oxidized iron fastening to the interior surfaces of the several system components. This results primarily from the air induction of the iron laden water from the well into the pressure and aeration tanks. It is well known that the consequences of the “coating” or fastening of oxidized iron to the interior surfaces of system components include restricted flow and diminished efficiency of the several system components. Ultimately, the entire system must be dismantled and cleaned or replaced.
U.S. Pat. No. 3,649,532 to McLean is an example of such a approach of introducing the water into an aerator device. Air is entrained and mixed by turbulence into the water in a significant quantity, the water sucking air into the aerator device as it flows into the pressure tank. This air entrained water will initiate the forming of oxidized iron fastening to the interior surfaces of the several system components of the McLean system.
Similarly, U.S. Pat. No. 5,147,530 discloses a complicated loop system of treating well water in which a venturi nozzle mixes air into water during the entire pump cycle.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages will be more clearly understood and appreciated from the following Detailed Description of the preferred embodiment of the present invention when taken in conjunction with the accompanying drawings which illustrate the Water Treatment System of the present invention wherein:
FIG. 1 is an elevation of an embodiment of the Water Treatment System of the present invention partially broken away for clarity of illustration, with arrows schematically indicating the direction of water flow during the treatment mode.
FIG. 2 is an elevation of an embodiment of the Water Treatment System of the present invention partially broken away for clarity of illustration, with arrows schematically indicating the direction of water flow during the backwash mode.
FIG. 3 is an elevation of an embodiment of the Water Treatment System of the present invention partially broken away for clarity of illustration, with arrows schematically indicating the direction of water flow during the air injection mode.
FIG. 3 a is an elevation of an enlarged view of the air injection assembly of the control valve which is activated only during the air injection mode of FIG. 3 with arrows schematically indicating the direction of water and air flow during the air injection mode.
FIG. 4 is an elevation of an embodiment of the Water Treatment System of the present invention partially broken away for clarity of illustration, with arrows schematically indicating the direction of water flow during the rinse mode.
DETAILED DESCRIPTION
Referring now to the Figures there is shown a Water Treatment System 10 which is particularly adapted to provide potable to an associated plumbing system (not shown).
The Water Treatment System 10 is fluidly connected by inlet line 12 to pressurized source such as a submersible well pump (not shown). The inlet line is fluidly connected via a check valve 14 to a control valve 16 .
The operation of the well pump could be controlled by a cut-in, cut-out pressure switch (not shown) which senses the fluid pressure downstream of the well pump, all as well known in the prior art.
The Water Treatment System 10 is fluidly connected by outlet line 20 , at the control valve 16 , to an associated potable water plumbing system (not shown).
Control valve 16 may be selected from a wide variety of control valves such as the 2510 Econominder (T.M. of the Fleck Company) as manufactured by the Fleck Company. The control valve 16 may be used as manufactured except for several modifications which will be discussed further below.
The control valve 16 automatically controls the flow of water and time durations during the four modes of operation of the present invention and is typically an electro-mechcanically driven device as is the 2510 Econominder. As such, it is electrically connected to 115 volt receptacle (not shown).
The control valve 16 attached to a treatment vessel or tank 18 . Typically the control valve is threadably attached to the treatment vessel 18 at the top thereof. The treatment vessel 18 may be selected from a wide number available vessels used in well water applications such as molded fiberglass tanks manufactured by International Water Werks under their designated Model Numbers 1048 (10 inches in diameter and 48 inches in height), 1054 (10 inches in diameter and 54 inches in height) and 1248 (12 inches in diameter and 48 inches in height). The treatment vessel 18 may typically have an inside diameter of between ten and twelve inches and have an interior height of between 48 and 54 inches. As shown in FIG. 1 , Line A represents the high pressure water level cut-out point of the well pump and Line B represents the low pressure water level cut-in point of the well pump. As further shown in FIG. 1 , there is a pocket of compressed air 26 contained at the top of vessel 18 .
Also contained within vessel 18 is filter media 28 which comprises a about 98% by weight of calcium carbonate and about 0-2% by weight of magnesium oxide. The percentage of magnesium oxide is increased as the acidity of the untreated water increases.
An example of such magnesium oxide 28 is that supplied by Martin Marietta Magnesia Specialties, Inc. of Manistee, Mich. 49660 under their MagChem label; sized prilled 30 .
An example of such calcite material is the limestone (with small amounts of calcium magnesium oxide and crystalline silica quartz) supplied by Specialty Minerals of 260 Columbia Street, Adams, Mass. 01220.
Further contained within vessel 18 is a gravel type filter media 30 . An outlet riser tube 22 having a strainer basket 24 at one end thereof disposed in the gravel media 30 . The outlet riser tube 22 is fluidly connected at its other end to the control valve 16 and is in fluid communication with the outlet line 20 via the control valve 16 .
An example of such gravel 30 is course sand supplied by Southern Products & Silica Company, Inc. of P.O. Box 189, Highway 1 N, Hoffman, N.C.; sized (31610) individual pieces ranging from about ⅛ to ¼ inches in diameter.
Typically for the aforementioned 1048 tank the air pocket 26 comprises about 0.5 cu. ft. (depending upon the air pressure): 1 to 2 lbs. of the magnesium oxide could be used with about 100 lbs. of the limestone comprising about 1 cubic feet by volume along with about 0.5 cu. ft. by volume of the gravel.
Typically for the aforementioned 1054 tank the air pocket 26 comprises about 0.5 cu. ft. (depending upon the air pressure): 1 to 2 lbs. of the magnesium oxide could be used with about 125 lbs. of the limestone comprising about 1.25 cubic feet by volume along with about 0.5 cu. ft. by volume of the gravel.
Typically for the aforementioned 1248 tank the air pocket 26 comprises about 0.5 cu. ft. (depending upon the air pressure): 1 to 2 lbs. of the magnesium oxide could be used with about 125 lbs. of the limestone comprising about 1.25 cubic feet by volume along with about 0.75 cu. ft. by volume of the gravel.
The present invention essentially comprises four modes of operation; the treatment mode as depicted in FIG. 1 and the three modes of FIGS. 2-4 which may be broadly described as the regeneration modes; i.e. the backwash mode of FIG. 2 , the air injection mode of FIGS. 3 and 3 a and the rinse mode of FIG. 4 . Referring now to FIG. 1 , the treatment mode involves drawing non-aerated water from a water source such as a well, pressurized by a pump (not shown) through inlet line 12 and check valve 14 to control valve 16 . The check valve is adapted to allow fluid flow toward the control valve 16 but checks fluid flow in the opposite direction.
The control valve 16 fluidly connects the inlet line 12 and the top of the treatment vessel 18 . The untreated water then flows through compressed air pocket 26 . It is important to note that this is the first time the untreated water is exposed to air. Hydrogen sulfide and offensive odors are released from the well water and is captured by the air pocket 26 .
It is well known that oxygen readily dissolves in water under pressure. Water just below water levels A or B accordingly contains such dissolved oxygen as well as ferrous bicarbonate and ferric oxides.
As water continues to flow, as depicted by the flow arrows in FIG. 1 , the water ph is neutralized upon contact with calcite mineral filter media 28 . Oxygen reacts with soluble iron compounds. The oxidation reaction of Fe++ to Fe+++ produces ferric oxides. The ferric oxides fasten to the calcite mineral 28 and accordingly, essentially all ferric oxides are caught or captured on the calcite mineral filter media 28 .
Sediments in the water flow are also captured by the calcite mineral filter media 28 . Filter media 30 completes the filtering process as the water flow through the strainer basket 24 , up riser tube 22 and to the outlet line 20 via control valve 16 . The thus treated water enters the associated potable water system (not show) with essentially every trace of iron, sulfides, odor and sediment removed. This treatment process is continuous as such treated water is drawn from the treatment vessel 18 by the demands of the associated potable water system. Typically, the treatment mode runs continuously for approximately twenty-four hours before regeneration is required. This period is controlled by the control valve 16 .
Referring now to FIG. 2 , the backwash mode, which could be considered as the first of the regeneration modes, begins after the treatment mode and is typically six minutes in duration at a flow rate of one gallon per minute to two gallons per minute. The flow rate will vary according to the volumetric dimensions of the treatment vessel 18 as will be further discussed below. The timing, time period, flow rate and flow patterns are controlled by the control valve 16 .
As implied by the title of this mode the flow of water is reversed as depicted by the flow arrows in FIG. 2 .
Non aerated water is pumped through inlet line 12 and check valve 14 to the riser tube 22 via control valve 16 . The water flow continues through strainer 24 and gravel media 30 . The air pocket 26 , which is now saturated with hydrogen sulfide and other objectionable gases and depleted of oxygen, all occurring during the treatment mode, is released via the control valve 16 , to drain pipe 32 .
The filter media 28 is lifted slightly. The calcite granules that comprise the filter media 28 are in close contact rubbing and scouring each other thus removing ferric oxides that are fastened to the filter media 28 . Such loosened ferric oxides are carried upward by the water flow flushed from the treatment vessel 18 to the drain pipe 32 via control valve 16 .
The duration of the backwash mode can be increased later if the treatment vessel 18 is not been completely cleansed. By monitoring the discharge from the drain pipe 32 during the backwash mode it can be determined if the discharge is clear. After the Treatment System has been functioning a few weeks the backwash discharge should be clear at first then darken, turning orange or brown, depending upon the quantity of iron being removed. Thereafter the discharge from the drain line 32 should become clear again before the backwash mode is complete.
The following are examples of the backwash flow rates:
Treatment Tank Size
(diameter × height in
inches)
Backwash flow rate
10 × 48
1.0 gpm
10 × 54
1.5 gpm
12 × 48
2.0 gpm
Referring now to FIG. 3 and FIG. 3 a , the air injection mode, which could be considered as the second of the regeneration modes, begins after the backwash mode and is typically twenty-two minutes in duration. The flow rate will vary according to the volumetric dimensions of the treatment vessel 18 . The timing, time period, flow rate and flow patterns are controlled by the control valve 16 .
The air injection mode involves drawing non-aerated water from a water source such as a well, pressurized by a pump (not shown) through inlet line 12 and check valve 14 to control valve 16 . Control valve closes the internal bypass (not shown) around the in-line venturi 36 contained in the injector body portion 34 of the control valve. Water flow is then directed through screen 38 for removing particulate matter in the water that clog the venturi. As water passes through the venturi 36 , a pressure differential is created at the throat 40 of the venturi 36 .
A bore 42 axially coextensive with the throat 40 accepts a pressure sensitive valve 44 , as for example, a Schrader valve such as the type of Schrader valve employed in U.S. Pat. No. 5,147,530 to Chandler. The use of the Schrader valve is a modification to the standard issue Fleck Company Model 2510 Econominder.
The Schrader valve opens in response to the pressure differential at the throat 40 allowing for ambient air to enter the bore 42 to mix with the water flowing through the venturi 36 . The air entrained water is directed by the control valve 16 to the top of the treatment vessel 18 . This is the only time that any water is made to flow through the injector body 34 and its venturi 36 .
Pressure inside the treatment vessel 18 quickly drops as water inside treatment vessel 18 flows down through filter media 28 , gravel 30 , strainer 24 , riser tube 22 through control valve 16 and out drain pipe 32 .
As air entrained water flows into the top of the treatment vessel 18 air is released to form air pocket 26 . Water flows downward, as above discussed, and slowly rinses the lifted and loosely packed filter media 28 of untreated water present from the backwash mode. The water level is controlled by the control valve 16 to be about 1 ½ inch above the filter media 28 when the air injection mode is terminated.
Several sizes of venturis 36 are available from the manufacturer of the control valve 16 , as for example from the Fleck Company. Choosing the size or flow rate of the venturi is important for optimal regeneration and effective water treatment. The following are examples of flow rates:
Treatment Tank Size
Injector Venturi flow
(diameter × height in
rate @ 40 p.s.i.
inches)
pump pressure
10 × 48
.45 gpm
10 × 54
.45 gpm
12 × 48
.84 gpm
Referring now to FIG. 4 , the rinse mode, which could be considered as the third and final regeneration mode, begins after the air injection mode and is typically four minutes in duration. The flow rate will vary according to the volumetric dimensions of the treatment vessel 18 . The timing, time period, flow rate and flow patterns are controlled by the control valve 16 .
The rinse mode involves bypassing the air injector body 34 and the venturi 36 therein thereby compressing the air pocket 26 . Drawing non-aerated water from a water source such as a well, pressurized by a pump (not shown) through inlet line 12 and check valve 14 to control valve 16 , air pocket 26 , filter media 28 , gravel, strainer 24 , riser tube 22 , control valve and out the drain line 32 .
The filter media 28 is compressed to tightly packed state and the pressure in the treatment vessel 18 rises to equilibrium with the pump cut-off pressure. At this point the rinse mode is terminated and the regeneration cycle is complete.
The treatment system according to this invention is ready to supply treated water completely void of iron, hydrogen sulfide, obnoxious odors, sediment and acidity to its associated potable water system.
This is accomplished without a separate aeration tank, an air regulating device or air vent, use of an air compressor, in-line cartridge filter, devices including a venturi that restrict the flow of water from the well pump to the pressure switch and pressure system.
Several tests were conducted employing the present invention on well water applications. The results of these tests, which confirm the efficacy of this invention, are as follows:
Test No. I
Untreated Well Water Analysis
pH: 5.5 Ferrous Bicarbonate: 3.0 ppm Hydrogen Sulfide: 0.10 ppm Well Pump:: ½ hp deep well jet pump
Maximum pressure: 35 psi Maximum flow rate @ 35 psi: 3 gpm
Fleck 2510 Econominder control valve Treatment vessel; 10 inch diameter; 48 inch height Calcium carbonate 98%; Magnesium 2% Backwash flow rate: 1 gpm; injector size #1*
Treated Well Water Analysis
pH: 7.0 Ferrous Bicarbonate: 0.0 ppm Ferric Hydroxide: 0.0 ppm Hydrogen Sulfide: 0.0 ppm
Test No. II
Untreated Well Water Analysis
pH: 5.8 Ferrous Bicarbonate: 7.5 ppm Hydrogen Sulfide: 0.15 ppm Well Pump:: ½ hp submersible pump
Maximum pressure: 55 psi Maximum flow rate @ 55 psi: 12 gpm
Fleck 2510 Econominder control valve Treatment vessel; 12 inch diameter; 48 inch height Calcium carbonate 99%; Magnesium 1% Backwash flow rate: 2 gpm; injector size #2*
Treated Well Water Analysis
pH: 7.0 Ferrous Bicarbonate: 0.0 ppm Ferric Hydroxide: 0.0 ppm Hydrogen Sulfide: 0.0 ppm
Test No. III
Untreated Well Water Analysis
pH: 8.0 Ferrous Bicarbonate: 0.75 ppm Hydrogen Sulfide: 0.05 ppm Well Pump:: 1½ hp submersible pump
Maximum pressure: 60 psi Maximum flow rate @ 60 psi: 29 gpm
Fleck 2510 Econominder control valve Treatment vessel; 10 inch diameter; 54 inch height Calcium carbonate 100% Backwash flow rate: 1.5 gpm; injector size #1*
Treated Well Water Analysis
pH: 8.0 Ferrous Bicarbonate: 0.0 ppm Ferric Hydroxide: 0.0 ppm Hydrogen Sulfide: 0.0 ppm
*Injector specifications as found at page 27 in Fleck Co. Service Manual dated June 1995 covering, among other things, their Model 2500 Econominder Control Valve and associated parts.
While particular examples of the present invention have been shown and described, it is apparent that changes and modifications may be made therein without departing from the invention in its broadest aspects. The aim and purpose of the appended claims, therefore, is to cover all such changes and modifications as fall within the true spirit and scope of the invention. | A method, system and apparatus for treating water is provided including a treatment mode comprising the steps of drawing said water from a pressurized water source through a controlling device to a treating vessel, the water inlet of said treating vessel being substantially at the top of a treating vessel, contacting said water with pressurized air present at the top of said treating vessel to release substantially all hydrogen sulfide and offensive odors present in the water and to dissolve oxygen in the water which reacts with soluble iron in the water to form ferric oxides, flowing the water through a filter bed of calcite mineral to remove substantially all sediment present in the water and to neutralize the ph of the water and to remove substantially all the ferric oxides from the water, the ferric oxides fastening to the calcite minerals and to already fastened ferric oxides, flowing the water to a final media means and to the outlet of the treating vessel. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an intruder barrier and in particular, to an intruder barrier of the type which is rotatably mounted on the top of a wall whereby a person attempting to pass over the barrier is prevented from obtaining an effective hand-grip on either the wall or barrier.
2. Description of the Prior Art
In many instances where security devices are required, they are not required to provide an absolute bar to the professional or skilled thief but are more often required to deter vandals or, for example, where there is a likelihood of danger, to prevent children and other unauthorised personnel entering a premises. This is particularly the case, for example, in power stations and the like premises where the perimeter walls, fences and portions of the building musts be so protected as to prevent children and other unauthorised personnel climbing on to or over them. Thus, there are many cases where the security device is not so much to prevent unauthorised entry of the professional thief as to provide a safety device which will prevent untoward accidents. Needless to say, in the latter case the security aspect in also important.,
Static barriers are well known such as for example, spiked railings, barbed wire or pieces of broken glass embedded in the top of the wall. While some of these methods may restrict the activities of vandals unfortunately, they are not particularly efficient and can be readily easily overcome. More importantly they present a considerable safety hazard.
Further it is known from British Patent Specification No. 612,265 to provide apparatus for preventing or obstructing the scaling of walls, fences and the like barrier which comprises a substantially cylindrical member constituted by a series of rods, bars or sheet material arranged around the perimeters of a number of co-axial discs to produce a cage-like body mounted to rotate on bearing brackets adapted to be secured to the top of a wall or fence. Such devices consist, in their simplest form, of a substantially cylindrical member mounted in bearings to rotate on a substantially horizontal axis along a wall or fence top whereby a person attempting to pass over the barrier is prevented from obtaining an effective handgrip on the wall or barrier which rotates. These devices can be readily easily jammed in one position so that it is then only a question of climbing over a stationary barrier. Thus these devices while more suitable than spiked railings, barbed wire or capping members with inserted broken glass are not, unfortunately, as suitable as they could be for the purpose.
In Deutsche Offenlegungsschrift No. 2,206,436 there is described an intruder barrier substantially similar to the intruder barrier of British Patent Specification No. 612,265 except that this intruder barrier is mounted on a support so as to be movable at least partly at right angles to its longitudinal direction. Generally the device is roughly vertically displaceable, however, this intruder barrier is not necessarily any more efficient in use than the simpler constructions of intruder barrier and additionally, is more complex and costly to manufacture.
The tern "wall" is used in this specification not only to designate a solid wall such as a conventional perimeter wall but also a wall forming part of a building or any type of fence or railing. Additionally, the term "wall" includes the sides of any structure such as a tower or structural steel building or support. The object of the present invention is to provide an improved intruder barrier of the type hereandbefore described which will be efficient in operation while at the same time relatively inexpensive to manufacture.
A further object of the invention is to provide an intruder barrier which will not constitute a man-trap in use.
A still further object of the invention is to provide an intruder barrier that will be particularly userful for mounting on easy scale perimeter fences, for example, chain link fences.
SUMMARY OF THE INVENTION
According to the invention there is provided an intruder barrier for mounting on the surface of a wall comprising:
a scaling barrier rotatable about a longitudinal axis, said barrier being formed by a plurality of blades radially arranged relative to the axis; and
a support framework for mounting the barrier on the wall with it's longitudinal axis substantially parallel to the surface of the wall.
In one embodimentof the invention the blades are rotatably mounted on a support shaft which is, in turn, mounted on a support framework, the support shaft defining the longitudinal axis. In another embodiment of the invention each balde diverges from an apex formed by bending a sheet of material intermediate it's ends, portion of the material at the apex being cut-away to interlock with the apex of another blade, or blades thus forming a hole for reception of the support shaft. Preferably, in this latter embodiment there are at least four blades each pair of blades being formed from the one sheet of material. Ideally when there are four blades the angle of the apex between each pair of blades is approximately a right angle. The advantages of the present invention are many and it may be mentioned that the apparatus can be manufactured at a relatively low cost, is simple to erect and generally efficient in use. Further the invention does not constitute a man-trap or any other device that is likely to cause damage to unauthorised intruders while, at the same time, it prevents children or other less skilled personnel from climbing the perimeter wall.
The intruder barrier according to the present invention is particularly suitable for mounting on easily scaled perimeter fences, for example, a chain-link fence. It provides a more efficient barrier than the more conventional means used, such as, the cranking of the uprights away from the vertical, adjacent the top of the fence to provide an overhang or the use of barbed wire strands with the attendant dangers to personnel and consequently to the occupier under public liability legislation.
It should also be noted that a great advantage of the present invention is that it is equally difficult to get out of a premises as it is to get into it and, therefore, it will deter anybody attempting to enter the premises since he or she will be aware that there is no easy exit back over the barrier.
When manufactured of a metal mesh such as expanded metal mesh the metal mesh is almost impossible to climb as the mesh tends to sag and bend under weight while at the same time the edge of the mesh is sufficiently sharp as to cut into a persons hand if any pressure or load is applied and at the same time there is no question of severe injury.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevation of an intruder barrier according to the invention mounted on a wall,
FIG. 2 is an elevation on an enlarged scale of portion of the intruder barrier of FIG. 1,
FIG. 3 is a cross-sectional view in the direction of the arrows II--II of FIG. 2,
FIG. 4 is an elevation similar to FIG. 2 of portion of another construction of intruder barrier,
FIG. 5 is a cross-sectional view in the direction of the arrows V--V of FIG. 4,
FIG. 6 is an exploded view of portion of the intruder barrier of FIG. 4, and
FIG. 7 is a sectional view showing the barrier mounted on top of a wall.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings and initially to FIGS. 1 to 3 thereof there is illustrated an intruder barrier mounted on a wall 1. The intruder barrier comprises a scaling barrier, indicated generally by the reference numeral 2 formed by a plurality of blades 3 secured to tubing 4 which is rotatably mounted on a support shaft 5. The support shaft 5 forms a longitudinal axis for the scaling barrier which is substantially parallel to the surface of the wall 1. A pair of wall engaging uprights 6 form a support framework for the scaling barrier 2. The blades 3 are of open mesh or net configuration and in this embodiment are manufactured from expanded metal mesh and are welded to the tubing 4 at 7.
The blades 3 are thus constructed of a semi-rigid material which will deform under load but at the same time is not easily doformable. The exposed edges of each blade 3 forms a relatively sharp cutting edge. It will also be noted that there is more than one set of laterally spaced blades on the support shaft 5. Preferably, the minimum spacing A between the bottom of each blade 3 and the top surface of the wall 1 is of the order of 12 cms while at the same time the spacing between two adjacent blades 3 is so arranged to prevent somebody climbing beneath them and over the wall 1. In use, the blades 3 rotate freely under load and present a formidable barrier to a would-be vandal.
Referring to FIGS. 4 to 6 there is illustrated an alternative construction of intruder barrier according to the present invention, like parts are identified by the same reference numerals as used with reference to the description of the embodiment of FIGS. 1 to 3. In this embodiment a pair of blades 3 is formed from the one sheet of material being bent intermediate its ends to form an apex 8 from which the two blades diverge at approximately a right angle. The apices of two pairs of blades 3 interlock to form a hole 9 for reception of the support shaft 5.
It will be appreciated that it is not necessary that the blades be manufactured from an expanded metal mesh material nor indeed, is it necessary to manufacture a pair of blades from the one sheet of material. A blade may in fact be formed by bending a sheet of material intermediate its ends and cutting away portion of the material at the apex to interlock with the apex of another blade or blades thus forming a hole for the reception of a support shaft. The advantage of a mesh or net like material is that there is no need to cut away portion of the material at the apex. The additional advantages of the use of a mesh configuration are firstly, that there is relatively little resistance to air or wind passage therebetween and thus the blades will not rotate in the wind. Another advantage of the use of an expanded metal mesh is that in addition to sagging and bending under weight and having sharp edges so as to cut into a persons hand the actual material itself is sufficiently sharp as to make it very difficult to grip or hold. Also it is very difficult to cut weldmesh as it has not got uniform cross-sections such as, for example, conventional wire has. It is, however, preferable that there be at least four blades and in fact that when there are four blades that the angle at the apex between each pair of blades is approximately a right angle.
Preferably, the intruder barriers according to the present invention are generally of relatively short length as shown thus further foiling an attempt to lock them for scaling.
In a particularly suitable construction of intruder barrier in accordance with the invention it is preferable that there be at least four blades each pair of blades being formed from the one sheet of the material. This has the advantage of saving on material. Ideally when there are four blades the angle at the apex between each pair of blades should be approximately a right angle.
As mentioned above the material forming each blade may be a semi-rigid material deforming under load. Ideally the material is not readily deformable, that is to say it is not easily deformed under load but at the same time is sufficiently deformable as to make it diffcult to jam or otherwise secure in one position.
In accordance with the invention the intruder barrier is so adapted to be secured to the top of a wall and in use project beyond one face thereof, as shown in FIG. 7. Thus, when the intruder barrier projects beyond the face of the wall it is all the more difficult to climb it. Further the intruder barrier may be secured to or incorporated in a vertical wall and adapted to project beyond that face of the wall. This may be of considerable importance where the wall is very high and it would be dangerous if children were to climb to the top of the wall and then fall when trying to climb over an intruder barrier on the top of the wall. | An intruder barrier for mounting on the top or side face of a wall is provided. The intruder barrier consists essentially of a scaling barrier formed from a number of blades radially arranged and rotatable about a longitudinal axis so that any attempt to climb the wall is foiled as the blades simply rotate thus not providing a firm hold for the would-be intruder. | 4 |
BACKGROUND OF THE INVENTION
The invention relates to artificial resin materials degradable under the influence of water, as well as throw-away packaging materials, such as film, wrappings, cups, bottles, trays, boxes and the like, which usually are used for the packaging of consumer goods, such as foodstuffs, groceries and household articles in general.
As is known, because of the increasing use of plastic packaging materials that subsequently are thrown away, serious problems of pollution and waste have arisen because most plastic materials that are used for packagings, have a long service life in the open air and consequently when thrown away or piled on dumping-grounds for household refuse, are degraded to a very small extent.
A solution for these problems of pollution and waste can, of course, be found by using plastic materials for packaging purposes that, when they are thrown away or dumped on dumping-grounds, are degraded and start forming a part of the soil by the action of water, rainfall, moisture, wind erosion or biochemical processes and in a harmless form are incorporated in the natural environment. Against this desired degradation of the plastic materials the need should be weighed, however, that the durability of the material is preserved under normal conditions of processing and storage and that the degradation proceeds gradually, so that use in packaging is possible.
In prior art Netherlands patent application 71 05713 it has been proposed to prepare polymeric packaging materials that degrade under the influence of the ultraviolet light of the sun, but indoors have an unlimited service life if they do not come into contact with direct sunlight. A drawback of these polymeric packaging materials is, however, that the problem of degradation when they are dumped on dumping-grounds and refuse dumps is not sufficiently solved, since in such cases they are not exposed to to sunlight.
OBJECTS OF THE INVENTION
It is the object of the invention to provide plastic materials, suitable for the manufacture of packaging materials, which degrade under the influence of water but under other conditions do not deteriorate perceptibly in quality. On storage and use indoors they have a substantially unlimited service life. Besides and simultaneously with the said hydrolytic degradation of the plastic materials according to the invention there will also take place slowly proceeding secondary oxidative and other kinds of processes, i.a. by chain degradation of the polymers, low molecular products being produced that eventually by biochemical attack can be degraded to carbon dioxide and water, in accordance with the natural degradation of vegetable or animal materials
SUMMARY OF THE INVENTION
According to the invention the method for the preparation of plastic materials degradable under the influence of water is characterized in that a composition of polymers is prepared that mainly consists of (a) one or more copolymers of an alkenic unsaturated monomer and maleic acid anhydride, (b) one or more polymers of vinyl esters of lower aliphatic monocarboxylic acids and/or copolymers of them with other vinyl monomers and (c) one or more compounds, having the general formula ##EQU1## in which R represents an uni- or polyvalent alkyl or aralkylhydroxy radical and R' an uni- or polyvalent alkyl, aryl, aralkyl or alkarylcarboxyl radical.
GENERAL CONSIDERATIONS OF THE INVENTION
Compositions of polymers according to the invention can be used for the manufacture of packaging materials that are excellently suitable as throw-away packagings, because the material when dumped on dumping-grounds and refuse dumps, under the influence of water, moisture and air gradually degrades into products harmless to the natural environment and that do not disturb the ecological balance. In so doing, the whole process in general lines proceeds in three phases, in the first phase, which normally takes three days, a swelling and hydrolysis of the polymeric material occurrs and a water-soluble substance is formed. In the second phase, in a space of time of some weeks to some months, further hydrolysis and also oxidation takes place, depolymerization of the high molecular products occurring. Finally, in the third phase, which can extend over a period of some years, the degradation by biochemical influences (microflora, bacteria, etc.) into the "natural" products acetic acid and other organic acids, carbon dioxide and water takes place.
The copolymers of alkenic unsaturated monomers and maleic acid anhydride incorporated as component (a) in the compositions of polymers according to the invention are the main component of the latter. Preferably, such a copolymer of styrene and maleic acid anhydride is used, which product has already been known for a long time and has been extensively described in the literature (see e.g. R. H. Boundy, "Styrene, its polymers, Copolymers and Derivatives," Reinhold Publishing Corporation, New York, 1952, pp.860-865 and "Encyclopedia of Polymer Science and Technology", Interscience Publishers, New York, Vol. 1, pp.81-85. This copolymer has a highly polar character but is insoluble in water, however. Under the influence of water it changes, however, dependent on conditions of pH and temperature, into a polymer that is soluble in water because free carboxylic groups or carboxylate ions are formed. Use is made of this property, e.g. when this copolymer is applied as a thickener in aqueous solutions and as a soil-improving agent. For use as a plastic material in manufacturing films and the like this copolymer has been found unsuitable so far because of bad mechanical properties (much too brittle at ambient temperature) and because the moisture sensitivity is too high, particularly in the pH range >7.
It was found now, however, that the copolymer of styrene and maleic acid anhydride, as a result of the combination with components (b) and (c) according to the invention, as a composition of polymers with desired mechanical properties, such as flexibility, impact resistance, tensile strength and the like, can be made excellently useful, while retaining its water or moisture sensitivity, so that a hydrolytic degradation can occur into a water-soluble product. Moreover, the sensitivity to water of the total composition of polymers can be controlled by means of the mutual ratios of the composing components (a), (b) and (c).
It is surprising that the desired mechanical properties are rendered permanent to the copolymer of styrene and maleic acid anhydride only, if a combination of both components (b) and (c) is added to it. When adding only component (c), it is true that initially an improvement in the mechanical properties is attained, but it is not of a permanent nature. On the other hand the addition of this component (c) is necessary, though, in order to attain the desired water-sensitivity of the combination of polymers, since when only component (b) is added a permanent improvement in the mechanical properties is attained, but the water-sensitivity decreases.
Of the polymers of vinyl esters of lower aliphatic mono carboxylic acids incorporated as component (b) in the compositions of polymers according to the invention, polyvinylacetate is preferably used. On this product, which has versatile uses, there is comprehensive literature (see,for instance, "Encyclopedia of Polymer Science and Technology", Interscience Publishers, New York, Vol. 15, pp.577-663). Like the copolymer of styrene and maleic acid anhydride the polymer has a highly polar character. In mechanical properties it differs considerably, however, from the last-mentioned copolymer, because the former is of a plastic or rubbery character. For use in the invention the polyvinylacetate should have a sufficiently high molecular weight, i.e., of at least 200,000. Under certain conditions this polyvinylacetate can be mixed in all proportions with the copolymer of styrene and maleic acid anhydride used as component (a). As has been said previously, by adding polyvinylacetate to the copolymer of styrene and maleic acid anhydride, the mechanical properties of the latter product are considerably and permanently improved, enabling the processing and application as a synthetic resin material for packaging purposes and the like.
The compounds, having the general formula ##EQU2## and incorporated as component (c) in the compositions of polymers according to the invention, can be considered as esters of the so-called hemiformals, i.e., the primary addition products of alkanols to formaldehyde, having the formula
ROCH.sub.2 OH.
Since hemiformals as such cannot be isolated, for the preparation of the present esters, one cannot start directly from these hemiformals, but other methods should be followed for their preparation that are known per se. As suitable methods of preparation i.a. may be mentioned: 1. Conversion, with alkali or alkaline earth salts of monocarboxylic acids, of α-halogen ethers obtained by reaction of formaldehyde with alkanols and halogen hydride according to the reaction equations: ##EQU3## (see F. E. Clark, J.Am.Chem.Soc.39, 712 (1917). 2. Conversion of cyclic formals, obtained by reaction of formaldehyde with diols, with acid anhydrides according to the reaction equations: ##EQU4## (see United States patent 2,416,024)
Consequently in this reaction, compounds are produced, which, besides the characteristic oxymethylene ester group, also contain a "normal" ester group.
Characteristics for the compounds, having the general formula ##EQU5## include their easy hydrolyzability with water, the original starting products being formed again according to the reaction equation: ##EQU6##
In contrast with the hydrolysis of "normal" esters, for which mostly highly acidic or basic reaction conditions and high temperatures are required, the hydrolysis of the oxymethylene esters proceeds easily with water, having a pH=7 and at ambient temperature. Use is made of this property with advantage when these compounds are applied in the combinations of polymers according to the invention. Moreover, it was surprising that the addition of these compounds did not cause a perceptible deterioration of the mechanical properties of the compositions of the synthetic resins, provided that, in choosing the suitable compounds a number of factors is taken into account, being related to i.a. the volatility, the compatibility in mixing the components (a) and (b) and the hydrolysis rate at neutral pH. It has been found that when the compounds are correctly chosen, component (c) can be incorporated in the compositions of polymers in an amount, varying between 5 to 50 per cent by weight, calculated on the total weight of the composition of polymers.
With a view to the choice of the compounds according to the invention to be applied as component (c), furthermore their availability plays a part, their cost, the availability of the raw materials and the like to be used for their preparation, as well as the innocuity of their decomposition products for the environment.
In the compounds having the formula ##EQU7## both radicals R and radical R' may be derived from univalent as well as from polyvalent hydroxy and carboxyl compounds, respectively. That is, radical R is an alkyl or aralkyl compound, having 1, 2, 3 or more hydroxy groups in the molecule and radical R' is an alkyl, aryl, aralkyl or alkaryl compound, having 1, 2, 3 or more carboxyl groups in the molecule. Basically, compounds are possible, in which both R and R' are univalent compounds; compounds in which R is a univalent compound and R' is a polyvalent compound; compounds in which R is a polyvalent compound and R' is a univalent compound; and compounds in which both R and R' are polyvalent compounds. The compounds of the first-mentioned type, i.e., those in which R is an alkanol or aralkanol and R' is an alkyl, aryl, aralkyl or alkaryl monocarboxylic acid group, generally are less eligible for application in the combinations of polymers according to the invention because either their boiling-point is too low, or their miscibility with both other components (a) and (b) is not as good. Consequently, compounds of the last-mentioned three types are preferred, in which either R, or R', or both, have been derived from polyvalent compounds.
As examples of compounds which radical R in the above formula may represent, can be mentioned i.a. methanol, ethanol, n-propanol, n-butanol, glycols, glycerol, pentaerythritol and sorbitol. Examples of carboxyl compounds which radical R' may represent, are i.a. formic acid, acetic acid, propionic acid, malonic acid, succinic acid, adipic acid, benzoic acid and phthalic acid.
The compositions of polymers prepared according to the method of the invention can be processed into degradable plastic materials according to techniques known in the art. Thus, from their solutions in volatile organic solvents, films of various thicknesses can be manufactured. These films can also be manufactured according to the usual blow-moulding method if a suitable range of ratios of the 3 compounds is chosen. The compositions of polymers of the present invention can also be processed into moulded products by means of rolling, extrusion, injection moulding, vacuum forming and the like.
As it is known in this field (see US Patent specification 3,536,461) the copolymers of the type (a) as further above defined can be modified with small amounts -- e.g. some percentages by weight -- of a higher monofunctional alcohol having at least 12 carbon atoms, e.g. a fatty alcohol such as stearyl alcohol. This may be of advantage as regards the workability of the three-component mixture of the present invention as well as regards the mechanical properties of the products obtained.
The plastic material thus obtained is clear, transparent and colorless. Its mechanical properties, such as elasticity, tensile strength, flexibility and the like can be adapted for specific applications by varying nature and mutual ratios of components (a), (b) and (c). Filling agents, dyes or pigments and other additives can be added to the combination of polymers before or during processing. Compositions of polymers according to the invention can also be mixed with other polymers and/or resins. The plastic material obtained from the compositions of polymers is resistant to hydrocarbons, higher alkanols, fats and oils.
As has been stated already, the degradation process of the plastic materials manufactured according to the invention, in outline proceeds in three phases. Upon closer observation of the whole process it has been found that in the first of these phases hydrolysis of component (c) of the composition of polymers takes place, water-soluble degradation products being formed, viz. alcohols, formaldehyde and carboxylic acids. In this process, the formation of carboxylic acids is of great importance, since these contribute to the prevention of too rapid an attack on the whole material. For the hydrolysis of component (a) of the composition of polymers depends on the pH and in particular takes place quickly in the alkaline range. Thus, because of the formation of the carboxylic acids from the hydrolysis of component (c), now a certain extent of stabilization of the material against too rapid a degradation and its subsequent loss of strength occurs. This is particularly importance when the plastic material is used in bats for household refuse for which strength preservation during a period of some days is very important.
Only after component (c) has decomposed entirely and the acid formed in the process has been neutralized, does the second phase of the accelerated degradation set in. In this phase component (a) is slowly hydrolyzed into water-soluble polymeric products and component (b) is slowly degraded and hydrolyzed into polyvinyl alcohol. It is known from literature that both the styrene-maleic acid anhydride copolymer and polyvinyl alcohol can be applied as soil-improving agents. So, both products are innocuous for the environment and even can contribute to improvement of composting techniques.
Finally, in the third phase of the degradation process both polymeric products will be degraded oxidatively and hydrolytically into low molecular weight compounds, which thereupon finally will be converted by microorganisms into carbon dioxide and waater. It is important, however, that after some weeks to some months have passed, the original plastic materials in the soil or in dumping-grounds have been converted into decomposition products that are innocuous for the environment and finally into water-soluble decomposition products.
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is further elucidated with some embodiments in the following examples.
EXAMPLE I
Preparation of styrene-maleic acid anhydride copolymer 208 gs. of styrene (2 mol) and 196 gs. of maleic acid anhydride were dissolved in 1600 gs. of 2-butanone, whereafter as catalyst 0.5 gs. of azo-bis-isobutyronitrile was added. The mixture was completely polymerized in a nitrogen atmosphere in a period of approx. 4 hours, while being stirred and heated at approx. 70°-80°C. The dry, solid polymer could be obtained from the solution as a white powdery substance with a melting-point above 200°C by precipitating with methanol, filtering off, rinsing out with methanol and drying.
EXAMPLE II
A. Preparation of tetramethylene-bis (oxymethylene acetate) CH 3 -COO-CH 2 O-CH 2 CH 2 CH 2 CH 2 -OCH 2 OOCCH 3 . To a reaction vessel of 1 L capacity, provided with a stirrer, thermometer and reflux-condenser, were added 200 gs. of acetic anhydride and then 100 gs. (1.2 mol) of anhydrous sodium acetate were suspended therein. Then 93.5 gs. (0.5 mol) of tetramethylene-bis-(chloro methylether) were added, and a rise in temperature of approx. 10°C. occurred. Next, the mixture, while being stirred, was heated for 1 hour at 100°C. The sodium chloride produced was filtered off after cooling and rinsed with two portions of approx. 50 mls. of ether each. From the filtrate and the washing liquid collected, firstly the acetic acid anhydride and the ether were removed under reduced pressure, whereupon the remaining product was subjected to fractional distillation at a pressure of 0.9 mm. After first runnings, which were stripped off at 117°-120°C/0.9 mm (approx. 10 gs.) the desired product was distilled over at 120°-122°C/0.9 mm, while 13 gs. of residue were obtained. Yield approx. 79 gs. (68%), n D 22 = 1.4306; d 21 = 1.098.
B. Preparation of pentaerythritol-bis (oxmethylene acetate)-bis ##EQU8## (acetate).
To 160 gs. (1 mol) of molten pentaerythritol-bis(formal) were slowly added, while the solution was being stirred at 70°-80°C, a mixture of 1 gram of concentrated sulphuric acid and 255 gs. (2.5 mol) of acetic acid anhydride. By cooling, the temperature of the reaction mixture was maintained at approx. 70°C for a period of approx. 3 hours, whereupon a quantity of 2 to 3 gs. of sodium acetate were added to neutralize the sulphuric acid.
The excess of acetic acid anhydride (0.5 mol) was then distilled off at a pressure of 15 mm. and after impurities had been distilled off the product was distilled in vacuum. The ester was obtained in a yield of 98-100%. Boiling-point 157°C/0.02 mm. n D 23 = 1.4452. Ester equivalent weight = 90.8 (theoretically 91.0).
In an analoguous way the pentaerythritol-bis(oxmethylene propionate)-bis (propionate) was prepared by reaction with propionic acid anhydride.
EXAMPLE III
A solution of styrene-maleic acid anhydride copolymer in 2-butanone, as obtained according to Example I, was mixed with a solution of approx. 20 per cent by weight of commercially available polyvinyl acetate (trade name MOWILITH M 70, supplier Farbwerke Hoechst A. G.) in 2-butanone. The average molecular weight of this polymer amounts to approx. 1 × 10 6 . The two solutions were mixed with each other in such quantities that the mixture contained equal quantities by weight of the polymers.
To separate amounts of the mixture, quantities were added of the compounds prepared according to Example II, and varying from 5 to 50 per cent by weight, based on the total weight of the combination of polymers.
From the viscous solutions thus obtained plastic films were manufactured, varying in thickness from 10 μ to 500 μ, by casting on a glass sheet and subsequent evaporation of the solvent. By stretching these films, their mechanical properties could even be improved.
Of three samples of the films manufactured by casting, having a thickness of approx. 0.1 mm, some mechanical properties were determined by means of a tensile test. For this purpose, strips, having a width of 1.5 cm were longitudinally cut out of the films, which were kept for two months at ambient temperature and normal degree of humidity. The length at the start of the tensile test amounted to 10 cm and the drawing rate was 5 cm/min. Samples 1 and 2 were taken from films, manufactured from a mixture with approx. 25 per cent. by weight of pentaerythritol-bis(oxmethylene acetate)-bis and sample 3 from film, manufactured from a mixture with approx. 30 per cent by weight of this compound. For comparison, as sample 4 a commercially available polyethylene film of the same thickness was subjected to the same tensile test. The results are given in the following table:
yield stress strength at E-modulus elongation aT fracture break -sample kg/cm.sup.2 kg/cm.sup.2 kg/cm.sup. 2 kg/cm.sup.2avg. dev. f.* avg. dev. f.* avg. dev. f.* avg. dev. f.* strength strength strength strength__________________________________________________________________________1 189 13 145 13 7500 700 105 402 205 21 174 18 8500 1300 110 703 146 9 168 14 6000 1000 160 184 119 3 151 14 2400 350 400 70__________________________________________________________________________ *standard deviation
EXAMPLE IV
With samples of the casting-films manufactured according to Example III and consisting of equal parts by weight of styrene-maleic acid anhydride copolymer and polyvinyl acetate and 25% by weight of pentaerythritol-bis (oxmethylene acetate)-bis(acetate), and another film having the same composition but made with the corresponding propionate compound, respectively, the following tests were carried out to demonstrate their sensitivity to water. The thickness of the films was 80-100 μ:
A. Accelerated degradation in water with phosphate buffer at pH=8 and a temperature of 80°C
Some strips of the films were kept in continuous contact with the hot water. After a certain period of time the loss of weight was determined and the progress of the attack was plotted graphically as a function of time.
From the tests it was found that after approx. 15-20 minutes the pentaerythritol-bis(oxmethylene acetate)-bis(acetate) had substantially disappeared from the film by hydrolysis and solvation in water. This manifested itself i.a. by loss of mechanical strength (becoming brittle) of the dried material.
After approx. 14-15 hours the styrene-maleic acid anhydride copolymer had also dissolved entirely and a fleecy, shapeless substance was left, mainly consisting of highly swollen polyvinyl acetate.
From infrared-analysis results it appeared that saponification was beginning in this residue.
The samples with pentaerythritol-bis(oxmethylene propionate)-bis(propionate) showed an approximately twofold decrease in degradation rate of the film.
B. Degradation in water at pH=6-7 and a temperature of 15°-20°C
Strips of the films were suspended in test tubes, filled with water. After 24 hours a slight turbidity and a slight swelling of the film occurred. After 3 to 5 days component (c) had, dependent on the thickness of the film, substantially disappeared from the film and the swelling started to increase at an accelerated rate, the strength of the material decreasing at a slow pace. After 2-3 weeks had elapsed, component (a) had disappeared and a soft fleece of polyvinyl acetate remained. In this test it was also found that the degradation of the film in which as component (c) the propionate compound had been incorporated proceeds more slowly (by a factor 1.5-2).
After some months fungoid growth was found in the water, which indicates to a biochemical conversion of the decomposition products.
C. Degradation in alkaline aqueous solution at pH>9 and ambient temperature
Upon introducing strips of the films into solutions of ammonia, sodium hydroxide, soda and organic amines, at ambient temperature a very strong swelling and a fast degradation were found. Already after some hours the total degradation had reached an advanced stage.
D. Degradation on burying
On burying films it was found that these had substantially lost their mechanical strength after some weeks and that the material disintegrated. The temperature, humidity, pH and thickness of the film were the most important factors influencing the degradation.
Upon burying in a mass of vegetable compost that became overheated (temperature approx. 70°C), after a week had elapsed, only with difficulty could residues of the film be retrieved. | Water-degradable synthetic resin compositions substantially composed of a 3-component mixture of
A. one or more copolymers of an alkenic unsaturated monomer and maleic anhydride
B. one or more hydrophilic polymers of vinyl esters of lower aliphatic monocarboxylic acids and/or copolymers thereof with other vinyl monomers and
C. one or more compounds having the general formula (R)OCH 2 OCO(R'). The compounds are mixed by dissolving them in a solvent and the foils or articles are produced therefrom. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Application No. 62/067,079, filed on Oct. 22, 2014 and titled “Material Handling Device”, the entire contents of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a material handling device, commonly referred to as a shovel.
DESCRIPTION OF THE PRIOR ART
[0003] Shovels are used in many applications for moving material between locations or accumulating and moving waste for disposal. Shovels consist of a blade, usually with upturned edges to contain material of varying sizes, with the blade coupled to handle to facilitate manipulation and movement.
[0004] The handle is disposed at a convenient angle to the blade to allow the user to move the material. Because the user needs to get hold of the handle when the blade is in the material, the handle is usually arranged at an angle to the blade so the end of the handle is raised from the surface. The shovel is dimensioned to maximise the load that may be carried at any one time, depending on the material with which it is intended to be used and the environment in which it is used. An issue arises when the shovel is used on an inclined or sloped surface such as a roof. It is desirable to minimise the number of movements and number of trips for the relocation of the material. However, this suggests a large blade area where a larger amount of waste material may be accumulated. A larger blade area suggests an increase in the length of the handle to provide leverage for lifting. Moreover, the inclination of the handle relative to the blade means that one or other will project upwardly when the shovel is laid on the roof, causing a potential trip hazard and limited contact with the surface.
[0005] U.S. Pat. No. 6,412,841 provides a multiuse cleanup tool system construction wherein it can be utilized as a dustpan or a shovel. However, such a tool still poses limitations as it is not effective on sloped surfaces such as roofs and risks slipping or falling off the surface creating a potential safety risk.
[0006] To attempt to enhance the ability to work on sloped surfaces, U.S. Pat. No. 7,025,397 shows a scoop for use on non-horizontal work surfaces. The patent shows the use of two baseplates connected to meet at a 120-170 degree angle with further plates attached to close blade in the to form a pan. The side of the scoop can have handles for lifting. However, this design also lacks a conventional handle to allow for ease in manoeuvrability and relies on friction between the scoop and surface to retain the scoop on the sloped surface when not attended by a user.
[0007] It is desirable to obviate or mitigate at least one of the above-mentioned drawbacks.
SUMMARY OF THE INVENTION
[0008] Below are example embodiments of the material handling device and example aspects thereof. Other embodiments and aspects are provided in the detailed description and the figures.
[0009] Accordingly, the present invention provides a shovel comprising a blade, a handle connected to the blade by a pivot assembly. The pivot assembly includes a latch to control relative movement between the blade and the handle. The latch is movable between a locked position in which relative movement is inhibited, and a released position in which such movement is permitted. An anchor is mounted on the shovel and may be deployed to engage a surface upon which the shovel is placed.
[0010] Preferably, the anchor is a pin mounted on the handle and moveable between a stored position and the deployed position. As a further preference a pair of anchors is provided at spaced locations on the handle.
[0011] It is also preferred that the latch is operated remotely from a distal end of the handle.
[0012] The blade can have various configurations, based on the application. It can consist of a singular piece of curved material or a single plate coupled with a plurality of plates to form walls around the single piece. The shovel can be formed from either a metal, metal alloys, or from plastics. The blade can also include a variety of different ribbing.
[0013] In a preferred embodiment, when the shovel is placed in a manner such that the anchoring pins are perpendicular to the surface, the anchoring pins can be driven into the surface. The number of anchoring pins can range from a single pin to a plurality of pins housed within anchor assemblies spaced along the elongated handle respectively. A hammer or similar device can be used to strike the pins and drive them into the surface. Once the anchoring pins are driven into the surface they are able to retain the shovel and inhibit it from sliding and falling. When it is desired for the shovel to be moved the pins can be pulled out from the surface and the shovel can be relocated as desired.
[0014] In a further aspect, the present invention also provides a shovel having a blade, a first handle secured to the blade at a rear portion thereof and projecting rearward from the blade, and a second handle secured to said blade and projecting forwardly from the rear edge of the blade.
[0015] When relocating the shovel the second handle hanging over the blade can be used to assist in lifting the load. When the shovel is heavy it can be strenuous to lift and carry the shovel from a point away from the center of mass. Placing the handle in a manner that projects over the shovel blade places the handle closer to the center of mass and makes the process of relocating the shovel more ergonomic.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] An embodiment of the invention will now be described by way of example only with reference to the accompanying drawings in which
[0017] FIG. 1 is a perspective view of a roof with a shovel placed on the roof
[0018] FIG. 2 is a top perspective view of the shovel of FIG. 1
[0019] FIG. 3 is a view similar to FIG. 2 on an enlarged scale
[0020] FIG. 4 a is an enlarged view of a portion of FIG. 2 in a first condition
[0021] FIG. 4 b is a view similar to FIG. 4 a in a second condition
[0022] FIG. 5 is a front perspective view of the shovel in the alternate configuration of FIG. 4 b
[0023] FIG. 6 is a cross sectional view across the line 6 - 6 ;
[0024] FIG. 7 a is a perspective view of the shovel in one configuration
[0025] FIG. 7 b is a perspective view of the shovel in an alternate configuration to FIG. 6 b
[0026] FIG. 8 is a view similar to FIG. 1 showing the shovel used in a different configuration.
[0027] The features of the invention will become more apparent in the following detailed description in which reference is made to the appended drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0028] Referring to FIG. 1 , a roof 102 is clad with shingles 104 that periodically require removal. To facilitate removal of debris such as removed shingles 106 , a shovel 100 is used to collect debris and transfer it to a disposal site.
[0029] Referring to FIGS. 2 and 3 , a shovel 100 comprises a blade 202 and a handle 216 . The blade 202 and handle 216 are interconnected by an attachment assembly 205 . The assembly 205 is mounted on the blade 202 by a bracket 204 using fasteners 302 . In between the bracket and the blade there is a reinforcement plate 300 .
[0030] A first handle 208 is attached to the bracket 204 using fasteners 306 . The handle 208 includes a pair of upstanding arms L-shaped 209 and a bar 211 extending between the arms 209 . The arms 209 project forwardly over the blade 202 to locate the bar 211 forwardly of the attachment assembly 206 .
[0031] The attachment assembly 206 also includes a pivot assembly 210 , best seen in FIG. 3 . The pivot assembly includes a pair of spaced plates 206 that are secured to the bracket 204 . The plates 206 include a plurality of bored out holes 304 and a plurality of adjustment holes 418 as shown in FIG. 4 . A shaft 308 is coupled to the back of the pivot assembly 210 and is fastened to the attachment assembly 206 using fasteners 310 that pass through apertures 420 ( FIG. 4 a ) in respective ones of the spaced plates 206 .
[0032] As shown in FIGS. 4 a and 4 b the adjustment holes 418 on plates 206 are spaced along an arc centered on the aperture 420 . The pivot assembly 210 further includes a clevis 314 with a pair of arms 324 extending from the clevis base 322 . The arms 324 are spaced apart to be received between the plates 206 and each has a bore 326 to receive shaft 308 . The shaft 308 thus defines an axis of rotation of the clevis 314 relative to the blade 202 . Each of the arms 324 has a through hole 328 spaced from the bore 326 along the arc of the holes 418 . The through-hole 328 receives a locking pin 416 that can slide relative to the arm 324 to engage one of the holes 418 . The pins 416 are biased by springs 414 that act between heads of the pins 416 and a central boss 316 projecting from the clevis base 322 . Movement of the pins 416 is controlled by a release mechanism located at the clevis.
[0033] The release mechanism includes a latch base 400 slidably mounted in the boss 316 of the clevis 314 . The base 400 is coupled to a plurality of latch levers 404 via links 406 . The latch levers 404 are pivotally mounted on the clevis 314 on an axial bearing 410 and the opposite end engage a circumferential recess 408 formed on the heads of the pins 416 . The pivot assembly 210 is enclosed by a top plate 226 fastened to the clevis 314 using the fasteners 312 .
[0034] The boss 316 of the clevis 314 includes a rear facing cylindrical recess to receive a shaft 217 of the handle 216 . The shaft 217 terminates in a grip 218 allowing the user to firmly grasp the handle 216 to maneuver or manipulate the device.
[0035] A trigger 224 is located within the grip 218 and includes a lever 219 pivotally connected to the grip 218 by a pin 610 ( FIG. 6 ).The lever is connected to a cable 612 that extends through the handle 216 and is connected to the latch base 400 .
[0036] The shaft 217 of the elongated handle 216 carries a pair of anchor assemblies, 212 , 220 at spaced locations. The first anchor assembly 212 is secured adjacent the inner end of the shaft 217 using fastener 318 and the second anchor 220 secured using fastener 320 .
[0037] Referring again to FIG. 6 , each of the anchor assemblies 212 , 220 includes an anchor pin 214 slide-able in a boss 600 . The elongated handle has a transverse pinhole 612 , dimensioned to receive an anchoring pin 214 . The anchors 212 , 220 include a compression spring 602 within the boss 600 that acts between an end plate 604 and the pin 214 to bias the pin to a retracted position in which the lower end of the pin 214 is located within the boss 600 .
[0038] FIGS. 4 a and 4 b show alternate configurations of the pivot assembly 210 . In FIG. 4 a the pivot assembly is locked with the pin 416 engaged in one of the holes 418 . When the angle between the blade 202 and elongated handle 216 needs to be adjusted, the trigger 224 is actuated by operating the lever 219 . The lever 219 then pulls the cable 612 causing the latch base 400 to recede, thereby causing the pivot assembly to adopt the configuration as denoted by FIG. 4 b . The receding of the latch base 400 causes the link bar 406 to pull the latch levers 404 and pivot them about the bearing 410 . As the latch lever 404 rotates about the axial bearing 410 it acts through the head against the bias of the spring 414 to retract the pin 416 from engagement with adjustment hole 418 . The user can then adjust the angle of the handle 216 by pivoting about the shaft 308 . When the angle is adjusted as desired the user releases the remote latch 224 causing the latch base 400 to return to its original position under the bias of the springs 414 , reengaging the latch lock 416 and locking it into the desired adjustment hole 418 . In this manner, alternative configurations can be obtained for the shovel 100 , as illustrated in FIG. 5 , which shows the shovel 100 after the adjustment of the angle between the blade 202 and the elongated handle 216 .
[0039] Referring to FIGS. 6, 7 a and 7 b , when the shovel 100 is desired to be secured on a sloped surface, such as when it is being loaded with debris, the orientation of the handle is adjusted so that it is generally parallel with the base of the blade 202 . In this configuration, the the nails 214 are perpendicular or near perpendicular to the surface 102 . The nail head 606 of the anchor pins 214 can be driven downwardly by a tool such as a hammer. The anchor pins 214 are driven out of the boss 600 and in to the underlying surface, such as the roof 102 , as seen in FIG. 1 .
[0040] When it is desired to remove or relocate the tool, the anchoring nail 214 can be pulled out of the surface using a tool such as a hammer.
[0041] One exemplary application of the tool is shown in FIG. 1 . The shovel 100 is used on the sloped surface of the roof 102 . The anchor pins 214 are driven into the surface of the roof 102 , securing the shovel 100 from slipping or sliding. When the shingles 104 of the roof 102 are removed they can be gathered in the blade 202 of the shovel 100 . The shovel 100 can hold debris 106 , the debris comprising removed shingles along with other waste from working on the roof 102 .
[0042] When it is desired for the shovel to be relocated the anchor pins 214 can be pulled out of engagement with the roof 102 and the angle between the blade 202 and elongated handle 216 can be adjusted using the pivot assembly 210 after pulling the trigger 224 . Then, when the shovel is in the desired configuration the shovel can be lifted at the first handle 208 as shown in FIG. 2 . The handle 208 hangs forward over the blade 202 allowing the user to lift the tool from closer to the center of the mass after the debris has been collected in the blade 202 . The ability to lift from the center of mass offers a more efficient means to manoeuvre the shovel 100 .
[0043] The adjustability of the handle 216 relative to the blade 202 facilitates the use of the shovel 100 in different orientations on the roof 102 , as shown in FIG. 8 . In this orientation, the blade 202 faces down the roof and is adjusted relative to the handle 216 to minimise the angle between them. The blade thus projects upwardly from the roof to provide a more horizontal surface than the roof itself. This permits debris to be cleared from the lower portions of the roof and from the eaves troughs and placed on the shovel in a stable manner. The handle is secured to the roof by the anchor pins 214 that prevent sliding down the roof and tipping of the shovel when loaded. The shovel may be released by withdrawing the anchor pins 214 and moved as previously described.
[0044] The shovel 100 is shown in the exemplary embodiments as having two anchors to house the anchor pin 214 , however; it can be appreciated that only one anchor may be used, or several anchors can be utilized along the length of the elongated handle 216 .
[0045] It can be appreciated that though the specification provided details the use of the shovel on a sloped surface, the shovel can still be utilized any surface in the same method of a traditional shovel or shovel.
[0046] The particular design of the blade, elongated handle, the pivot assembly, and anchors are selected to satisfy structural conditions due to static and dynamic loads in repeated use within working environments.
[0047] Below are general example embodiments and example aspects of the material handling device.
[0048] In a general example embodiment, a shovel is provided which includes: a blade, a handle pivotally connected to the blade by a pivot assembly at one end to permit pivotal movement of the handle relative to the blade, and at least one anchor assembly mounted on the handle; the anchor assembly including a fastener operable to secure the shovel on a surface.
[0049] In an example aspect of the shovel, the pivot assembly includes a lock assembly, the lock assembly operable between a locked position, in which relative movement between the blade and handle is inhibited, and a released position in which relative movement between the blade and handle is permitted. In another aspect, a pair of plates are attached to the blade and spaced along an axis perpendicular to the longitudinal axis of the handle, the plates each having a corresponding aperture; and a rod member extends between the plates and is fastened at the apertures; and a housing is attached to the plates and the rod member, wherein the housing is pivotable about the rod member, and the housing has a bore to receive the handle. In another aspect, the housing houses the lock assembly. In another aspect, the plates each have a plurality of corresponding adjustment holes spaced along an arc centered on the aperture, and the lock assembly comprises locking pins operable by the movement of a release mechanism to engage and disengage with the adjustment holes to respectively inhibit and permit relative movement between the housing and the plates. In another aspect, the locking pins are biased to be engaged into the adjustment holes. In another aspect, the handle supports a trigger for the lock assembly, the trigger being operable to operate the release mechanism to further operate the lock assembly between said locked and released positions. In another aspect, the trigger includes a pivotable lever, the lever connected to a cable that extends through a longitudinal bore in the handle and connects to the release mechanism such that pivoting the lever disengages the locking pins from the engagement holes. In another aspect, the handle of the shovel includes an elongate shaft and a grip, wherein one end of the shaft is received into the bore of the housing and the grip is situated at the opposing end of the shaft. In another aspect, the trigger is proximal to the grip. In another aspect, trigger is incorporated in the grip. In another aspect, the shovel has a plurality of anchor assemblies provided at spaced locations on the shaft. In another aspect, a first anchor assembly is attached to the shaft proximate to the blade. In another aspect, the shovel further includes a second anchor assembly attached to the shaft proximate to the grip. In another aspect, the fastener of each of the first and second anchor assemblies is at least one pin. In another aspect, each of the anchor assemblies includes at least one boss in which the at least one pin is slideable, and the shaft has a transverse pinhole dimensioned and positioned to receive each of the at least one anchoring pin. In another aspect, the anchor assembly further includes a biasing element within the at least one boss to act between an end plate and the pin to bias the pin to a retracted position in which the lower end of the pin is located within the at least one boss. In another aspect, the second anchor assembly is incorporated in the grip. In another aspect, the shovel has an additional handle attached to the shovel proximate to the blade, and the additional handle projects above and over the blade.
[0050] In another general example embodiment, a shovel is provided which includes: a blade, a first handle connected to the blade, and a second handle attached to the shovel proximate the blade wherein the second handle projects above and over the blade.
[0051] In an example aspect of the shovel, the first handle projects away from the blade. In another aspect, the second handle projects in the opposite direction of the first blade. In another aspect, the first handle is pivotally connected to the blade by a pivot assembly at one end to permit pivotal movement of the first handle relative to the blade.
[0052] In another general example embodiment, a shovel is provided which includes: a shovel comprising: a blade, a handle pivotally connected to the blade by a pivot assembly at one end to permit pivotal movement of the handle relative to the blade; wherein the pivot assembly includes a lock assembly such that the lock assembly is operable between a locked position, in which relative movement between the blade and handle is inhibited, and a released position in which relative movement between the blade and handle is permitted; and a trigger for the lock assembly attached to the handle distal from the lock assembly, wherein the trigger includes an actuator and a link extending from the actuator to a release mechanism such that moving the actuator operates the lock assembly between the locked and unlocked position.
[0053] In an example aspect of the shovel, the actuator is a pivotable lever. In another aspect, the link is a cable. In another aspect, the lever is connected to the cable and the cable extends through a longitudinal bore in the handle, and the cable connects to a release mechanism such that pivoting the lever operates the lock assembly between the locked and unlocked position. | A material handling device to be used on non-horizontal platforms such as roofs, hills, construction sites, and other sloped surfaces. The device is comprised of a large blade for collecting debris or other materials such as shingles. The blade connects to a first handle that hangs forwardly over the opening of the blade. This handle is meant to assist lifting by placing the handle over the center of gravity of the load in the shovel. The blade is also attached to an angle adjustment pivot assembly. The pivot assembly is attached to an elongated handle. The adjustment mechanism adjusts the angle between the blade and the shaft. At the first end of the shaft is an anchor assembly, comprising an anchoring pin. The anchoring pin can be hammered into the surface to secure the shovel from falling or slipping. The shaft is then connected at its second end to a second anchor. The second anchor comprises a second anchoring pin to be used in the same manner as the first, an end handle for manoeuvring the shovel, as well as a remote latch mechanism to control the angle between the blade and the shaft. | 4 |
This application is a continuation of application Ser. No. 019,125 filed Feb. 26, 1987, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a liquid jet recording head and more particularly it relates to a liquid jet recording head which discharges a recording liquid as liquid droplets and which can make a gradation record.
2. Related Background Art
Hitherto, non-impact recording methods have attracted attention because they produce little noise. Especially, the liquid jet recording method (ink-jet recording method) is a very useful method which makes a high-speed recording possible and which, besides, makes it possible to record on normal paper without the special treatment of fixation. Thus, many proposals have been made for various systems using such method and apparatuses for practicing them and some of them have been further improved and commercialized. Until now, efforts have been made for practical use of these methods.
Above all, those which are disclosed in Japanese Patent Application Laid-Open No. 51837/1979 and West German Laid-Open Application (DOLS) No. 2843064 have characteristics different from other ink-jet recording systems in that heat energy is allowed to act on a liquid to obtain power to discharge a recording liquid as liquid droplets.
That is, according to the recording systems disclosed in the above publications, the liquid which has undergone the action of heat energy changes in its state with an abrupt increase in volume, which includes generation of bubbles, and action based on said change in state permits the recording liquid to be discharged as droplets from orifices of the tip portion of the recording head and these droplets adhere to a recording member to make a record.
Furthermore, the ink-jet recording system disclosed in DOLS 2843064 has the advantage that images of high resolution and high quality can be obtained at high speed because the recording head part can easily be formed as a high density multi-orifice device of full-line type.
While, as explained above, liquid jet recording apparatuses have many advantages, in order to record images of higher resolution and higher quality, it has been required to give gradation to the picture elements to record images containing halftime information.
Hitherto, as systems for providing such liquid jet recording apparatus with gradation controllability, there have been known a first system, (1) according to which one picture element is composed of plural cells arranged in a matrix form and gradation of the desired level is digitally expressed depending on the number of cells and state of arrangement of these cells which are occupied by image forming elements realized in the cells arranged in matrix form, and a second system (2) according to which one picture element is formed of respective image forming elements and the desired gradation is analoguely expressed by changing optical density of the image forming elements.
However, in the case of the liquid jet recording methods which records by discharging liquid by heat energy, according to the above (1) gradation control system (the first system), the area of one picture element per se increases, which results in a reduction of resolution, etc. Furthermore, because of digital control, steps of gradation are large and sometimes the image obtained lacks fineness in texture. On the other hand, according to the above gradation control system (2) (the second system), in general, the size of one picture element, namely, the size of the image forming element, may be changed by changing electrical energy applied to an energy generator and in this case, sometimes, sufficient gradation control cannot be obtained.
Therefore, as disclosed, for example, in Japanese Patent Application Laid-Open No. 132259/1980, there has been proposed a recording head wherein plural heater elements are arranged in line with the discharge direction in the nozzle and the number of operating heater elements is controlled to change the size of the heat acting area, whereby modulation of volume of bubbles is effected by variation of area in which the bubbles are generated.
Moreover, according to the recording head disclosed in U.S. Pat. No. 4,251,824, at least two heating elements different in area of heater are arranged in the discharging direction in a nozzle and one suitable heater is selected in accordance with input signal to make dot diameter changeable, thereby to control gradation.
That is, in the case of the above-mentioned recording heads, plural heating elements are arranged in along the liquid supply direction in a nozzle and the heat acting area is changed by selection of these heater elements or operation of plural heating elements in combination, whereby dot diameter is changed to control gradation.
However, when plural heating elements are arranged in the liquid supply direction in the nozzle as mentioned above, the relative distance between said heating elements and discharge opening of nozzle is varied.
Especially when the entering direction of ink into the heat acting part and the discharging direction of the ink from the heat acting part are different as disclosed in U.S. Pat. No. 4,330,787 and 4,459,600, that is, when the discharge openings are provided at a face opposite to the heat acting face, and when relative positional relation between the center of bubble generation, namely, the center of the heat acting part, and the discharge opening changes as a result of using the abovestated construction, sometimes, there occurs deviation in the discharge direction of the ink. Furthermore, in some cases, such recording head is not suitable for highspeed recording due to change of discharging characteristics. Especially when the number of the heating elements increases, the above-mentioned tendency becomes conspicuous and so hitherto, area or the number of the heating elements has been subject to those limitations.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a liquid jet recording head which is free from the above-mentioned problems and which makes it possible to make gradation recording with constantly stable performance.
The above object has been accomplished according to the present invention by a liquid jet recording head which has discharge ports for discharging a recording liquid, a liquid passage communication with the discharge ports and plural electricity-heat transducers provided with a heating resistive layer and a pair of electrodes electrically connected to said heat resistive layer, wherein the plural electro-thermal converting members, are laminated and the discharge openings are provided right above the heat acting face of the respective laminated electro-thermal converting members.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic plan view of one construction example of an electricity-heat transducer on a substrate according to the liquid jet recording head of the present invention.
FIG. 2 is a cross-sectional view along the line A--A in FIG. 1.
FIG. 3 is an oblique view of the liquid jet recording head of the present invention.
FIG. 4 is an oblique partial view of the recording head of FIG. 3 shown in perspective.
FIG. 5 is an oblique view of the recording head according to an another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, the preferred embodiments according to the present invention will be illustrated below.
FIGS. 1-3 show one embodiment of the present invention. Reference number 1 indicates a wafer obtained, for example, from a single crystal ingot of silicon Si, and on Si wafer 1 is formed a silica (SiO 2 ) layer 10, as a lower layer, of about 3 μm thick by thermal oxidation. On layer 10 is formed a first heating resistor layer 11 of hafnium boride HfB 2 having a thickness of about 0.2 μm, for example, by a sputtering method using a magnetron. On this layer 11 is further formed first electrode layer 12 of aluminum Al having a thickness of about 0.2 μm by vacuum deposition and thereafter, first electrodes 12A and 12B and first heater 11A having a heating area of about 100 μm×100 μm are formed in the form of a pattern by photolithography. The wafer may be made of glass, ceramics or plastics. In the present embodiment, a support is composed of a Si wafer and silica layer.
Then, thereover is deposited silica (SiO 2 ) at a thickness of about 0.2 μm, for example, by a bias sputtering method. In this embodiment, it is important that when the thus formed silica (SiO 2 ) insulating layer becomes too irregular at the edge portions of heaters formed thereafter in the form of a laminate, bubbling from the heating surface becomes unstable. Therefore, in this example, it is attempted to keep the insulating layer formed between upper and lower heaters as smooth as possible. Reference number 13 indicates a first insulating layer formed according to this idea.
After the first electrodes 12A and 12B and the first heater 11A have been thus covered with insulating layer 13, the similar procedures are repeated to provide, in the form of a pattern, second electrodes 22A and 22B of aluminum at a thickness of about 0.2 μm and a second heater 21 of HfB 2 having an area of about 75 μm×75 μm and a thickness of about 0.2 μm and then to cover these electrodes and heater with second insulating layer 23 of silica (SiO 2 ) having a thickness of about 0.2 μm.
Successively, there are formed third electrodes 32A and 32B of aluminum and third heater 31 of HfB 2 having a thickness of about 0.2 μm and an area of about 50 μm×50 μm and then formed thereon a first protective layer 33 of silica (SiO 2 ) having a thickness of about 0.6 μm by a bias sputtering method. Reference number 34 indicates a second protective layer, which is formed, for example, of tantalum Ta at a thickness of about 0.3 μm by a sputtering method using a magnetron. In FIG. 2, reference numbers 21 and 31 indicate second the heat resistive layer and third heat resistive layer, respectively, reference numbers 22 and 32 indicate the second electrode layer and third electrode layer, respectively, and reference number 34 indicates the second protective layer.
On the thus constructed substrate is provided orifice plate 3 having orifices 2 perforated therethrough and is further formed liquid chamber 4 and liquid supply system 5 is fitted to the substrate as shown in FIG. 3 to obtain a liquid jet recording head.
A pulse signal is applied selectively or simultaneously to first electrodes 12A and 12B, second electrodes 22A and 22B and third electrodes 32A and 32B of the recording head, thereby to obtain records with droplets of such diameters as shown in Table 1, respectively.
As is clear from Table 1, the discharge characteristics are closely proportioned to the effective area of the heater without bringing about great changes in discharge speed or frequency characteristics. It is a matter of course that such result is attributable to the fact that as shown in FIG. 4, orifice 2 is positioned just above the center line of the laminated heaters (C shows the center line) and thus the relative position between orifice 2 and respective heaters 11A, 21A and 31A is kept a constant value.
Further, the above fact also can be realized in the case that the distances between an orifice and each of heaters are kept to be constant.
TABLE 1______________________________________Electrode Diameter of liquid droplets______________________________________The first heater 100 μmThe second heater 56 μmThe third heater 25 μm______________________________________
The above explanation refers to the example of use of three heaters in the form of a laminate, but the number of heaters is not limited thereto and the number may be optionally increased or decreased.
Furthermore, the sizes of the heaters are also not limited to those of the above example and may optionally be chosen and moreover, one of them may be chosen or plural heaters may be simultaneously used in combination.
Further, although in the above embodiment, the rates of resistance per unit area of the laminated heat resistive layers are the same, that is the laminated heat resistive layers are made of the same material, or instead, different materials may be used for the respective the laminated resistive layers.
Further, although in the above explained embodiments, the discharge ports are arranged just above the heat acting surface of the laminated electro-thermal converting member, the present invention is not limited to only the above cases.
For example, the discharge ports may be arranged so that the discharge direction of the liquid for recording from the discharge ports is the same as the liquid supply direction to the heat acting surface.
FIG. 5 shows such an ink jet recording head, show there is. FIG. 5 is an oblique view, embodiment.
In FIG. 5, liquid path wall forming layer 42 is formed on an electro-thermal converting member bearing substrate 41 by photo-sensitive material, etc., and a top plate is adhered thereon. The liquid for recording is supplied from an opening 44, a liquid chamber 45 and a liquid flow path 46 to be discharged from a discharge port 2. A good graduated recording can be also realized by the use of an ink jet head shown in FIG. 5.
According to the liquid jet recording head of the present invention, since plural electricity-heat transducers are provided in the form of a laminate on a substrate, the relative position between discharge orifices and respective electricity-heat transducers can be kept constant in both the distance and the direction, since physical conditions at discharging of liquid droplets do not change even if heating area or quantity of heat is changed due to selection or combination of these electricity-heat transducers, a record having gradation can be made while maintaining a stable discharging performance, and furthermore, the plural electricity-heat transducers can be readily contained in one nozzle without their occupying of a large space. As a result, it also becomes possible to make a liquid path in a multi orifice type of high density.
As described hereabove, according to the present invention, by laminating plural electricity-heat transducers together with intervening insulating layers on a substrate of a liquid path, the relative position between nozzle orifices and the electricity-heat transducers is kept constant, and thus it becomes possible to maintain discharge performance at stable state and to accomplish superior gradation recording.
The material of the first and second insulating layer may include, in addition to the materials described above, thin-film materials such as transition metal oxides, such as, titanium oxide, vanadium oxide, niobium oxide, molybdenum oxide, tantalum oxide, tungsten oxide, chromium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, yttrium oxide, manganese oxide and the like; other metal oxides, such as aluminum oxide, calcium oxide, strontium oxide, barium oxide, silicon oxide and the like; and complexes of the above metals; high dielectric nitrides, such as silicon nitride, aluminum nitride, boron nitride, tantalum nitride and the like; complex of the above oxides and nitrides; semiconductive materials such as amorphous silicon, amorphous selenium and the like, which are of low resistance in a bulk state but are rendered highly resistive in a manufacturing process such as the sputtering process, CVD process, vapor deposition process, vapor phase reaction process or liquid coating process. The film thickness is usually 0.1-5 μm, preferably 0.2-3 μm and more preferably 0.5-3 μm. Further organic materials for the above purpose include resins, for example, silicon resin, fluorine-contained resin, aromatic polyamide, addition polymeric polyimide, polybenzimidazole, polymer of metal chelate, titanate ester, epoxy resin, phthalic resin, thermosetting phenolic resin, p-vinyl phenol resin, Zirox resin, triadine resin, BT resin (addition polymerized resin of triazine resin and bismaleimide) and the like. Alternatively, the protection layer may be formed by vapor-depositing polyxylene resin or a derivative thereof.
Alternatively, the second upper protection layer 209 may be formed by plasma polymerizing method from various organic compound monomers such as, thiourea, thioacetamide, vinylferrocene, 1,3,5-trichlorobenzene, chlorobenzene, styrene, ferrocene pyrroline, naphthalene, pentamethylbenzene, nitrotoluene, acrylonitrile, diphenylselenide, p-toluidine, p-xylene, N,N-dimethyl-p-toluidine, toluene, aniline, diphenylmercury, hexamethylbenzene, malonitrile, tetracyanoethylene, thiophene, benzeneselenol, tetrafluoroethylene, ethylene, N-nitrosodiphenylamine, acetylene, 1,2,4-trichlorobenzene, propane and the like.
In manufacturing a high density multi-orifice type recording head, the protection layer may be preferably formed by an organic material which is readily processed by fine photolithography. More preferably examples of such material include, for example, polyimidoisoindoloquinazoline dione (trade name: PIQ available from Hitachi Kasei, Japan), polyimide resin (trade name: PYRALIN available from DuPont); cyclic polybutadiene (trade name: JSR-CBR available from Japan Synthetic Rubber, Japan); photosensitive polyimido resins such as Photoneece (available from Toray, Japan), photoreactive polyamic acid for lithography (trade name: PAL available from Hitachi Kasei, Japan) and the like. ##STR1##
The material of the protection layer further may include an element of the group IIIa of the periodic table such as Sc or Y, an element of the group IVa such as Ti, Tr or Hf, an element of the group Va such as V or Nb, an element of the group VIa such as Cr, Mo or W, an element of the group VIII such as Fe, Co or Ni, an alloy of the above metals such as Ti-Ni, Ta-W, Ta-Mo-Ni, Ni-Cr, Fe-Cr, Ti-W, Fe-Ti, Fe-Ni, Fe-Cr, Fe-Ni-Cr, a boride of the above metals such as Ti-B, Ta-B, Hf-B or W-B, a carbide of the above metals such as Ti-C, Zr-C, V-C, Ta-C, Mo-C or NiC, and a silicide of the above metals such as Mo-Si, W-Si or Ta-Si, and a nitride of the above metals such as Ti-N, Nb-N or Ta-N. The layer may be formed by vapor deposition process, sputtering process, CVD process or other process and the film thickness thereof is usually 0.01-5 μm, preferably 0.1-5 μm and more preferably 0.2-3 μm. The material and the film thickness are preferably selected such that a specific resistivity of the layer is larger than specific resistivities of the ink, the heat generating resistive layer and electrode layer. For example, it has a specific resistivity of 1Ω-cm or less. An insulative material such as Si-C having a high anti-mechanical shock property is preferably used.
The underlying layer principally functions as a layer to control conduction of the heat generated by the heat generating portion to the support. The material and the film thickness of the underlying layer are selected such that the heat generated by the heat generating portion is more conducted to the heat applying portion when the thermal energy is to be applied to the liquid in the heat applying portion, and the heat remaining in the heat generating portion is more rapidly conducted to the support when the heat conduction to the heating portion 202 is blocked. The material of the underlying layer 206 includes, in addition to SiO 2 described above, inorganic materials as represented by metal oxides such as zirconium oxide, tantalum oxide, magnesium oxide and aluminum oxide.
The material of the heat generating resistive layer may be any material which generates heat when energized.
Preferably examples of such materials are tantalum nitride, nickel-chromium alloy, silver-palladium alloy, silicon semiconductor, or metals, such as hafnium, lanthanum, zirconium, titanium, tantalum, tungsten, molybdenum, niobium, chromium, vanadium, etc., and alloys and borides thereof.
Of the materials of the heat generating resistive layer, the metal borides are particularly suitable, and of those, preference may be placed on hafnium boride for its most excellent property, and there follow zirconium boride, lanthanum boride, tantalum boride, vanadium boride and niobium boride in the order as mentioned.
The heat generating resistive layer can be formed of those materials by an electron beam vapor deposition process or a sputtering process.
The film thickness of the heat generating resistive layer is determined in accordance with an area and material thereof and a shape and a size of the heat applying portion and power consumption so that a desired amount of heat per hour may be generated. Usually, it is 0.001-5 μm and preferably 0.01-1 μm.
The material of the electrode may be any conventional electrode material such as Al, Ag, Au, Pt or Cu. It is formed by those materials into desired size, shape and thickness at a desired position by a vapor deposition process. | A liquid jet head having: a discharge port for discharing liquid; a liquid path communicating with the discharge port; and a plurality of electro-thermal converting elements for generating thermal energy used for discharging the liquid, wherein each of said electro-thermal converting elements has heat resistive layer and at least one pair of electrodes electrically connected to the heat resistive layer, and the heat resistive layers are laminated together with intermediate layers of insulator to form a laminate in a direction perpendicular to a direction at which the liquid is supplied to a heat acting surface of the electro-thermal converting elements. | 1 |
FIELD OF THE INVENTION
[0001] Dampening devices for vibrating drumheads and percussion instruments, more specifically a dampening device comprising an elastomeric body which incorporates a base substrate.
BACKGROUND OF THE INVENTION
[0002] Vibrating surfaces are used to generate, at least when struck by a skilled musician, pleasing musical tones. Percussion instruments, including drums, vibrate at fundamental wavelengths defined in part by the diameter of the instrument. Drums and percussion instruments can also vibrate in such a way as to produce unwanted and undesirable overtones, sometimes referred to as ring or over-ring. There have been a number of devices in the prior art that have been designed to dampen the vibration of a percussion instrument, for example a drumhead, to help eliminate unwanted, overtones and over-ring.
[0003] Most of the prior art devices feature contacting the drumhead with substance, the substance capable of absorbing some of the higher overtones. For example, U.S. Pat. No. 5,637,819 discloses a gel patch wherein the gel is two-phase colloidal system consisting of a solid and liquid phase, containing in an exemplary embodiment, 3% soybean oil.
[0004] U.S. Pat. No. 4,154,137 discloses a mute element that includes a support arm structure for supporting the mute element from the sidewall of the drum, against the drumhead.
[0005] The gel patch and the base supported dampener achieve similar results, albeit the gel patch does not require the external support arm.
[0006] Prior art “patch type” dampening materials, when applied to the vibrating dome head, have had some shortcomings. Among these shortcomings are the seepage of oil, sometimes with an unsightly stain, onto the surface of the drumhead by the material comprised in the gel patch. Another shortcoming includes the inability to effectively “stick” to the drumhead. Yet another shortcoming disclosed in some of the prior art patch dampening devices is their relative ineffectiveness at dampening certain overtones. Last, some patch materials may ‘dry out’ over a period of time, thus lessening their dampening ability.
[0007] With a view towards minimizing or eliminating some of these shortcomings, applicant provides a drum, drumhead, and percussion instrument dampening material that comprises a patch including an elastomeric body, typically silicon free polyurethane, and a flexible substrate or base, typically open cell foam. The resulting patch has been found to effectively adhere to a vibrating drumhead surface without leaving unsightly stains and to provide a long life with effective dampening of drum overtones. Furthermore, applicants dampening material has been shown to adhere to both top (batter) and bottom (resonant) drumheads with equal effectiveness. Applicants material may also be moved or relocated on the surface of drumheads and other percussion instruments numerous times without leaving any residues behind.
[0008] Applicants herein also provide for a novel method of making a novel patch, wherein a two part mix is combined, typically at a one-to-one ratio, as liquid, while it is being applied to a flat surface. The liquid may be self leveling and upon leveling the substrate or base is applied to the mix, typically so the mix saturates the substrate and then the mix is allowed to cure.
BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENT
[0009] FIG. 1 is a top elevational view of a base or substrate for use with applicants novel dampening material.
[0010] FIG. 2 is a side elevational view, cutaway in cross section, illustrating a “sandwich” variety of applicants novel dampening material.
[0011] FIG. 3 illustrates an embodiment of applicants novel dampening material, in side elevational view, showing that the embodiment may include a tabular substrate, at least partially saturated with a curable liquid polyurethane mix, which may extend substantially beyond one surface of the substrate and, on an opposite surface either does not extend at all beyond the substrate or extends only in a thin layer beyond the substrate.
[0012] FIG. 4 illustrates yet another embodiment of applicants novel invention including a substrate, for example open cell foam, that is at least partially saturated with a curable liquid polyurethane mix and in which there is little or no extension of the polyurethane mix beyond the borders of the at least partially saturated foam substrate.
[0013] FIG. 5 illustrates a side elevational view of applicants novel dampening material supplied as an elongated tape, from which sections may be cut, to be applied to a vibrating surface.
[0014] FIGS. 6A, 6B and 6 C illustrate in top elevational views, just three of the forms in which applicants novel dampening device may be provided, for attachment to a vibrating surface.
[0015] FIGS. 7A-7H provide illustrations for a process for manufacturing applicants novel dampening material.
[0016] FIG. 8 is a perspective view illustrating the application of applicants novel dampening material to a drumhead for effectively dampening the same.
[0017] FIG. 9 illustrates, in side elevational view, a manner of “stacking” two of applicants novel patches to perform effective dampening for a vibrating drumhead.
[0018] FIG. 10 is a side elevational view, cutaway of an alternate embodiment showing the use of a woven base as a substrate for applicants novel dampening material.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0019] FIG. 1 illustrates a base or substrate 12 , for example, a dry open cell foam substrate before applicants mix is added.
[0020] FIGS. 2, 3 and 4 are side views cutaway of applicants novel dampening material ( 10 ). In FIG. 2 it is seen that one embodiment includes a dampening material 10 with a cured polyurethane mix ( 14 ) forming a bottom surface and top surface to at least partially polyurethane mix saturated foam substrate or core ( 12 ). In this embodiment of a dampening material it is seen that core ( 12 ) is approximately centrally located between top and bottom surface portions comprising a cured polyurethane mix.
[0021] Turning now to FIG. 3 it is seen that the at least partially saturated foam core has a thin or no layer on one side and a thicker layer of cured polyurethane mix extending beyond the other side of the at least partially saturated foam core or substrate ( 12 ).
[0022] FIG. 4 illustrates a third embodiment of applicants novel dampening material ( 10 ) which includes an at least partially saturated core ( 12 ) with little or no additional cured mix extending beyond the saturated core.
[0023] Thus it is seen that applicants novel dampening material ( 10 ) may come in different forms. First, it may include an at least partially saturated core which may stand alone or which may have, on one side or the other (or both sides) a layer of cured polyurethane mix which is typically integral with the foam of the foam core. However, the substrate or foam core may be closer to the top or the bottom of the patch of dampening material and the core need not be centered as illustrated in FIG. 2 . Applicants have found that when the core is closer to one side of the dampening material then the other (for example FIG. 3 ) there is a tackiness differential between the two surfaces, with a more tacky surface on one side, which side would face the vibrating drumhead, for adhering the patch or dampening material to the drumhead.
[0024] FIG. 5 illustrates a roll of tape ( 16 ) which includes releasable protective sheets 16 A and 16 B on the top and bottom surfaces of an elongated, rolled section of applicants novel dampening material ( 10 ), to protect the sticky surfaces. These are typically peeled off before use of the patch.
[0025] FIGS. 6A, 6B and 6 C illustrate a circular ( 60 ), rectangular ( 62 ) and complex ( 64 ) shape in which applicants novel dampening material ( 10 ) may take. Typically a rectangular shape has proven effective but for some purposes different shapes or sizes may be used to effect different damping characteristics.
[0026] FIGS. 7A through 7H illustrate a preferred method of making applicants novel material ( 10 ). The steps illustrated may be broken down generally into three categories. First, preparing a table ( 24 ). Second, pouring or applying a polyurethane mix ( 52 ), typically in a one-to-one ratio and typically self leveling, onto the table. Third, combining the core substrate, typically foam and the mix. The mix is then allowed to cure and the dampening material ( 10 ) is removed from the table.
[0027] FIGS. 7A and 7B illustrate a method of preparing a flat top, typically glass table ( 24 ). A flat top table ( 24 ) is provided typically including a flat, transparent glass member. A release sheet ( 36 ), such as a sheet of FEP, is laid across the table after the table is sprayed with a cleaner ( 38 ) or water. Bubbles are usually squeegeed out from between the release sheet and the table using a squeegee ( 40 ). Applicants have found that, instead of a release sheet, a 1.5 mil polyurethane sheet may be provided. This will become a “skin” to the less sticky side of the patch. That is, where the method set forth, above and below discloses lift off of the patch from the release sheet, in a preferred embodiment a 1.5 mil sheet is laid on the table and the mix has some adherence and bonding to the sheet. When the process is completed, the cured mix is lifted off with the polyurethane sheet, which becomes a “skin” to one side of the patch (typically the non-sticky side). This allows easy handling by the musician drummer—one can handle the patch by the protected “skinned” side and keep their fingers off the sticky side.
[0028] FIG. 7C illustrates a sheet of dry, open cell foam substrate ( 12 ) laying on top of the table ( 24 ) and more specifically shows a step of applying a polyurethane border ( 70 ) around the sheet of the foam, but typically not touching the foam edges. This border is used to define the area in which the mix will be laid which is illustrated in 7 D. Turning back to FIG. 7C , after the border is applied, the sheet of foam is removed and now the step of layering the mix to the table, as illustrated in FIG. 7D is commenced. In this step, a gun or applicator ( 28 ) is filled with mix ( 52 ). The mix is typically a liquid polyurethane that cures to form a resilient substantially oil free, elastomeric body. One such two part mix is available from KBS Chemical from Fort Worth, Tex. as part numbers P-1011 (polyol) and U-1010 (urethane).
[0029] Applicator ( 28 ) typically has a nozzle that will allow the polyol and urethane to combine into a one-to-one ratio and mix as its being applied. A crisscross action has been found to be an effective method of application of the mix on the table enclosed by the border ( 70 ). The mix is typically self leveling and the crisscross pattern will cause it to flow together, somewhat. However, manual application, such as illustrated in FIG. 7E may assist the mix ( 52 ) to level and to “debubble”. The worker may manipulate the mix into the dry areas as illustrated in FIG. 7E .
[0030] FIG. 7F illustrates the placement step wherein the foam substrate ( 54 ) is placed on the level mix ( 52 ). The mix is worked into the substrate. Alternatively, the substrate may be laid onto the table dry and mix applied to the substrate.
[0031] FIG. 7G illustrates a step of soaking wherein the dry, open cell foam substrate ( 54 ) becomes at least partially saturated, and typically saturated, with a polyurethane mix. Manual pressing on the surface of the foam as well as squeegeeing (illustrated) will assist in urging the polyurethane mix into the substrate ( 54 ) and will help work out bubbles in the mix and substrate. After the desired degree of saturation is reached, the polyurethane mix is allowed to cure. After curing, typically at room temperature for approximately two to four hours, the dampening material ( 10 ) is lifted from the table as illustrate in 7 H.
[0032] If one desires that the at least partially saturated foam substrate core ( 56 ) should have a top and layer of polyurethane mix ( 52 ) as illustrated in FIG. 2 (“sandwich”), then a greater volume of polyurethane mix, above and below the core is required. One can control the existence of or thickness of a polyurethane mix layer outside the core by increasing the volume of polyurethane mix applied. If only a saturated core is desired with substantially more polyurethane mix extending beyond the boundaries of the core, then the core can be squeegeed clean of any excess mix before curing.
[0033] For example, the following procedure may be used for one desiring to make a saturated foam core with substantially little or no layer of cured polyurethane mix on either side. A 12 inch by 36 inch 0.070 inch thick foam sheet above is placed on the table. About 150 cc of polyurethane mix is placed in the applicator ( 28 ). The steps described above are undertaken and about 30 cc of uncured mix is squeegeed off the top of saturated foam core, with the edge of the squeegee resting gently up against the top surface of the saturated foam core when the squeegee is drawn across the face of the foam core. The estimate of 30 cc's may be made by simply eyeing the excess material or placing it on a piece of FEP film and weighing it.
[0034] For the preparation of a “one-sided” dampening patch, one would simply squeegee off less of the excess squeegeed off to make a substantially “borderless” foam core. For example, if about 20 cc's is removed from the original 150 cc's applied, this would result in about a 0.005 inch layer of cured mix beyond the substrate. The thickness may be estimated and a shinier finish results when a thin layer of mix is provided. Use of this procedure with a 0.070 inch thick foam results in a total thickness of about 75 mil plus or minus 10%.
[0035] When the sandwich variety of dampening material (mix extending as layers on both sides of the core) is desired one would proceed as above but allow the top layer to cure. After the top layer is cured the piece is flipped over and about 30 to 40 cc's of mix is applied to the reverse side of foam, allowed to level and squeegeed to provide a total thickness of, typically about 0.090 inch.
[0036] FIG. 8 illustrates a drum Dr having the drumhead Dh, the drum being typical of known percussion instruments. Applicants apply their adhesive material or patch ( 10 ) to an area of the drumhead, typically on the underside surface, for effectively dampening overtones.
[0037] FIG. 9 illustrates the stacking of two of applicants novel adhesive patches, one to the other, for variety in dampening characteristics.
[0038] FIG. 10 illustrates a variation of applicants novel dampening material that includes a woven core, which woven core may be either metallic or non metallic. For example, a metallic woven core may be a woven aluminum mesh, for example between 0.11 and 0.25 inch thick. The non metallic mesh may be woven fiberglass for example typically between 7 and 20 mil.
[0039] A typical size of applicants typical rectangular patch is between 1 inch wide and 3 inches long (60-70 mil thick±5 mil) and a typical area is between 1 sq. inch and 12 sq. inches. The dampening material typically has a resilient, elastomeric body and has a sticky or tacky surface typically in the range of 1 to 7 inch pounds. The tackiness may be selective as set forth above, with one side of the patch being tackier then the other. It has been found that applicants material, with a minimum of about 1 inch pound, preferably about 2 inch pounds and up to 7 inch pounds, can easily stick to the underside of a drumhead. Most prior art patches are not sticky enough to stay on the underside of the drumhead. Applicant has provided a novel patch that can stick to the underside of a drumhead.
[0040] In the manufacture of applicants novel dampening materials a large flat stock may be made (see FIG. 7H ), which flat stock may be cut into strips and rolled up and may be die stamped into a variety of shapes (see FIGS. 6 A-C). One such open cell foam substrate ( 12 ) is available from Reilly Foam Corporation, Conshohocken, Pa. as “100100 PPI Z”. The foams open cells allow the dampening material to at least partially absorb a poured polyurethane mix which will then cure at room temperature to be integral. The preferred mix contains little or no silicone or other oils. The preferred mix, after 24 hours attached to a drumhead leaves only a slight mark, compared to unsightly oil spots left by other oil bearing prior art patches.
[0041] An alternate preferred embodiment of applicants present invention comprises only a resilient pliable body of polyurethane mix, which is substantially oil free. This mix is available, as above, from KBS Chemical in Forth Worth. It makes an effective dampening material, with adhesive properties that allow it to stick to the surface of a vibrating drum, for a period of time without leaving an oil residue.
[0042] Applicant, in an alternate preferred embodiment, has found a thin patch, about 30 mil (+5 mil) has allowed a musician to “fine tune” a percussion instrument. Prior art patches do not illustrate such a thin dimension.
[0043] Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limited sense. Various modifications of the disclosed embodiments, as well as alternative embodiments of the inventions will become apparent to persons skilled in the art upon the reference to the description of the invention. It is, therefore, contemplated that the appended claims will cover such modifications that fall within the scope of the invention. | A device for dampening a vibratable surface, such as a drumhead. By dampening the vibrations of a vibratable surface, such as a drumhead, the tone may be altered, as by removing some of the higher pitched overtones of the vibratable surface. The patch comprises a resilient, pliable adhesive body that has an intrical, flexible. And a preferred embodiment, the body is substantially oil free polyurethane mix and the flexible base is foam. A method of manufacturing the patch is provided. The method includes a step of combining, on a flat top surface such as a table, a curable liquid mix and an open cell foam, and allowing the mix to cure. | 1 |
PRIOR APPLICATIONS
This application claims priority to U.S. Provisional Application No. 61/596,187, filed Feb. 7, 2012, and U.S. Provisional Application No. 61/596,571, filed Feb. 8, 2012, and U.S. Provisional Application No. 61/597,749, filed Feb. 11, 2012, which are incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
The present invention is directed to compression latches of the type used to latch gasket-lined doors or gasket-lined door jambs. Compression latches have been designed to secure gasketed doors, trunk lids, panels, covers, and other structures. Such compression latches require a pawl and a clamp or other member to compress a generally elastomeric gasket or O-ring when securing the door, trunk lid, panel, cover or other structure.
The take-up, i.e., the compression distance moved by the pawl, clamp, or other member, to pull a door against a door jamb establishes the degree of compression of the gasket and the sealing force thereof. The linear travel of a pull member, once a door makes contact with a cabinet, establishes the sealing force of the gasket. Gasketed enclosures are often found in industry. These can include computer and communications cabinets, electrical transformer enclosures, sterilizing and autoclave enclosures, incubation and artificial environment enclosures, cooling chambers and freezers, humidity and controlled environment chambers, and various types of ovens, among others.
Compression latches are generally manually operated. As such, they can be operated by a handle or a lever. Levers are found on latches where the compression forces required against a gasket are greater, or the length of travel of the pull is longer. However, compression latches are specifically adjusted or specifically designed or selected for the particular application and the particular environment in which they are used. Such particular application and particular environment can also dictate other operating features for a latch, such as the requirements for handle and door locking and position holding, as well as the proximity distance of the lock on a door to a door jamb when the pull of the latch begins to operate.
SUMMARY OF THE INVENTION
The present invention is designed to latch the door to an oven. Such an oven may be designed for many different purposes, such as a climate chamber, a drying oven, an annealing or tempering oven, or a food processing oven, among others. Each of these ovens has a gasket or seal which is compressed when the oven door is fully closed. Thus a compression latch operation is well suited for these structures.
The compression latch of the present invention is lever operated. This enables that a first latch unit can be mounted near the top of the oven door and a second latch unit can be mounted near the bottom of the door. A bar-type handle is attached to and vertically extends between the two latch levers. The vertical bar handle operates both levers and therefore both latches in unison. The latches engage respective striker-keepers mounted on the body of the oven.
It is important that the vertical bar have a specific fully closed position, a specific fully open position, and a discernable intermediate position where a technician knows the latch is still fully closed but about to start to open. This would assist in minimizing accidental openings allowing the escape of hot air and gases towards the technician.
When closing the door it is desirable that the latch pawl comes into contact with its striker/keeper at a specific distance before the door is fully closed. In this way, the further movement of the vertical bar and thereby the further movement of the respectively connected latch levers, contributes to the compressing forces each latch exerts on the door gasket. For example, the latch pawl can engage the striker/keeper when the door is 10-20 mm from being fully seated against the gasket. This would require a linear movement of a pawl/pull member slightly more than that distance in order to compress the gasket.
It is also desirable that the latch housing size be minimized so that the latch can be used with small ovens and/or relatively thin oven doors. An envelope size for the latch housing can be in the range of 40-70 cubic centimeters. An example might be about 33 millimeters long by about 85 millimeters wide by about 20 millimeters high.
It is further desirable that the handle lever of each latch, itself, has a stable locked state when the latch is in the fully open position, and that this locked state be released only when the door is pushed to the closed position with a manual force by a technician, wherein the locked state of the latch is released for the latch to move into a closing mode to engage the keeper/striker to lock and seal the door.
These are objectives that are realized in the latch design of the present invention that provides a compression operation from a small package which promotes user friendly smooth operation. The latch housing has a snap-in feature which minimizes the tooling and components needed for installation. The operation of the latch is effected by the movement of a lever handle from left to right and vice versa with an over center position indicator providing an indication when the latch is locked. A blocking feature inhibits the latch from being locked when the door is open. The design is such that a positive movement by a technician is needed to close the latch and to open it.
The latch includes a series of links which fold into one another resulting in a very small package when the latch is closed. In a closed position the footprint of the latch is essentially rectangular except for a housing mounting leg at one side and a snap-in clamp at the other side.
When manually operated, the handle lever rotates in a semi-circle, from a closed secure position, to a closed but about to engage to an open position (at the top of the arc), to beyond the top to an operational area of the semi-circle where the latch opens.
The latch utilizes a rectangular keeper/striker cup, mounted to the door jamb, having a pull engaging lip and a striker plate. An elongate lever, operated by the vertical handle, is mounted to a first pivot point for rotation. That pivot point holds a torsion spring which biases the lever to a closed position.
The lever is pinned to an elongate first link at one end of the link. The first link has a pivot point at about its mid-length for its rotation thereon. The other end of the link is pinned to a second link and pinned to a first end of an elongate pawl
The lever operated compression latch has an elongate, hook-ended pawl with a pawl body having a longitudinal slot. The pawl is cam guided, and pin rotated and translated, to engage with and withdraw from a keeper cup. A fixed position cam post rides within the pawl slot and controls the pawl lateral translation. This cam also defines a pivot point about which the pawl rotates. The compound movement of the pawl includes a lateral translation towards the keeper cup while rotating there into, followed by a lateral withdrawal to exert a compression force between the latch body which is attached to a door and the keeper cup which is attached to a door frame thereby compressing the gasket.
A series of interconnected links is operated by the lever handle to fold into one another to provide a compact envelope when the latch is closed. These links expand outwardly to open the latch and disengage the pawl from the keeper when operated by the lever movement to the open state. Of this series of links, a pair of release links operates in contact with one another, and rotates on respective individual pivot points to extend outwardly from the latch envelope to engage a striker plate portion of the keeper cup. This striker engagement causes the release links to push the latch and the door from a sealing engagement of the keeper and door jamb for a short distance, prior to the latch and the door thereafter being separated and fully opened. This short distance of movement prior to the open state is a safety measure.
The striker engagement of the release links also causes the latch links to fold inwardly, which rotates and translates the pawl into keeper engagement and compression. This operation is facilitated with a floating spring having one end operating as a pivot member. A detent engages one of the links to provide a physical indication to the handle lever between the hard closed position and the closed about to open position.
From the fully closed position, when the handle, i.e., lever rotates, the pawl becomes free to translate out of the latch towards the keeper cup and the release links push the latch away from the keeper cup. This releases the compression state. Then after a slight lag and a further rotation of the lever, the pawl rotates. The pawl rotation is about 75 degrees from the keeper engagement position to a position fully rotated from the keeper and into the latch housing. When the latch is fully open, the handle lever is positively held in the open position. When the latch is fully open, the release levers are in the fully outwardly extending position. The handle lever, itself, is only released from the fully open position when the release levers strike the striker plate of the keeper cup. This causes the first and second links to rotate which releases the handle for movement.
The first link has a finger on its handle lever engaging end which engages an indentation in the handle lever to hold it fixed in the open position. The release linkage rotation causes the first link to rotate out of the fixed holding engagement with the handle lever.
The operation of the latch pawl is such that when the pawl force is released from exerting force against a gasket, the pawl finger hook continues to overlap the pull engaging lip of the striker cup. The handle when the pawl is in this position is held in a detent movement inhibited position which must be overcome by an additional force. This additional force overcomes the detent and moves the drive links, i.e., the first and second links connected to the pawl. The further movement of these drive links rotates the pawl to clear the finger hook from the striker cup and then rotates the pawl to withdraw it into the latch body. When the pawl is in the fully retracted position the release links are in their fully extended position. With the release links in the fully extended position the drive links cannot move the pawl.
BRIEF DESCRIPTION OF THE DRAWINGS
The features, advantages and operation of the present invention will become readily apparent and further understood from a reading of the following detailed description with the accompanying drawings, in which like numerals refer to like elements, and in which:
FIG. 1 is a perspective view of the latch on an oven;
FIG. 2 is a perspective view of the door of the oven slightly open with the latch in an intermediate position;
FIG. 3 is a perspective view of the oven door fully open, and there being the use of two latches, i.e., an upper and lower one, with the lower latch in dashed lines and a handle bar connecting the upper and lower latches also shown in dashed lines;
FIG. 4 is a top view of the oven of FIG. 1 with the latch fully opened and the door freely opened;
FIG. 5 is a right-hand operation latch top view with the keeper/striker in dashed lines and the latch in the fully open position;
FIG. 6 is a top view of the latch of FIG. 5 in the intermediate or partial release position;
FIG. 7 is a top view of the latch of FIG. 5 in the fully open position with the release linkage extended and the hook-ended pawl rotated into the latch housing, and showing a top view of the keeper/striker;
FIG. 7 a is a perspective view of the latch;
FIG. 8 is a perspective view of a keeper/striker cup used with the latch with the back of the cup exploded away;
FIG. 9 is a plan/top view of the latch in the extreme closed position, the top housing member being removed;
FIG. 10 is a plan/top view of the latch in the engaged position, the top housing member being removed;
FIG. 11 is a plan/top view of the latch in the detent position, the top housing member being removed;
FIG. 12 is a plan/top view of the latch in the extreme open position, the top housing member 119 being removed;
FIG. 13 is a perspective exposed view of the latch components;
FIG. 14 is a plan/top view of the latch with the top of the housing removed and the latch in the closed position engaging the keeper/striker;
FIG. 15 is a front view of the latch of FIG. 14 in the closed position showing sectional cuts A, B, and C;
FIG. 16 is a plan/top view of the closed latch of FIG. 15 at section A-A;
FIG. 17 is a plan/top view of the closed latch FIG. 15 at section B-B;
FIG. 18 is a plan/top view of the closed latch FIG. 15 at section C-C;
FIG. 19 is a plan/top view of the latch with the top of the housing removed and the latch in the engaged position with the hooked finger of the pawl within the cup portion of the keeper/striker;
FIG. 20 is a front view of the latch of FIG. 19 in the engaged position showing sectional cuts D, E and F;
FIG. 21 is a plan/top view of the engaged latch of FIG. 20 at section D-D;
FIG. 22 is a plan/top view of the engaged latch of FIG. 20 at section E-E;
FIG. 23 is a plan/top view of the engaged latch of FIG. 20 at section F-F;
FIG. 24 is a plan/top view of the latch with the top of the housing removed and the latch in the detent position;
FIG. 25 is a front view of the latch of FIG. 24 in the detent position showing sectional cuts G, H and J;
FIG. 26 is a plan/top view of the detented latch of FIG. 25 at section G-G;
FIG. 27 is a plan/top view of the detented latch of FIG. 25 at section H-H;
FIG. 28 is a plan/top view of the detented latch of FIG. 25 at section J-J;
FIG. 29 is a plan/top view of the latch in the extreme open position;
FIG. 30 is a front view of the latch of FIG. 29 in the open position showing section cuts K, L and M;
FIG. 31 is a plan/top view of the open latch of FIG. 30 at section K-K;
FIG. 32 is a plan/top view of the open latch of FIG. 30 at section L-L;
FIG. 33 is a plan/top view of the open latch of FIG. 30 at section M-M;
FIG. 34 is a plan view of the latch with the tip of the housing removed and where the detent ball is in the depressed position where the pawl continues to be extended into the keeper and the release links are beginning to extend;
FIG. 35 is a front view of the latch of FIG. 34 in the detent ball depressed position showing section cuts N, P and R;
FIG. 36 is a plan/top view of the latch of FIG. 34 at section N-N;
FIG. 37 is a plan/top view of the latch of FIG. 34 at section P-P;
FIG. 38 is a plan/top view of the latch of FIG. 34 at section R-R;
FIG. 39 is a plan/top view of the closed latch of FIG. 14 in the sectional view B-B of FIG. 17 , but with the keeper/striker and its back plate mounted to a door jamb with mounting screws and nuts, and the gasket compressed, where the latch is positioned within the door; and
FIG. 40 is a plan/top view of the latch in the engaged detent position of FIG. 27 showing section H-H.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a latch 100 mounted on a door structure 501 of an enclosure such as an oven 500 , FIGS. 1-4 , which latch 100 has an extreme fully closed position, a detent position indicating a closed latch about to be opened, a further detent position indicating a partially opened latch, and an extreme fully open position. The latch is operated by a lever/handle. When in the extreme open position the lever/handle is held in a fixed abutment position so that it cannot be rotated towards the closed position. A release structure frees the handle when it moves against a striker plate mounted on a door jamb structure.
FIGS. 1, 2, 3, and 4 show the latch 100 mounted on an oven door 501 and the latch and door in the closed, partially released opened, opened with two latches and opened with a single latch, respectively.
FIGS. 5, 6 and 7 show the closed, engaged, and open positions of the latch 100 , respectively. The latch 100 is designed such that the operator will not cause it to strike against the door jamb mounted keeper/striker 201 while in the closed position, FIG. 5 , nor will the operator cause the latch to strike against the door jamb mounted striker 201 while in the in the engaged position, FIG. 6 .
FIG. 7 a shows a perspective view of the latch, while FIG. 8 shows an exploded perspective view of the keeper/striker 201 , 202 for the latch 100 . The latch housing 101 , 119 is a relatively quick installation. On one side there is an ear 401 with a vertical opening or channel 403 for a pin or screw 404 . On the other side there is a spring clamp 402
With the top housing member 119 removed, the latch is shown in detail in plan top views in FIGS. 9, 10, 11, and 12 . In FIG. 9 , the latch 100 is in the closed position. In FIG. 10 , it is in the engaged position where the pawl 111 has traveled into the keeper/striker 201 cup so that the door is somewhat opened as shown in FIG. 2 , but the pawl still engages the keeper to prohibit the complete opening of the door. In FIG. 11 , the latch is in the detent position where the lever/handle 112 will not move freely indicating the door should not be closed in the latch in that position. In FIG. 12 the latch is in the open position where the release links can engage the keeper striker plate 201 to close the latch.
FIG. 13 is a perspective exploded view of the latch showing its components. Shown is a top housing member 119 and a bottom housing member 101 and two interacting linkages, which for the purposes of describing the function of the latch 100 will be known as the main (drive) linkage, and the release linkage.
The main/drive linkage has a pawl operation housing pivot pin 105 a , a lever handle operation housing pivot pin 105 b , an upper main/drive link 108 , a pawl pivot pin 109 , a handle pivot pin 110 , a pawl 111 with a hooked end 230 , a lever handle 112 , a lower main/drive link 114 , a main/drive linkage biasing spring 117 , and a lever handle biasing spring 118 . The housing pawl operation pivot pin 105 a and housing lever/handle operation pivot pin 105 b are rotational fits in the bottom housing member 101 and the top housing member 119 , and provide motion constraints for the pawl 111 and lever/handle 112 . Link 108 and link 114 pivot about their mid-points each being rotationally constrained between the bottom housing member 101 and top housing member 119 . The pawl pivot pin 109 and lever/handle pivot pin 110 are rotationally constrained at opposite ends between the link 108 and the link 114 . The pawl 111 is rotationally constrained to the pawl pivot pin 109 and has a sliding/rotational fit to the pawl operation housing pivot pin 105 a . The lever/handle 112 is rotationally constrained to the lever/handle housing pivot pin 105 b and has a sliding/rotational fit to the handle pivot pin 110 .
This arrangement enables a controlled linear and rotational transformation of the pawl 111 in relation to bottom housing member 101 , through an angular movement of the lever/handle 112 about the lever/handle operation housing pivot pin 105 b . The main/drive linkage spring 117 provides a bias to the main linkage 108 , 112 , driving it to either extreme of its available motion, while the lever/handle biasing spring 118 provides a bias to the lever/handle 112 , driving a rotation about lever/handle housing pivot pin 105 b.
The arrangement of the linkage and geometry of the components ensures that at one extreme the main/drive linkage can only be driven via the lever/handle 112 , henceforth known as being in the locked position, while at the other extreme, the main linkage cannot be driven by lever/handle 112 , henceforth known as being in the open position.
The release linkage consists of lower fixed pivot link 106 , a lower floating pivot link 107 , a bearing 113 , an upper floating pivot link 115 and a upper fixed pivot link 116 . The link 106 and the link 107 are rotationally constrained at one end between bottom housing member 101 and top housing member 119 , while their other ends are rotationally constrained to link 107 and link 115 the pin position of which is movable. The other ends of link 107 and the link 115 are rotationally constrained to the pawl pivot pin 109 in the main/drive linkage.
The bearing 113 is a rotational fit to link 106 and acts as a roller to reduce friction between any surfaces it comes into contact with. This release linkage provides a means of moving the main/drive linkage from its extreme open position.
Both linkages are constrained between the bottom housing member 101 and top housing member 119 , which provide the only mechanical fixings for the whole latch assembly 100 . Each of the upper main/drive link 108 and the lower main/drive link 114 have a stub shaft 120 which extends through a stub shaft journal hole 120 in the respective adjacent outer face of the upper and lower housing members. This provides the central pivot point for these two links
Further, an arrangement consisting of a detent spring 102 , a steel ball 103 and detent retainer 104 provide an intermediate stop/detent position between the locked and open positions of the main linkage. This structure provides a physical indication that the lever has moved from the full closed/locked position to an intermediate position where opening is about to begin. The detent retainer 104 is pressed into the bottom housing member 101 , as an interference fit, forming a retaining feature for a steel ball 103 , which is biased in place by the detent spring 102 .
The main drive link spring 117 is a torsion spring with two arms each with a downward pointed end (foot). One end of the spring 117 is pinned to the bottom housing member 101 at a fixed point 220 and the other end of the spring 117 is pinned to the pivot point pin 109 between the main/drive links 114 and 108 . This permits the spring 117 to float between different positions.
The lever/handle biasing spring 118 is a torsion spring with one short straight arm and a longer arm with a downward extending pointed end (foot). This spring 118 sits in a torroid-shaped cavity 221 in the top face of the lever/handle 112 , a short radial extending slot 222 extend from the torroid cavity 221 . The short leg of the spring 118 sits in the slot 222 while the coil of the spring 118 sits in the torroid-shaped cavity 221 . The longer arm of the spring 118 has its downward end secured to a receiving hole 223 in the adjacent sidewall casting of the bottom housing member 101 .
The latch 100 essentially has three, two-piece links. The links are structured with top and bottom members being a “pair” so that they may be separated to install, i.e., receive the respective pivot pins. One paired release link 106 , 116 has a fixed housing pin 105 b and a floating pin 224 tying it to the second paired release link 107 , 115 .
The other end of the second link 107 , 115 is pinned 225 to the end of the pawl and the main/drive link 108 , 114 with the pawl pivot pin 109 into which one end of the main/drive linkage spring 117 fits its upper arm downward leg. The opposite end of the main/drive links 108 , 114 is each tied to the lever/handle 112 having the elongate cavity 226 with the side recess 227 . The lever/handle 112 rotates counter clockwise to open the latch and clockwise when the latch is being closed.
FIG. 14 shows a plan/top view of the latch 100 in the closed position with the pawl 111 engaging the keeper/striker 201 . The spring 117 has its downward leg engaging a point 220 on the bottom housing. The handle spring 118 has one leg engaging a bottom housing receiving hole 223 and the other leg positioned within a slot 222 in the lever handle 112 . FIG. 15 shows a front view of the latch handle 112 extending outwardly (from a door) when the latch 100 is in the closed position showing sectional cuts A, B, and C through the latch 100 . FIG. 16 shows the closed latch 100 engaging the keeper striker 201 with it pawl 111 hooked finger portion 230 .
FIG. 17 illustrates the hold closed position where the drive link pin 110 is held in the side recess 302 of the three lobed guide slot 301 . This slot 301 has a main slightly curved portion which is formed by a left lobe area 231 and a right lobe area 232 , which actually operates as a cam guideway for the pin 110 which operates as a cam follower. The side recess 302 , in the middle, holds the pin 110 , FIG. 17 , when the latch is in the extreme closed position. This is really a stop or detent-hold position, establishing a final clockwise rotation position for the lever/handle 112 . It also prevents link 108 and link 114 from rotating in a clockwise rotation. This in turn prevents the pawl 111 from moving, thus holding any compressive load generated between the latch and the keeper.
FIGS. 19, 20, 21, 22, and 23 show different sectional cut views of the latch 100 in the engaged position. The engage position is where the hooked finger 230 still engages the cup of the keeper/striker 201 to hold the door 501 closed and the gasket 323 still compressed, but the latch 100 is about to open.
In the engaged position, as shown in FIG. 22 , the lever/handle 112 has been freely rotated counterclockwise about 10 degrees, at which point it provides a resistance indication, indicating that the latch while still closed is about to open. This resistance indication arises because the cam follower, i.e., pin 110 , is moved out of the side recess 302 to come into contact with the far side of the guide slot 301 , FIG. 22 . But as the pin 110 moves out of the side recess 302 , the links 108 , 114 and the pawl 111 will be free to move, releasing any compression generated between the latch and the keeper 201 .
In normal use, rotating the handle though the initial 10 degrees releases the compression, which moves the main linkage 108 , 114 , the pawl pivot pin 109 , the handle pivot pin 110 and the pawl 111 to an indeterminate position where the pin 110 will move someway into the right hand lobe of the guide slot 301 in the handle 112 , coming to rest when the compression force is reduced to zero.
As the lever/handle continues to rotate counterclockwise, the pin 110 is caused to move by the slot towards the right lobe. This action will start to rotate the link 108 clockwise which in turn will push the pawl 111 outwardly, being guided by its pawl slot 210 operation with the pawl operation housing pin 105 a . The secondary linkage 106 , 107 , 115 and 116 is also moving during this time and can assist the operator in overcoming any resistance or restriction caused by the gasket 323 taking a set and preventing the door form opening.
FIGS. 24, 25, 26, 27 and 28 show different sectional cut views of the latch 100 in the detent position.
When cam follower, pin 110 , is fully in the right lobe, because the lever/handle 112 has been rotated counterclockwise about another 15 degrees, the detent position is attained, FIG. 27 . At this point there is sufficient resistance/friction in the mechanism to overcome the forces from the springs 117 and 118 . So in normal use, the user can move the lever/handle 112 counterclockwise to the stop caused by the detent feature. If the lever/handle 112 is released by the user at this point, it should remain in this position. This is to enable the door to be left ajar to release any pressure, steam or other gas from the inside of the enclosure while the pawl 111 remains engaged with the keeper 201 .
In the full detent position, the detent ball 103 is driven by the detent spring 102 and guided by the detent retainer 104 to contact the detent feature (dimple) 303 in the end of the main drive link 108 , FIG. 28 . This establishes the full lateral (straight outwardly transition) movement of the pawl, FIG. 27 where the latch and the door is held in the “cracked-open” position shown in FIG. 2 . In FIG. 27 the pawl 111 is shown in its fully outwardly extending position. The further movement of the pawl will be a counterclockwise rotation about its housing pin 105 a . This is only a transitional position. It is not intended that the latch can be left in this position as the “vent” position is the one recited above.
The further counter clockwise rotation of the lever/handle 112 brings the latch to the open position, FIG. 29 , where the pawl 111 is fully counterclockwise rotated into the housing (about 75 degrees). In this position the lever/handle 112 cannot rotate counterclockwise further because its right edge abuts the bottom housing member 101 wall, FIGS. 29 and 31 . FIGS. 29, 30, 31, 32 and 33 show the latch 100 in different sectional cut views in the extreme open position with the lever handle 118 held fixed from movement by the detent operation of the ball 103 against the detent indentation of the lower main drive link 114 , shown in FIG. 28 . FIG. 24 shows a plan view of the latch 100 where the detent ball 103 (shown in FIG. 28 ) engages the detent indentation 233 , and holds the lever handle 112 positively in the fully open position.
As shown in FIG. 28 , the detent spring 102 exerts a force against the detent retainer 104 which holds the detent ball 103 to engage the detent indentation (depression) 233 .
The lever/handle 112 and thereby the latch 100 is held in the open position with the cam pin 110 fully in the left lobe of the guide slot 301 , FIG. 32 . In this position, the end of the main/drive link 114 abuts the abutment shoulder 305 on the handle, FIG. 33 . It is the pin 110 located within the left hand lobe of the guide slot 301 which prevents the lever/handle 112 from rotating. The abutment shoulder(s) 305 on the lever/handle 112 are only required during the latch closing movement, interacting with the end of the main/drive links 108 , 114 to prevent the pin 110 from entering the side recess 302 of the guide slot 301 in the lever/handle 112 which would cause the mechanism to lock up.
However, FIG. 33 does not show the lever/handle 112 as it is the lower link 114 which abuts the shoulder 305 . The upper main/drive link 108 is shown in FIG. 31 and the lower link 114 is shown in FIGS. 32 and 33 .
The benefit of the fixed pivot points is that they constrain a component's motion to one degree of freedom, thus enabling precise control of their movement. Controlled linear and angular displacement can only be achieved through either floating pivots, and/or sliding joints, although using a round pin within a slot enables a joint to slide and pivot within the same feature.
The floating main spring 117 ensures that the pawl 111 completes its full travel during either opening or closing, wherein the latch needs to change from one state to another without relying upon the operator. Thus, during opening, once the handle is rotated passed the detent position, the main spring 117 will drive the mechanism form the detent state to the fully open state without further movement of the handle.
During closing, the release linkage will push the main/drive linkage from the fully open state, through the detent state, where the main spring 117 will drive the main/drive linkage to ensure the pawl 111 is fully engaged with the keeper 201 . This ensures that the pawl does not unintentionally clash with the keeper. The detent state has been set to coincide with the “flip point” of the main mechanism so that the force required to hold the mechanism in that position is at it lowest despite the force being generated by the floating main spring 117 being at its greatest.
This is because the fixed end of the floating spring, the pivot point at the center of the pawl pin 109 and the center of ration of the main/drive links 108 , 114 are collinear at this point. Rotation of the main/drive links 108 , 114 in either direction will move the pawl pin 109 out of line with the fixed end of the floating spring and the center of rotation of the drive links 108 , 114 . The force of the floating main spring 117 will drive the rotation of the main/drive links 108 , 114 further in that direction. This effect can be achieved by another mechanism, but that would require springs to be located on or within one of the moving components, thereby requiring them to be larger, more expensive to produce and more complicated to assemble.
FIGS. 35, 36, 37, and 38 show different sectional cut views of the latch 100 held in the detent state.
The keeper/striker 201 and its back plate 202 are held to the door jamb 320 with mounting screws 322 and nuts 321 , FIGS. 39 and 40 . In the fully engaged (locked) position, FIG. 39 , the pawl 111 hooked end 230 is fully exerted against the cup lip 234 to compress the gasket 323 . The travel of the pawl 111 is controlled by the operation of the cam pin 105 a which operates within the pawl slot 210 . In the fully engaged and gasket depressed state, the link 114 has pulled the pawl 111 fully into the housing so that the pin 105 a abuts the keeper/striker 201 end of the pawl 111 , FIG. 39 , and the gasket 323 is fully depressed to the sealing state.
In the release state, the link 114 has rotated so that the pawl 111 has moved outwardly from the housing so provide a space 235 between the main body of the oven and the oven door. FIG. 40 . In this state, the pin 109 has been moved along the pawl slot 210 and the push-out link 115 has started to rotate outwardly.
The latch is held in the door 501 by the spring clamp 402 , on one side, and by the ear 401 having the channel 403 for receiving a mounting screw 404 which seats against the inside face of the door 501 , on the other side.
Many changes can be made in the above-described invention without departing from the intent and scope thereof. It is therefore intended that the above description be read in the illustrative sense and not in the limiting sense. Substitutions and changes can be made while still being within the scope and intent of the invention. | A lever operated compression latch has an elongated, hook-ended pawl carrying a longitudinal slot, and is cam guided and pin rotated while translated to engage and withdraw from a keeper cup. The compound movement of the pawl includes a lateral translation towards the keeper cup while rotating there into, followed by a lateral withdrawal to exert a compression force between the latch body which is attached to a door and the keeper cup which is attached to a door frame. A series of interconnected links is operated by a lever handle to fold into one another to provide a compact envelope when the latch is closed and to expand outwardly to open the latch and disengage the pawl from the keeper when operated by the lever. Of this series of links, a pair of release links operates in contact with one another, and rotates on respective individual pivot points to extend outwardly from the latch envelope to engage a striker plate portion of the keeper cup. This striker engagement causes the release links to push the latch and the door from a sealing engagement with the keeper and door jamb for a short distance, prior to the latch and the door thereafter being fully opened. This striker engagement of the release links also causes the latch links to fold inwardly which rotates and translates the pawl into keeper engagement and compression. This operation is facilitated with a floating spring having one end operating as a pivot member. A detent engages one of the links to provide a physical indication to the handle lever between the hard closed position and the closed about to open position. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application Ser. No. 60/973,746 19 Sep. 2007. The disclosure of this application is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to deuterium-enriched eplivanserin, pharmaceutical compositions containing the same, and methods of using the same.
BACKGROUND OF THE INVENTION
[0003] Eplivanserin, shown below, is a well known 5-HT2A receptor antagonist.
[0000]
[0000] Since eplivanserin is a known and useful pharmaceutical, it is desirable to discover novel derivatives thereof. Eplivanserin is described in U.S. Pat. No. 5,166,416; the contents of which are incorporated herein by reference.
SUMMARY OF THE INVENTION
[0004] Accordingly, one object of the present invention is to provide deuterium-enriched eplivanserin or a pharmaceutically acceptable salt thereof.
[0005] It is another object of the present invention to provide pharmaceutical compositions comprising a pharmaceutically acceptable carrier and a therapeutically effective amount of at least one of the deuterium-enriched compounds of the present invention or a pharmaceutically acceptable salt thereof.
[0006] It is another object of the present invention to provide a method for treating sleep maintenance insomnia, comprising administering to a host in need of such treatment a therapeutically effective amount of at least one of the deuterium-enriched compounds of the present invention or a pharmaceutically acceptable salt thereof.
[0007] It is another object of the present invention to provide a novel deuterium-enriched eplivanserin or a pharmaceutically acceptable salt thereof for use in therapy.
[0008] It is another object of the present invention to provide the use of a novel deuterium-enriched eplivanserin or a pharmaceutically acceptable salt thereof for the manufacture of a medicament (e.g., for the treatment of sleep maintenance insomnia).
[0009] These and other objects, which will become apparent during the following detailed description, have been achieved by the inventor's discovery of the presently claimed deuterium-enriched eplivanserin.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0010] Deuterium (D or 2 H) is a stable, non-radioactive isotope of hydrogen and has an atomic weight of 2.0144. Hydrogen naturally occurs as a mixture of the isotopes 1 H (hydrogen or protium), D ( 2 H or deuterium), and T ( 3 H or tritium). The natural abundance of deuterium is 0.015%. One of ordinary skill in the art recognizes that in all chemical compounds with a H atom, the H atom actually represents a mixture of H and D, with about 0.015% being D. Thus, compounds with a level of deuterium that has been enriched to be greater than its natural abundance of 0.015%, should be considered unnatural and, as a result, novel over their non-enriched counterparts.
[0011] All percentages given for the amount of deuterium present are mole percentages.
[0012] It can be quite difficult in the laboratory to achieve 100% deuteration at any one site of a lab scale amount of compound (e.g., milligram or greater). When 100% deuteration is recited or a deuterium atom is specifically shown in a structure, it is assumed that a small percentage of hydrogen may still be present. Deuterium-enriched can be achieved by either exchanging protons with deuterium or by synthesizing the molecule with enriched starting materials.
[0013] The present invention provides deuterium-enriched eplivanserin or a pharmaceutically acceptable salt thereof. There are twenty-one hydrogen atoms in the eplivanserin portion of eplivanserin as show by variables R 1 -R 21 in formula I below.
[0000]
[0014] The hydrogens present on eplivanserin have different capacities for exchange with deuterium. Hydrogen atom R 1 is easily exchangeable under physiological conditions and, if replaced by a deuterium atom, it is expected that it will readily exchange for a proton after administration to a patient. The remaining hydrogen atoms are not easily exchangeable for deuterium atoms. However, deuterium atoms at the remaining positions may be incorporated by the use of deuterated starting materials or intermediates during the construction of eplivanserin.
[0015] The present invention is based on increasing the amount of deuterium present in eplivanserin above its natural abundance. This increasing is called enrichment or deuterium-enrichment. If not specifically noted, the percentage of enrichment refers to the percentage of deuterium present in the compound, mixture of compounds, or composition. Examples of the amount of enrichment include from about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16, 21, 25, 29, 33, 37, 42, 46, 50, 54, 58, 63, 67, 71, 75, 79, 84, 88, 92, 96, to about 100 mol %. Since there are 21 hydrogens in eplivanserin, replacement of a single hydrogen atom with deuterium would result in a molecule with about 5% deuterium enrichment. In order to achieve enrichment less than about 5%, but above the natural abundance, only partial deuteration of one site is required. Thus, less than about 5% enrichment would still refer to deuterium-enriched eplivanserin.
[0016] With the natural abundance of deuterium being 0.015%, one would expect that for approximately every 6,667 molecules of eplivanserin (1/0.00015=6,667), there is one naturally occurring molecule with one deuterium present. Since eplivanserin has 21 positions, one would roughly expect that for approximately every 140,007 molecules of eplivanserin (21×6,667), all 21 different, naturally occurring, mono-deuterated eplivanserins would be present. This approximation is a rough estimate as it doesn't take into account the different exchange rates of the hydrogen atoms on eplivanserin. For naturally occurring molecules with more than one deuterium, the numbers become vastly larger. In view of this natural abundance, the present invention, in an embodiment, relates to an amount of an deuterium enriched compound, whereby the enrichment recited will be more than naturally occurring deuterated molecules.
[0017] In view of the natural abundance of deuterium-enriched eplivanserin, the present invention also relates to isolated or purified deuterium-enriched eplivanserin. The isolated or purified deuterium-enriched eplivanserin is a group of molecules whose deuterium levels are above the naturally occurring levels (e.g., 5%). The isolated or purified deuterium-enriched eplivanserin can be obtained by techniques known to those of skill in the art (e.g., see the syntheses described below).
[0018] The present invention also relates to compositions comprising deuterium-enriched eplivanserin. The compositions require the presence of deuterium-enriched eplivanserin which is greater than its natural abundance. For example, the compositions of the present invention can comprise (a) a μg of a deuterium-enriched eplivanserin; (b) a mg of a deuterium-enriched eplivanserin; and, (c) a gram of a deuterium-enriched eplivanserin.
[0019] In an embodiment, the present invention provides an amount of a novel deuterium-enriched eplivanserin.
[0020] Examples of amounts include, but are not limited to (a) at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, to 1 mole, (b) at least 0.1 moles, and (c) at least 1 mole of the compound. The present amounts also cover lab-scale (e.g., gram scale), kilo-lab scale (e.g., kilogram scale), and industrial or commercial scale (e.g., multi-kilogram or above scale) quantities as these will be more useful in the actual manufacture of a pharmaceutical. Industrial/commercial scale refers to the amount of product that would be produced in a batch that was designed for clinical testing, formulation, sale/distribution to the public, etc.
[0021] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof.
[0000]
[0022] wherein R 1 -R 2 , are independently selected from H and D; and the abundance of deuterium in R 1 -R 21 is at least 5%, provided that when R 18 is D, then at least one other R is D. The abundance can also be (a) at least 10%, (b) at least 14%, (c) at least 19%, (d) at least 24%, (e) at least 29%, (f) at least 33%, (g) at least 38%, (h) at least 43%, (i) at least 48%, (j) at least 52%, (k) at least 57%, (l) at least 62%, (m) at least 67%, (n) at least 71%, (o) at least 76%, (p) at least 81%, (q) at least 86%, (r) at least 90%, (s) at least 95%, and (t) 100%.
[0023] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 1 is at least 100%.
[0024] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 2 -R 5 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0025] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 6 -R 7 is at least 50%. The abundance can also be (a) 100%.
[0026] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 8 -R 11 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0027] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 12 -R 17 is at least 17%. The abundance can also be (a) at least 33%, (b) at least 50%, (c) at least 67%, (d) at least 83%, and (e) 100%.
[0028] In another embodiment, the present invention provides a novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 18 -R 21 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0029] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof.
[0000]
[0000] wherein R 1 -R 2 , are independently selected from H and D; and the abundance of deuterium in R 1 -R 21 is at least 5%, provided that when R 18 is D, then at least one other R is D. The abundance can also be (a) at least 10%, (b) at least 14%, (c) at least 19%, (d) at least 24%, (e) at least 29%, (f) at least 33%, (g) at least 38%, (h) at least 43%, (i) at least 48%, (j) at least 52%, (k) at least 57%, (l) at least 62%, (m) at least 67%, (n) at least 71%, (o) at least 76%, (p) at least 81%, (q) at least 86%, (r) at least 90%, (s) at least 95%, and (t) 100%.
[0030] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 1 is at least 100%.
[0031] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 2 -R 5 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0032] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 6 -R 7 is at least 50%. The abundance can also be (a) 100%.
[0033] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 8 -R 11 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0034] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 12 -R 17 is at least 17%. The abundance can also be (a) at least 33%, (b) at least 50%, (c) at least 67%, (d) at least 83%, and (e) 100%.
[0035] In another embodiment, the present invention provides an isolated novel, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 18 -R 21 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0036] In another embodiment, the present invention provides novel mixture of deuterium enriched compounds of formula I or a pharmaceutically acceptable salt thereof.
[0000]
[0037] wherein R 1 -R 2 , are independently selected from H and D; and the abundance of deuterium in R 1 -R 21 is at least 5%, provided that when R 18 is D, then at least one other R is D. The abundance can also be (a) at least 10%, (b) at least 14%, (c) at least 19%, (d) at least 24%, (e) at least 29%, (f) at least 33%, (g) at least 38%, (h) at least 43%, (i) at least 48%, (j) at least 52%, (k) at least 57%, (l) at least 62%, (m) at least 67%, (n) at least 71%, (o) at least 76%, (p) at least 81%, (q) at least 86%, (r) at least 90%, (s) at least 95%, and (t) 100%.
[0038] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 1 is at least 100%.
[0039] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 2 -R 5 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0040] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 6 -R 7 is at least 50%. The abundance can also be (a) 100%.
[0041] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 8 -R 11 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0042] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 12 -R 17 is at least 17%. The abundance can also be (a) at least 33%, (b) at least 50%, (c) at least 67%, (d) at least 83%, and (e) 100%.
[0043] In another embodiment, the present invention provides a novel mixture of, deuterium enriched compound of formula I or a pharmaceutically acceptable salt thereof, wherein the abundance of deuterium in R 18 -R 21 is at least 25%. The abundance can also be (a) at least 50%, (b) at least 75%, and (c) 100%.
[0044] In another embodiment, the present invention provides novel pharmaceutical compositions, comprising: a pharmaceutically acceptable carrier and a therapeutically effective amount of a deuterium-enriched compound of the present invention.
[0045] In another embodiment, the present invention provides a novel method for treating sleep maintenance insomnia comprising: administering to a patient in need thereof a therapeutically effective amount of a deuterium-enriched compound of the present invention.
[0046] In another embodiment, the present invention provides an amount of a deuterium-enriched compound of the present invention as described above for use in therapy.
[0047] In another embodiment, the present invention provides the use of an amount of a deuterium-enriched compound of the present invention for the manufacture of a medicament (e.g., for the treatment of sleep maintenance insomnia).
[0048] The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. This invention encompasses all combinations of preferred aspects of the invention noted herein. It is understood that any and all embodiments of the present invention may be taken in conjunction with any other embodiment or embodiments to describe additional more preferred embodiments. It is also to be understood that each individual element of the preferred embodiments is intended to be taken individually as its own independent preferred embodiment. Furthermore, any element of an embodiment is meant to be combined with any and all other elements from any embodiment to describe an additional embodiment.
DEFINITIONS
[0049] The examples provided in the definitions present in this application are non-inclusive unless otherwise stated. They include but are not limited to the recited examples.
[0050] The compounds of the present invention may have asymmetric centers. Compounds of the present invention containing an asymmetrically substituted atom may be isolated in optically active or racemic forms. It is well known in the art how to prepare optically active forms, such as by resolution of racemic forms or by synthesis from optically active starting materials. All processes used to prepare compounds of the present invention and intermediates made therein are considered to be part of the present invention. All tautomers of shown or described compounds are also considered to be part of the present invention.
[0051] “Host” preferably refers to a human. It also includes other mammals including the equine, porcine, bovine, feline, and canine families.
[0052] “Treating” or “treatment” covers the treatment of a disease-state in a mammal, and includes: (a) preventing the disease-state from occurring in a mammal, in particular, when such mammal is predisposed to the disease-state but has not yet been diagnosed as having it; (b) inhibiting the disease-state, e.g., arresting it development; and/or (c) relieving the disease-state, e.g., causing regression of the disease state until a desired endpoint is reached. Treating also includes the amelioration of a symptom of a disease (e.g., lessen the pain or discomfort), wherein such amelioration may or may not be directly affecting the disease (e.g., cause, transmission, expression, etc.).
[0053] “Therapeutically effective amount” includes an amount of a compound of the present invention that is effective when administered alone or in combination to treat the desired condition or disorder. “Therapeutically effective amount” includes an amount of the combination of compounds claimed that is effective to treat the desired condition or disorder. The combination of compounds is preferably a synergistic combination. Synergy, as described, for example, by Chou and Talalay, Adv. Enzyme Regul. 1984, 22:27-55, occurs when the effect of the compounds when administered in combination is greater than the additive effect of the compounds when administered alone as a single agent. In general, a synergistic effect is most clearly demonstrated at sub-optimal concentrations of the compounds. Synergy can be in terms of lower cytotoxicity, increased antiviral effect, or some other beneficial effect of the combination compared with the individual components.
[0054] “Pharmaceutically acceptable salts” refer to derivatives of the disclosed compounds wherein the parent compound is modified by making acid or base salts thereof. Examples of pharmaceutically acceptable salts include, but are not limited to, mineral or organic acid salts of the basic residues. The pharmaceutically acceptable salts include the conventional quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. For example, such conventional non-toxic salts include, but are not limited to, those derived from inorganic and organic acids selected from 1, 2-ethanedisulfonic, 2-acetoxybenzoic, 2-hydroxyethanesulfonic, acetic, ascorbic, benzenesulfonic, benzoic, bicarbonic, carbonic, citric, edetic, ethane disulfonic, ethane sulfonic, fumaric, glucoheptonic, gluconic, glutamic, glycolic, glycollyarsanilic, hexylresorcinic, hydrabamic, hydrobromic, hydrochloric, hydroiodide, hydroxymaleic, hydroxynaphthoic, isethionic, lactic, lactobionic, lauryl sulfonic, maleic, malic, mandelic, methanesulfonic, napsylic, nitric, oxalic, pamoic, pantothenic, phenylacetic, phosphoric, polygalacturonic, propionic, salicyclic, stearic, subacetic, succinic, sulfamic, sulfanilic, sulfuric, tannic, tartaric, and toluenesulfonic.
EXAMPLES
[0055] Table 1 provides compounds that are representative examples of the present invention. When one of R 1 -R 21 is present, it is selected from H or D.
[0000]
1
2
3
4
5
6
7
[0056] Table 2 provides compounds that are representative examples of the present invention. Where H is shown, it represents naturally abundant hydrogen.
[0000]
8
9
10
11
12
13
14
[0057] Numerous 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, the invention may be practiced otherwise that as specifically described herein. | The present application describes deuterium-enriched eplivanserin, pharmaceutically acceptable salt forms thereof, and methods of treating using the same. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to electronic device testing, and more particularly to integrated circuit (IC) testing using few device pins.
[0003] 2. Description of the Related Art
[0004] Reduced pin count testing of electronic devices has been implemented in various ways. One way is to incorporate built-in self test (BIST) circuits into the device design. During testing, the BIST circuit translates incoming signals on a few pins into tests required to test and diagnose the device under test (DUT) and returns response signals containing test results.
[0005] Another way is to employ simultaneous bidirectional signaling (SBS) to combine the input to the DUT and the output from the DUT on a single line. This technique is described in a commonly owned application entitled, “A Very Small Pin Count IC Tester,” Ser. No. 10/375,025, filed Feb. 27, 2003, the entire contents of which are incorporated by reference herein. The use of SBS allows a single line to be used simultaneously for both input and output for the DUT. Hence, the time required for the test as well as the number of pins involved with the test are reduced.
[0006] Even with these reductions in the pin count and the resulting increase in the parallelism of the testing and decrease in the overall cost of testing multiple devices on a wafer, testing still remains very expensive.
SUMMARY OF THE INVENTION
[0007] An object of the invention is to provide a reduced pin count or, more generally, reduced connection count, test method and apparatus that reduces the overall cost of testing electronic devices, in particular those electronic devices that employ high-speed differential serial data streams for signaling.
[0008] The above object is achieved by employing simultaneous bidirectional signaling for test and response signals and combining device power and signal delivery on a single pair of wires. The power delivery is decoupled from the signal delivery, using inductors, so the device power supplied does not interfere with the test signals delivered from the device and the response signals delivered to the device. Further, SBS paths are decoupled, using capacitors, so that the tester transceiver and the device transceiver are not damaged by the power delivered to the device on the same wires.
[0009] The invention may be applied to testing of wafers having bump arrays that are uniform. It is noted that many wafers already have uniform bump arrays, because a specific bump pattern is required for each type of device that is formed on a wafer, and a plurality of identical devices are fabricated on a single wafer.
[0010] As will be described in more detail below, a common fixture may be used for a number of different types of wafers, independent of the topography, size, or power requirements of the devices on the wafers. The one requirement for using a common fixture is that the bumps on the tested wafer must be applied in view of the common fixture's layout so that they are aligned with the output lines on the fixture and connect to all of the signal circuits and power grids that are used in testing the ICs on the wafer.
[0011] ICs with a limited number of bumps may be designed with one test circuit and one power grid connected to a single pair of bumps. During testing of a wafer containing these ICs, power and signal delivery for each of the ICs are combined on a single pair of wires.
[0012] Larger ICs generally have higher power requirements and are designed with more than one power grid. However, they have a greater number of bumps, so the power and signal delivery need not be combined on a single pair of wires. Therefore, in general, each of the test circuits and power grids of larger ICs has connections to a different pair of bumps, such that during testing, only power is transmitted over some pairs of bumps and only test/response signals are transmitted over some pairs of bumps. When there are more bumps aligned with the output lines on the fixture than necessary, neither power nor test/response signals are transmitted over these bumps.
[0013] In accordance with the invention, connection count needed for testing is reduced. Furthermore, by taking advantage of the regularity of the device bump array on a wafer, wafers having ICs of different sizes and power requirements may be tested using a common fixture. This represents a significant cost saving, because very high connection count fixtures have become very expensive, in some cases costing more than the tester whose signals it is implemented to deliver.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0015] FIG. 1 is a block diagram showing a simplified version of the circuit design used in the invention;
[0016] FIG. 2 is a block diagram of a tester and a DUT in which the circuit design of FIG. 1 is incorporated;
[0017] FIG. 3 shows the connections between a tester and a wafer having multiple DUTs, each of which is connected to the tester by a single pair of wires;
[0018] FIG. 4 shows the connections between a tester and a wafer having multiple DUTs, each of which is connected to the tester by multiple pairs of wires;
[0019] FIG. 5A is a block diagram showing a connection between a tester and a DUT over which only power is transmitted;
[0020] FIG. 5B is a block diagram showing a connection between a tester and a DUT over which only test/response signals are transmitted; and
[0021] FIG. 5C is a block diagram showing a connection between a tester and a DUT over which neither power nor test/response signals are transmitted.
DETAILED DESCRIPTION
[0022] The present invention provides a system and method for testing electronic devices such as ICs. The invention is particularly useful in testing ICs with bump arrays. However, the invention reduces the number of connections between a tester and a DUT, regardless of the type of device being tested, and is applicable to other types of ICs.
[0023] FIG. 1 is a block diagram showing a simplified circuit design used in the invention. The left side of FIG. 1 shows circuit elements contained in the tester 100 and the right side of FIG. 1 shows circuit elements contained in the DUT 200 . The tester 100 includes a test generator 110 , a DC power supply 120 , and a differential transceiver 130 that is connected to a pair of wires 140 , 240 . The DUT 200 includes a BIST engine 210 , a power grid 220 , and a differential transceiver 230 that is connected to the pair of wires 140 , 240 .
[0024] The transceiver 130 of the tester 100 and the transceiver 230 of the DUT 200 , connected to each other through the pair of wires 140 , 240 , constitute simultaneous bidirectional signal transceivers. They are configured to transmit self-timed high-speed differential serial data streams in both directions over the wires 140 , 240 . The use of simultaneous bidirectional signal paths embodying self-timed high-speed differential serial data streams are known in the art and are described in “A 2.4 GBPS Simultaneous Bidirectional Parallel Link with Per Pin Skew Compensation,” Proceedings of ISSCC (2000), the contents of which are incorporated by reference herein. In response to instructions from the test generator 110 , which keeps track of the test information that is required to enable the BIST engine 230 , the transceivers 130 , 230 generate signals necessary to transmit a data packet or a series of data packets containing the required test information for enabling the BIST engine 230 . The BIST engine 230 receives the data packets, extracts the test information, and executes the test. The results of the test are then packaged by the BIST engine 230 and transmitted to the ATE 100 over the same wires 140 , 240 .
[0025] The current provided by the power supply 120 to the DUT 200 flows over the same wires that are used for simultaneous bidirectional signaling. As shown in FIG. 1 , the power supply 120 is connected to the wires 140 , 240 and the power grid 220 is connected to the wires 140 , 240 , so that power is supplied from the power supply 120 to the power grid 220 over the wires 140 , 240 . Power is decoupled from the test signals transmitted over the wires 140 , 240 by inductors. Inductors 150 , 151 decouple the power supply 120 from the test signals transmitted over the wires 140 , 240 , and inductors 250 , 251 decouple the power grid 220 from the test signals transmitted over the wires 140 , 240 . Local bypass capacitors 255 , 256 are connected in parallel between the two wires that connect to the power grid 220 . The bypass capacitors 255 , 256 , together with the inductors 250 , 251 , provide a low-pass filter that keeps the DUT power at the proper level.
[0026] Capacitors 150 , 151 are provided to decouple the transceiver 130 from the DC power voltages being supplied to the power grid 220 , and capacitors 250 , 251 are provided to decouple the transceiver 230 from the DC power voltages being supplied to the power grid 220 . By blocking the DC power voltages being supplied to the power grid 220 , the capacitors 150 , 151 , 250 , 251 allow the input signals to the DUT 200 and output signals from the DUT 200 to be set on average DC levels appropriate to the specific simultaneous bidirectional signal levels required by the specific DUT design, and prevent damage to the transceivers 130 , 230 by DC voltages that are outside the tolerance of these signal circuits.
[0027] FIG. 2 is a block diagram of the tester 100 and the DUT 200 in which the circuit design of FIG. 1 is incorporated. The tester includes a number of test instruments 170 , including analog test instruments and digital test instruments, that operate under the control of software, e.g., a test program 180 and a fixture 190 , which is commonly known as a loadboard. The fixture 190 is connected to the DUT 200 by a single pair of wires. As shown in FIG. 1 , this single pair of wires is used for simultaneous bidirectional signaling as well as for supplying power to the DUT 200 .
[0028] FIGS. 3 and 4 show small areas of wafers containing ICs of two different types. The ICs on the wafer of FIG. 3 are smaller than the ICs on the wafer of FIG. 4 . The wafer area shown in FIG. 3 contains 100 identical ICs and the wafer area shown in FIG. 4 contains 4 identical ICs. There may be other differences in device characteristics between the ICs on the wafer of FIG. 3 and the ICs on the wafer of FIG. 4 . As a consequence, the power and signal needs of the two wafers will be different.
[0029] In a preferred embodiment of the invention, the tester 100 tests multiple DUTs. In FIG. 3 , a small portion of the tester 100 is shown as testing a 300 mm wafer containing 60,000 identical ICs of which 100 are shown. In FIG. 4 , the tester 100 is shown as testing a 300 mm wafer containing 2400 identical ICs of which 4 are shown. The wafer bump configurations of these two wafers are identical. Therefore, a common fixture is used to test both of these wafers.
[0030] In general, a common fixture may be used to test wafers containing ICs of different types, so long as the wafers employ the same wafer bump configuration. Wafers can be configured to have the same bump configuration, because bump technology has no dependence on underlying device characteristics. The bumps are applied to the wafer in a series of manufacturing steps. This series of steps does not depend on the circuits being “bumped.” In order to employ a common fixture for different types of wafers, the bumps on the wafer are applied in view of the common fixture's layout so that they are aligned with the output lines on the fixture and connect to all of the test circuits and power grids that are used in testing the devices on the wafer.
[0031] In FIG. 3 , 100 ICs, each with 16 bumps, are shown. During test, each IC is connected to the tester 100 by a single pair of wires, but for simplicity only ten pairs of these connections are shown. Because each IC is connected to the tester by only a single pair of wires, the wires are used for both simultaneous bidirectional signaling and power transmission. Therefore, in the example of FIG. 3 , each IC has the internal circuit design of the DUT 200 shown in FIG. 1 , and the bumps are applied to the wafer so that during test the power grid and the transceiver of each IC are connected to the tester 100 through that IC's corresponding pair of wires.
[0032] On the tester side, each pair of wires is connected to a power supply 120 and a transceiver 130 as shown in FIG. 1 . The power supplies 120 are housed in one or more test instruments 170 and the transceivers are housed in one or more test instruments 170 . The fixture 190 is configured to provide the decoupling between the power and test signals (e.g., provision of inductors 150 , 151 and capacitors 160 , 161 ) that is shown in FIG. 1 .
[0033] In FIG. 4 , 4 ICs, each with 400 bumps, are shown. The fixture 190 that is designed for the wafer of FIG. 3 is also used to connect the wafer of FIG. 4 to the tester 100 . As in FIG. 3 , there are 100 pairs of wires connecting the tester 100 and the wafer being tested. Each IC in FIG. 4 has 25 pairs of wires connecting it to the tester 100 , but for simplicity only 5 pairs of wires are shown for IC 401 and IC 402 . Because each IC is connected to the tester 100 by multiple pairs of wires, depending on the IC design, one or more pairs of wires may be designated to only transmit power (see FIG. 5A ), and one or more pairs of wires may be designated to only transmit test and response signals (see FIG. 5B ). Also, one or more pairs of wires may be designated to transmit both power and test/response signals (see FIG. 1 ), or neither power nor test/response signals (see FIG. 5C ).
[0034] The designation is carried out under the control of the test program and is dependent on what components of the IC that the wires are connected to. If the wires are connected to a power grid 220 of the IC as shown in FIG. 5A , the wires are designated to only transmit power. If the wires are connected to a BIST engine 210 of the IC through a transceiver 230 as shown in FIG. 5B , the wires are designated to only transmit test and response signals. If the wires are connected to both the power grid 220 and the BIST engine 210 through a transceiver 230 , as shown in FIG. 1 , the wires are designated to transmit both power and test/response signals. The remaining wires are designated to transmit neither power nor test/response signals as shown in FIG. 5C .
[0035] For clarity, the following specific example is provided in connection with the wafer of FIG. 4 . In this example, it is assumed that each IC that is being tested requires power supplied to nine power grids, and test signals supplied to four BIST engines through corresponding transceivers. Because there are 25 available pairs of connections for each IC and only 13 pairs of connections are necessary to test one IC, it is determined that nine pairs of wires will be used for supplying power and four pairs of wires will be used for transmitting test/response signals. Twelve pairs of wires will be unused. The bumps are applied to the IC with the desired connections in mind so that, after the wafer is attached to the tester 100 for testing, nine pairs of wires are connected to the power grid of the IC and four pairs of wires are connected to the BIST engine through corresponding transceivers, while twelve pairs of wires are left open.
[0036] In another example, the tester 100 has all of the test transceivers contained in twenty-five instruments, each having two thousand transceivers. The tester 100 has all of the power supplies contained in ten instruments, each having two hundred power supplies. All of the power supplies are ganged and then distributed to the DUTs. In this example, the individual signal pairs are connected to fifty thousand (25×2000=50,000) individual sites directly, while each power supply is distributed to twenty-five signal pairs in parallel. The power distribution and a technique for disconnecting power connection to one or more of the DUTs are described in “Simultaneous Bidirectional Test Data Flow for a Low-cost Wafer Test Strategy,” ITC 2003 General Proceedings (2003), the contents of which are incorporated by reference herein.
[0037] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | Testing of an electronic device is carried out by combining power and signal delivery on a single pair of wires. The power delivery is decoupled from the signal delivery, using inductors, so the device power supplied does not interfere with the test signals delivered from the device and the response signals delivered to the device. Further, simultaneous bidirectional signal paths are decoupled, using capacitors, so that the tester transceiver and the device transceiver are not damaged by the power delivered to the device on the same wires. A common fixture may be used to test a number of different types of wafers, independent of the topography, size, or power requirements of the devices on the wafers, resulting in a significant cost saving, because fixture design has become very expensive, in some cases costing more than the tester whose signals it is implemented to deliver. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to apparatus and method for viewing the skin, and more particularly, for viewing the skin under different wavelengths and polarization of light.
BACKGROUND OF THE INVENTION
[0002] The monitoring and maintenance of healthy skin is an important concern for most people. Typically people examine their skin using a mirror in a setting with natural, incandescent and/or fluorescent lighting. This self examination process is used by a person to ascertain the condition of their skin and potentially to treat the skin with various therapies and preparations in order to improve the condition of the skin. For example, upon viewing the skin in the mirror and ascertaining that the skin looks oily, the selection and use of a washing and/or drying agent may be employed. The presence of wrinkled skin may indicate that a moisturizer or other wrinkle treatment would be advisable. People with acne frequently check their skin in the mirror to monitor and treat the acne condition. In addition to the skin conditions that are readily visible in normal lighting environments, there are also conditions that are invisible to inspection using a mirror in typical lighting. For example, conditions of the skin, such as the dilation of blood vessels below the surface, and UV photo damage to subsurface layers (mainly due to exposure to the sun), etc., will not necessarily be apparent by simply viewing the surface of the skin in a mirror. It is now known that inspection of the skin utilizing various wavelengths of light and/or polarized light can illuminate and reveal skin conditions which would otherwise be imperceptible. In addition, these alternative illuminating techniques can highlight and emphasize visible conditions, such as wrinkles or acne. Known techniques for sub-surface or enhanced surface viewing typically involve photography, wherein a flash unit which is capable of producing light of a particular wavelength is activated and an image captured with a camera. Various filters may also be employed in this process. For example, polarized photography has been utilized to enhance the surface or subsurface features of the skin by placing the polarizer in front of a flash unit and in front of a camera, and a photograph of the skin taken under these conditions. When the pictures obtained are examined, surface features of the skin, such as scales, wrinkles, fine lines, pores, and hairs are visually enhanced. When the polarizers are arranged perpendicular to each other, sub-surface features of the skin such as erythema pigmentation and blood vessels are visually enhanced. When the polarizers are in the same orientation, surface features of the skin such as scales, wrinkles, fine lines, pores and hairs are visually enhanced. Ultraviolet (UV) photography utilizing a flash unit filtered to produce ultraviolet A light and a camera is filtered so that only visible light enters the lens produces images that are visually enhanced with regard to pigmentation, the presence of the bacteria p. acnes and horn. A variation of ultraviolet photography has been termed the “sun camera” where ultraviolet A light is used to illuminate the skin and an ultraviolet A sensitive digital camera is used to record the ultraviolet light reflected from the skin. In this arrangement, both pigment distribution and the surface features of the skin are visually enhanced. While the foregoing photographic techniques have proven valuable and useful for analyzing the condition of the skin, they require fairly sophisticated and expensive equipment and the use of photographic techniques. There is a need therefore for an inexpensive and uncomplicated apparatus and method for enhanced visualization of the skin.
SUMMARY OF THE INVENTION
[0003] The problems and disadvantages associated with conventional apparatus and techniques utilized to view the skin are overcome by the present invention, which includes apparatus and methods for aiding a person illuminated by a light source to view their skin in a mirror. The light source emanates light that impinges upon the skin of the person, causing light to be reflected from the skin and causing the skin to emit light, the reflected and emitted light impinging on the mirror and further reflecting from the mirror to the eye of the person. The emanation of light from the light source and subsequent reflections and emanation from the skin and the mirror to the eye define a path of light energy from the light source to the eye. A light modification element other than a magnifying lens is interposed in the path of light energy between the light source and the eye of the person viewing the skin, the light modification element enhancing the visualization of at least one attribute of the skin. In accordance with a method for conducting self-examination of the skin in a mirror, a person illuminates the skin with a light source emanating light of a selected wavelength and state of polarization/nonpolarization to create a path of light energy from the light source to the eye of the person. A light modification element other than a magnifying lens is positioned in the path of light to enhance the person's view of themselves in the mirror, such that the perceptibility of an attribute of their skin is visually enhanced over that otherwise viewable in the mirror without the light modification element.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 is a perspective view of a person examining their skin in a mirror and using an embodiment of the present invention;
[0005] FIG. 2 is a diagrammatic view of the invention of FIG. 1 ;
[0006] FIG. 3 is another diagrammatic view of the invention of FIG. 1 showing different combinations of illuminating light and filtering for viewing surfaces S 1 through S 4 ;
[0007] FIG. 4 is a front view of the light source shown in FIGS. 1-3 ;
[0008] FIG. 5 is a perspective view of a person using a second embodiment of the present invention;
[0009] FIG. 6 is a diagrammatic view of a cross section of the invention shown in FIG. 5 taken along section lines VI-VI and looking in the direction of the arrows; and
[0010] FIG. 7 is a front view of the invention shown in FIGS. 5 and 6 .
DETAILED DESCRIPTION OF THE INVENTION
[0011] FIG. 1 shows a visualizing system 5 used by a person P examining her reflected facial image RI in a mirror 10 . Light source 12 illuminates the face of the person P, for example, at surface S 0 via illuminating light 14 . The illuminating light 14 reflects off the surface S 0 and/or causes the skin or other surface components of the surface S 0 as well as the subsurface layers of the skin proximate to S 0 to fluoresce. The resultant reflected and or fluorescent light 16 emanates from the surface S 0 and impinges on corresponding reflected surface S or on the mirror image RI. Light 16 is reflected from the mirror 10 as indicated by lines 18 and passes through lenses 20 a , 20 b of goggles/eyeglasses 22 where it enters the eye of the person P to allow examination of S 0 by that person. The light source 12 may have a polarizer and/or filter portion 24 which may be rotated relative to light source 12 and/or removed depending on the imaging that is desired. In FIG. 2 , the lens 20 a , of the goggles 22 is shown as being rotatable, for example if it is a polarizer. A polarizer and/or filter lens 24 may be interposed at the output of the light source 12 and/or in association with the goggles 22 , namely as one or more lenses 20 a . As used herein, the term “lens” is intended to include any light modifying element, e.g., filter elements, such as a filter excluding light of particular wavelengths and/or polarizing elements. More particularly, the lenses 20 a , 20 b of the goggles 22 may be composite, i.e., may be composed of multiple lenses/filters/polarizers to achieve a desired transmissibility to the reflected light 18 . Having passed through the lenses 20 a , 20 b of the goggles 22 , the observed light 19 can then be seen by the eye E of the person P. The foregoing apparatus and associated method therefore presents a system 5 whereby skin conditions may be visualized by utilizing a simple hand held light source 12 similar in size to a flashlight that produces specific and selectable wavelengths and/or polarization characteristics. These selected wavelength and/or polarizing characteristics of the light source are then coupled with selected filtering or polarization lenses associated with the goggles 22 in order to highlight specific skin conditions. While eyeglass-type goggles 22 with fixed lenses 20 a , 20 b are shown in FIG. 1 , goggles 22 utilizing frames for receiving clip-on or screw-on lenses may be employed. Stacking of lenses, if desired, may be accomplished by using conventional clip-on or screw-on arrangements that are known in the fields of optometry and photography, e.g., as illustrated by the various types of clip-on sunglasses, or clip-on or threaded filters for use on cameras. Similarly, while fixed lenses are shown, lenses that are rotatably mounted to the frame of the goggles 22 or that may be affixed to the goggles 22 in a plurality of orientations is within the scope of the present invention and would be useful for affixing polarizing lenses to the goggles 22 . Exemplary means for selecting and positioning lenses 20 a , 20 b singly or in combination are shown in FIGS. 8-12 . A system 5 in accordance with the present invention therefore allows a user to self-visualize and evaluate skin conditions in order to select and apply skin products based upon changing needs and/or to visualize skin improvement resulting from successful therapy with these products.
[0012] The system 5 comprehends a single-use device e.g., a pair of goggles with a single type of lenses 20 a , 20 b and a light 12 having a single illuminating light output, or may use multiple light sources/filters and goggle combinations. A plurality of different lenses/filters may be provided to cooperate with a single pair of goggles 22 and a single light 12 , or a set of different goggles 22 and/or set of different light sources 12 may be utilized.
[0013] Various selectable components and combinations of lenses 20 and lights 12 for the system 5 are illustrated in FIG. 3 wherein light sources 12 u , 12 b , 12 w radiate light in a specific range of wavelengths 13 u , 13 b , 13 w . In the case of the white light sources 12 w , the emitted white light 13 w is passed through polarizing elements, either 24 p1 or 24 p2 before it is reflected off the surface to be viewed, e.g., S 3 or S 4 . The UV light source 12 u is not filtered or polarized, such that the light 13 u emitted therefrom reflects from surface S 1 to produce resultant reflected light 16 . Similarly the blue light 13 b from the blue light source 12 b is not polarized or filtered prior to reflecting off surface S 2 to produce reflected light 16 . Having reflected off the surfaces S 1 , S 2 , S 3 , S 4 , the reflected light 16 may be further processed by a polarizer set at a specific orientation, e.g., 20 p1 , a light filter, e.g., a yellow light filter 20 y , or a UV light filter 20 nu . Having passed through the filters and/or polarizers 20 which are associated with the goggles 22 , the observed light 19 then enters the eye E of the person visualizing the skin.
[0014] FIG. 4 shows a configuration of multiple light sources (bulbs, LEDs filtered light emitters) 12 b , 12 w , 12 u that could be utilized in light 12 . The light 12 may have multiple emitters for emitting specific wavelengths of light upon selection via a switch disposed on the surface of the light 12 , for viewing specific skin features. The system 5 may be used for enhanced viewing of several different skin conditions/states. The following examples are illustrative.
[0015] For viewing skin wrinkles, the light 12 may include a white light source, such as a tungsten lamp, white LED, fluorescent bulb, or metal halide light. Illuminating light is filtered through a polarizing lens 24 disposed on the output of the light 12 . The light 12 may be held by the user and shone onto the face (or body) to be analyzed in front of a normal mirror. The user wears a set of goggles 22 that include polarizing filter lenses 20 a , 20 b oriented in the same polarization direction as the polarizing lens 24 . This configuration of the system 5 enhances the visualization of surface texture and wrinkles of the skin, while obscuring the skin's sub-surface characteristics that can obscure surface information.
[0016] To view skin inflammation and sub-surface blood vessels, the light 12 includes a white light source, such as a tungsten lamp, white LED, fluorescent bulb, or metal halide light. The illuminating light is filtered through a polarizing lens 24 on the output of the light 12 . The light 12 may be held by the user and shone onto the face (or body) to be analyzed in front of a normal mirror. The orientation of the polarization filter 24 is perpendicular to polarizing filter lenses 20 a , 20 b of the goggles 22 . In this configuration, the system 5 eliminates the visualization of the surface texture and wrinkles of the skin, while enhancing the skin's sub-surface characteristics such as the redness and vasculature under the skin's surface.
[0017] Acne related conditions, i.e., horn and bacteria may be viewed with a light 12 emitting blue light (380-420 nm), which can be produced by LED's, or white light from a tungsten bulb or metal halide or blue fluorescent source, that is shone onto the face of the user. The user wears goggles 22 with yellow lenses 20 a , 20 b , which block the incident blue light and allows for the visualization of porphyrin fluorescence (red color) showing where bacteria is active in producing porphyrins from sebum and the location of individual comedones expressing horn (epidermal cells with sebaceous material) which fluoresces white. Using this configuration of the system 5 , areas of acne activity prior to inflammatory breakout may be visualized.
[0018] The system 5 may be utilized to view UV photodamage, collagen and elastin florescence and pigmentation by using a light 12 emitting UV light (320-400 nm). UV light can be produced by a fluorescent black light bulb, a filtered tungsten lamp, a filtered zenon lamp, a UV LED, or filtered metal halide source. The UV light is shone onto the face or body of the user to fluoresce the collagen and elastin in the skin. The level of fluorescence is dependent on the amount of photo damage and skin age of the individual. The amount of pigment and distribution of pigment is highlighted by the underlying collagen and elastin fluorescence and indicates the extent of photodamage to the individual's skin. The user should wear goggles 22 with UV filtering lenses 20 a , 20 b that block UV radiation to protect the eyes from the potentially harmful UV.
[0019] FIG. 5 shows an alternative embodiment of the system 55 in accordance with the present invention utilizing an illuminating mirror 58 . The illuminating mirror 58 has a mirror portion 60 , which may be a conventional reflective mirror to provide a reflected image RI. The mirror portion 60 is surrounded by a ring-shaped light source 62 which may be in the form of a plurality of individual illuminating elements/ lights 80 that are disposed about the periphery of the mirror portion 60 . The lights 80 are mounted in housing 64 and the housing may accommodate a diffuser or polarizing ring 78 as shall be described below. The housing 64 is pivotally mounted on mounting ring 66 at pivots 70 to permit repositioning of the mirror along the axis established between the pivots 70 . In addition to pivoting, the illuminating mirror 58 can be rotated by sliding the mounting ring 66 through the support post 68 to establish a particular angular orientation of the light source 62 . This ability to rotate the illuminating mirror on the mounting ring 66 is useful in the instance where the light source 62 includes a polarizing element disposed thereover to polarize the light 72 emanating from the light source 62 . In this manner, the direction of the polarizing element can be changed to conduct various skin examinations, i.e., to position the polarizing element perpendicular to or parallel to the orientation of polarizer elements associated with the goggles 22 in a similar fashion as the polarizing elements 24 p1 and 24 p2 may be orientated relative to polarizing elements 20 p of the prior embodiment described above. As in the prior embodiment, light 72 projected from the light source 62 impinges upon a surface S 0 on the face of the person P and is reflected therefrom 74 to a corresponding point S 0r on the reflected image RI appearing in the mirror. The light is then reflected from surface S 0r towards the lenses 20 a , 20 b of the goggles 22 where it is then converted into the observed light 19 due to its passage through the lens elements 20 a , 20 b .
[0020] FIGS. 6 and 7 show that lights 80 within the light source 62 may be a plurality of independent bulbs or LEDs which generate specific wavelengths of light, viz., UV light 80 u , blue light 80 b , and white light 80 w . As noted above, various combinations of lenses, filters and polarizers can be used in conjunction with the lights 80 to produce a desired illuminating light 72 .
[0021] FIGS. 8 and 9 show goggles 82 having threaded flanges 84 for receiving one or more nested lenses 86 a , 86 b , which may be filters or polarizers as described above.
[0022] FIG. 10 shows conventional clip-on style lenses 88 with hooks for grasping the frame of a pair of goggles 22 .
[0023] FIGS. 11 and 12 show goggles 92 with a slotted frame 94 for receiving lens inserts 96 a , 96 b . In the embodiment shown, the lens inserts 96 a , 96 b are rotatable via tab 98 , e.g., to serve as adjustable polarizers. | An apparatus and method for aiding a person to conduct self-examination of the skin in a mirror has a light source emanating light that impinges upon the skin of the person, causing light to be reflected from the skin and causing the skin to emit light, the reflected and emitted light impinging on the mirror and further reflecting from the mirror to the eye of the person. A pair of goggles worn by the person has lenses that are light filters and/or polarizers. The light source may be in the form of a flashlight which has filters and/or polarizers disposed over the output. The lenses and polarizer are preferably removable and the polarizer may be rotatable to provide various illuminating light combinations. The image reviewed by the person as a consequence of the lenses in the goggles and over the flashlight are enhanced for viewing features of the skin depending upon the combination of lenses, filters, polarizers and their respective relative orientations. | 0 |
FIELD OF THE INVENTION
[0001] The invention generally relates to a device for securing an invasive medical implementation to a subject. Specific embodiments allow a user to secure a catheter to a patient rapidly and without the aid of prior surgical tapes, glues, dressings and/or foams.
BACKGROUND
[0002] Medical implementations such as catheters, medical lines, tubing and like articles are routinely used to move fluids to and from patients. A catheter typically includes a hard part which remains exterior to the patient, and a soft part, at least a portion of which is inserted into the patient. The hard part can include a connection point (sometimes called a hub) to which other medical implementations (eg., a syringe, fluid supply tube) can be joined. Following installation and securement (“catheterization”), the catheter is a convenient means for administering fluids such as drugs or withdrawing blood or other body fluids from the patient.
[0003] According to prior practice, a caregiver uses glue, foam, surgical tape, dressing or a combination thereof to secure the catheter against the skin of the patient. Typically, the caregiver covers the catheter insertion site with a dressing after swabbing the area with antiseptic. The entire procedure can take several minutes or more. In addition, catheterization can require frequent disconnection between of the catheter as new medical lines are added or replaced, thereby stressing securing tapes, glues or foams. In settings involving long-term catheter use, the caregiver must frequently clean the insertion site about the inserted (indwelling) catheter, change the dressings, and apply fresh antiseptic.
[0004] There has been increasing recognition that caregivers spend too much time securing catheters to patients. Moreover, prior practice has not been able to prevent catheter dislodgement and/or infection near insertion sites. Catheters that are taped or glued in place are readily pulled out during “routine” dressing changes. Surgical tapes and foams can be uncomfortable or irritating for some. Many patients cannot rest comfortably knowing that a secured catheter may dislodge from the insertion time during sleep. Young or elderly patients are especially vulnerable to these and related shortcomings.
[0005] It is becoming clear that prior catheter securement devices and procedures have not optimally served patients. These and other drawbacks have created a need for a more rapid and reliable device for securing catheters to patients. Accordingly, it would be desirable to have a device that can be used to secure a catheter to the skin of a patient that does not rely on use of prior tapes, glues, dressings and/or foams. It would be further desirable to have methods of using such a device so that the catheter can be rapidly and reliably secured to the patient.
SUMMARY
[0006] In broad terms, the invention provides a device for securing an invasive medical implementation such as a catheter to a patient. The device generally combines (1) an adherent surface that attaches the device to the skin and (2) a flexible clasping means to grasp the catheter and secure it to the device. Securement is typically reversible. Preferred practice of the invention avoids use of prior tapes, glues, dressings and/or foams to secure the medical implementation to the patient. Use of the invention can substantially reduce catheter securement times, thereby enhancing the reliability, comfort, and safety of catheterization. The invention is relatively simple to use and can be employed by experienced and inexperienced caregivers alike.
[0007] Accordingly, and in one aspect, the invention provides a device for securing a catheter to an insertion site of a patient. In one embodiment, the device includes at least one of and preferably all of the following as operably linked components:
[0000] (a) a flexible base comprising a sealed patient contacting surface,
(b) a solid portion joined to the flexible base and comprising a clasping means for securing the catheter; and
(c) a handle adapted to remove, with one digit (finger or thumb), a seal from the patient contacting surface. Preferably, the handle is joined to the seal which seal protects the adhesive on at least part of the surface sufficient to attach the secured catheter to the patient insertion site. In a particular invention embodiment, the device will be referred to herein as a “catheter clip” or like phrase.
[0008] In another aspect, the invention provides a unitary package that includes the device wherein the device is preferably sterile and includes a packing material substantially resistant to penetration by microorganisms, viruses and the like.
[0009] In yet another aspect, the invention provides a method of securing a catheter to an insertion site of a patient. In one embodiment, the method includes at least one of and preferably all of the following steps:
[0000] (a) providing a device comprising:
[0010] (i) a flexible base comprising a sealed patient contacting surface,
[0011] (ii) a solid portion joined to the flexible base and comprising a clasping means for securing the catheter to the device,
[0012] (iii) a handle region joined to the flexible portion and adapted to remove, with one hand, a seal from the patient contacting surface, thereby exposing the adhesive for releasably securing the catheter to the insertion site of the patient,
[0000] (b) removing, with at least one digit, the seal from the patient contacting surface of the flexible portion to expose the adhesive,
(c) guiding the device over the catheter,
(d) contacting the flexible base (patient contacting surface) to the patient sufficient to adhere the device thereto; and
(e) actuating the clasping means to grasp the catheter (preferably at or around the solid part), thereby securing the catheter to insertion site of the patient.
[0013] Further uses and advantages of the invention will be apparent from the following Drawings and discussion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1A is a drawing (top view) showing a catheter clip of the invention.
[0015] FIG. 1B is a drawing (top view) showing the catheter clip securing a catheter having lateral wings for stabilizing the catheters and connecting hubs.
[0016] FIG. 2 is a drawing (cross-sectional view) of the catheter clip securing a catheter against the skin of a patient.
DETAILED DESCRIPTION
[0017] In the present section, the invention is illustrated with regard to one or more particular embodiments. These embodiments are intended merely to illustrate certain principles of the invention and not to limit the invention or use thereof in any way.
[0018] FIG. 1A shows a particular embodiment of the invention (“catheter clip”) for securing a catheter to a skin insertion site of a patient. The catheter clip 10 includes a solid portion 50 joined to a flexible base 20 . The flexible base 20 includes an underlying patient contacting surface 41 (see FIG. 2 ) that is at least partially sealed with a suitable sealing medium such as paper or a plastic. The solid portion 50 includes a clasping means 51 adapted to grasp and securing the catheter to the catheter clip 10 . The clasping means 51 may include or consist of nearly any suitable plastic material provided it flexibly resists extension by a user. A cover 40 is in actuating contact with a handle 30 attached to the flexible base 20 . The handle 30 and the cover 40 are in sealing contact with a seal formed on at least part of the patient contacting surface 41 . Preferably, the seal will protect an adhesive on at least part of the patient contacting surface 41 , preferably substantially all of it. The amount of adhesive on the patient contacting surface 41 is not critical provided it is sufficient to attach the catheter clip 10 to the patient.
[0019] Referring again to FIG. 1A , the solid portion 50 , flexible base 20 and the handle 30 together define an open chamber 52 that includes a distal end 53 (shown contacting a first centerpoint) for receiving the catheter and a proximal end 54 (shown contacting a second centerpoint) for accepting the catheter from the distal end 53 toward the skin insertion site 90 (see FIG. 1B ). The first centerpoint of the distal end 53 and the second centerpoint of the proximal end define an axis 55 surrounded by the open chamber 52 . In preferred use, a catheter (typically the hard part) is placed along the axis 55 for securement to the catheter clip 10 by the clasping means 51 . As shown, the open chamber 52 further includes a top 56 defined by at least part of the solid portion 50 and a bottom 57 (see FIG. 2 ) opposite the top 56 and defined by the handle 30 and the flexible base 20 . In the embodiment shown, the top 56 is in actuating contact with the clasping means 51 , wherein actuation of the top 56 is sufficient to flex the clasping means 51 so that it grasps and secures the hard part of a catheter to the catheter clip 10 .
[0020] The flexible base 20 and optionally the solid portion 50 further define a compartment 70 positioned at or near the insertion site 90 . The compartment 70 is typically adapted to at least partially surround the patient insertion site including completely surrounding it. According to FIG. 1A , the top 56 substantially extends from the clasping means 51 to the compartment 70 . Optionally, the compartment 70 is in sealing contact with the seal of the patient contacting surface 41 . In one embodiment, the compartment 70 will include an effective amount of an antimicrobial (antiseptic) agent sufficient to minimize or eliminate infection at the insertion site. Suitable examples include certain alcohols and phenols known to have antiseptic properties (eg., isopropyl alcohol, phenol), iodine tinctures, chlorhexidine, povidone-iodine (Betadine®) and the like. Preferably, the agents are provided in the compartment 70 in a liquid, semi-liquid or cream format. Topical use antibiotics (eg., bacitracin zinc, polymysin B sulfate, and/or neomycin sulfate), preferably in cream form, can also be used alone or in combination with other antimicrobial agents.
[0021] In the embodiment shown in FIG. 1A , the flexible base 20 is substantially planar. Preferably, the flexible base 20 is composed of a material (or composite) of sufficient rigidity so that self-folding is minimized or eliminated. To further minimize self-folding, the catheter clip 10 includes extensions 60 , 61 , and 62 of the solid portion 50 which are positioned to help keep the flexible base 20 substantially extended. Additional rigidity is provided by firming contact between the extensions 60 , 61 and 62 and the flexible base 20 .
[0022] FIG. 1B shows the catheter clip 10 with a catheter 140 secured to the patient insertion site 90 which catheter 140 is composed of a catheter hard part 110 with a connecting hubs 111 , 112 , lateral wings 100 for stabilizing the catheter and a catheter soft part 80 extending from the insertion site 90 toward and under the skin 120 . The catheter 140 is secured to the catheter clip 10 by actuation of clasping means 51 as previously described. The catheter clip 10 is secured to the patient through the adhesive of the patient contacting surface 41 .
[0023] Referring now to FIG. 2 , the catheter clip 10 is shown in cross-section with the catheter 140 secured to the patient insertion site 90 . Also shown is the top 56 of the solid portion 50 with a protrusion 130 that extends acutely from the axis 55 (see also FIG. 1A ) and is in actuating contact with the clasping means 51 . The protrusion 130 is adapted to receive at least one digit from a user which digit engages protrusion 130 to flex the clasping means 51 , grasp the catheter 140 (preferably along the hard part 110 ), and secure it to the catheter clip 10 .
[0024] According to one use of the catheter clip 10 , a caregiver inserts the soft part 80 of the catheter 140 under the skin 120 at the patient insertion site 90 . Subsequently, the caregiver uses a finger to remove cover 40 and the handle 30 in sealing contact with the adhesive along the patient contacting surface 41 of the flexible base 20 , thereby removing the seal and exposing the adhesive. The catheter clip 10 is then guided around the patient insertion site 90 to reversibly attach the invention to the skin 120 of the patient. Using the same or different finger, the caregiver engages the protrusion 130 to flex the clasping means 51 and grasp the hard part 110 of the catheter 140 , thereby releasably securing the catheter 140 to the catheter clip 10 . The procedure is readily reversible. In one approach, the patient contacting surface 41 is removed from the patient. The clamping means 51 is flexed by the user to allow removal of the catheter 140 from the invention.
[0025] Manufacture
[0026] The invention can be readily made using one or a combination of approaches. In one method, the hard part of the catheter clip 10 is molded as a single-piece system with the clasping means 51 capable of convenient and repeated flexure. The hard part of the catheter clip 10 can be molded from a single polymer material in a one-shot injection molding operation. Many suitable materials could be used such as nearly any moldable plastic that is capable of being formed as provided herein and retaining its shape during use. More specific materials include, but are not limited to, many acrylic and polycarbonate materials, styrenes, and ABS. Other suitable materials include certain polyesters, nylons, and other polymer materials such as certain polyethylenes and polypropylenes. Certain memory plastics may also be used provided intended results are achieved. If two different materials are used, the device can be made by a two-shot process whereby both materials are injected at different gates into the mold cavity. Other processes are also feasible, such as insert molding. MRI compatible materials may be suitable for some invention applications.
[0027] Once the hard part of the catheter clip 10 is made, it can be joined using standard approaches to the soft part of the device which generally includes the flexible base 20 .
[0000] The flexible base 20 can be made using one or a combination of conventional approaches. In one method, the flexible base 20 comprises a relatively thin film, such as a thin urethane or silicone film, adhered to the handle 30 and cover 40 . The handle 30 and cover 40 can be made somewhat stiffer than the flexible base 20 facilitate handling. The handle 30 and the cover 40 may extend beyond an edge or edges of the thin film, so that the flexible base 20 can be handled relatively easily. In one embodiment, substantially all of the undersurface of the flexible base 20 (ie., the patient contacting surfacem41) is adhesively coated and contacted with a separate release seal which extends beyond the perimeter of the thin film and is in sealing contact with the handle 30 and cover 40 . Nearly any adhesive suitable for topical medical use can be applied to the thin film using standard methods. Examples include, but are not limited to, an acrylic adhesive containing an acrylic acid alkyl ester as a main component, a rubber adhesive containing a natural rubber and/or a synthetic rubber as a main component, as well as “pressure sensitive adhesives” (PSAs). See also U.S. Pat. Nos. 7,094,944; 6,936,661; and 6,805,961 and references disclosed therein for other suitable adhesives.
[0028] As will be apparent, the seal may protect the adhesive on at least part of the patient contacting surface 41 (e.g., less than about 50%, for instance, about 5%, 10%, 20% or about 30%), preferably substantially all of the surface (e.g., about 80%, 90%, 95% up to about 100%). The amount of adhesive on the patient contacting surface is not critical provided intended results are achieved.
[0029] Additional Embodiments
[0030] As will be appreciated, other embodiments of the catheter clip 10 are within the scope of the invention. For instance, and referring now to FIG. 1A , the clasping means 51 is shown as an integral part of the solid portion 50 . However in another embodiment, clasping means 51 may be joined to solid portion 50 through an elastic or semi-elastic polymer such as a memory plastic. Alternatively, the clasping means 51 can include or be joined to the solid portion 50 through a spring or related mechanism.
[0031] In another embodiment of the catheter clip 10 , the top 56 includes means (e.g., a spring or a rod) to position the clasping means 51 to a site desired by the user. It will be appreciated that in other embodiments, the top 56 and the clasping means 51 may be the same component.
[0032] In another embodiment, the compartment 70 can be quite small and be just sufficient to surround the insertion site of the catheter. In this embodiment, it will not be necessary to make the compartment 70 so that it is in sealing contact with other components of the device. Also in this embodiment, the use of an antimicrobial may not be necessary. Instead, it may be applied to the skin surface by the user.
[0033] Nearly any configuration of the protrusion 130 is acceptable provided intended results are achieved. For instance, and in one embodiment, the protrusion 130 will extend substantially perpendicular to the axis 55 of the open chamber 130 .
[0034] In yet another embodiment of the catheter clip 10 , only one or two of the extensions 60 , 61 , and 62 will be used to provide rigidity to the flexible base 20 . In yet another embodiment, the flexible base 20 will be of sufficient rigidity so that none of extensions 60 , 61 and 62 are needed.
Incorporation by Reference
[0035] The contents of all references (including literature references, issued patents, published patent applications, and co-pending patent applications) cited throughout this application are hereby expressly incorporated herein in their entireties by reference.
Equivalents
[0036] It will be appreciated that those skilled in the art, upon consideration of this disclosure, may make modifications and improvements within the spirit and scope of the invention. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents of the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims. | The invention provides a device for securing an invasive medical implementation, such as a catheter, to a patient. The device generally combines an adherent surface that attaches the device to the skin and a flexible clasping means to grasp the catheter and reversibly secure it to the device. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation-in-part application of U.S. patent application Ser. No. 913,754 filed June 8, 1978, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to optical waveguide filaments, and more particularly to an improved method of forming blanks from which such filaments are drawn.
Optical waveguides, which are the most promising medium for use in optical communication systems operating in the visible or near visible spectra, normally consist of an optical filament having a transparent core surrounded by a transparent cladding material having a refractive index lower than that of the core.
The stringent optical requirements placed on the transmission medium to be employed in optical communications systems has negated the use of conventional glass fiber optics, since attenuation therein due to both scattering and impurity absorption is much too high. Thus, unique methods had to be developed for preparing very high purity glasses in filamentary form. Certain glass making processes, particularly vapor deposition processes, have been commonly employed in the formation of optical waveguide blanks. In one such process, the source material vapor is directed into a heated tube wherein it reacts to form a material which is deposited in successive layers. The combination of deposited glass and tube is collapsed to form a draw blank which can be later heated and drawn into an optical waveguide filament.
In order to obtain uniform deposition along the length of the substrate tube, a serial deposition process has been employed. That is, reactants are fed into the end of the tube, but deposition occurs only in a narrow section of the tube which is heated by a flame. The flame moves up and down the tube to move the reaction and thus the region of glass deposition serially along the tube.
One of the limitations of such a process is a comparatively low effective mass deposition rate. To increase the deposition rate it appears to be necessary to increase the inside diameter of the substrate tube to provide a greater collection surface area. However, since heat is supplied from the outside of the tube, a larger tube diameter results in a lower vapor temperature at the axis of the tube. Moreover, the flow profile across the tube is such that maximum flow occurs axially within the tube. As tube diameter increases, a smaller portion of the reactant vapor flows in that region of the tube adjacent the wall where reaction temperature is higher and where the resultant sooty reaction products are more readily collected on the heated region of the tube.
It is therefore an object of the present invention to improve the deposition efficiency of a process whereby a reactant vapor flows into and reacts within a heated tube to form a layer therein.
SUMMARY OF THE INVENTION
Briefly, the present invention relates to a method and apparatus for manufacturing a preform which is intended to be subsequently drawn into an optical filament. This method is of the type that includes the steps of flowing a vapor mixture including at least one compound, glass-forming precursor, together with an oxidizing medium, through a hollow, cylindrical substrate, and heating the substrate and contained vapor mixture with a heat source that moves relative to the substrate in a longitudinal direction, whereby a moving hot zone is established within the substrate, such that a suspension of particulate, oxidic reaction product material is produced within the hot zone. The particulate material travels downstream where at least a portion thereof comes to rest on the inner surface of the substrate where it is fused to form a continuous glassy deposit. The improvement of the present invention comprises confining the flow of the vapor mixture to an annular channel adjacent the substrate surface in the hot zone whereby the deposition efficiency of the vapor mixture reaction is increased.
In accordance with a preferred embodiment of the present invention, a gas conducting baffle tube is disposed in one end of the cylindrical substrate, one end of the baffle tube terminating adjacent the hot zone. Means is provided for moving the tube longitudinally with respect to the substrate in synchronism with the movement of the heating means which generates the moving hot zone. Gas emanating from the baffle tube forms a gaseous mandrel in the hot zone which confines the vapor mixture to an annular channel adjacent the substrate surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a prior art apparatus for depositing a glass layer within a tube.
FIG. 2 shows a section of the tube of FIG. 1 depicting observed conditions during processing.
FIG. 3 is a schematic representation of an apparatus suitable for practice of the deposition process in accordance with the present invention.
FIGS. 4 and 5 are cross-sectional views of the apparatus of the present invention depicting conditions occurring during processing.
FIG. 6 shows the end of a modified baffle tube that can be employed in the apparatus of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 show a prior art system comprising a substrate tube 10 having handle tube 8 affixed to the upstream end thereof and exhaust tube 12 affixed to the downstream end thereof. Tubes 8 and 12 are chucked in a conventional glass turning lathe (not shown), and the combination is rotated as indicated by the arrow. The handle tube, which may be omitted, is an inexpensive glass tube having the same diameter as the substrate tube, and it does not form a part of the resultant optical waveguide. A hot zone 14 is caused to traverse tube 10 by moving heating means 16 as schematically depicted by arrows 18a and 18b. Heating means 16 can consist of any suitable source of heat such as a plurality of burners encircling tube 10. Reactants are introduced into tube 10 via inlet tube 20, which is connected to a plurality of sources of gases and vapors. In FIG. 1, flow meters are represented by a circle having the letter "F" therein. A source 22 of oxygen is connected by flow meter 24 to inlet tube 20 and by flow meters 26, 28 and 30 to reservoirs 32, 34 and 36, respectively. A source 38 of boron trichloride is connected to tube 20 by a flow meter 40. Reservoirs 32, 34 and 36 contain normally liquid reactant materials which are introduced into tube 10 by bubbling oxygen or other suitable carrier gas therethrough. Exiting material is exhausted through exhaust tube 12. Not shown is an arrangement of mixing valves and shutoff valves which may be utilized to meter flows and to make other necessary adjustments in composition.
Burner 16 initially moves at a low rate of speed relative to tube 10 in the direction of arrow 18b, the same direction as the reactant flow. The reactants react in hot zone 14 to produce soot, i.e., a powdery suspension of particulate oxidic material, which is carried downstream to region 42 of tube 10 by moving gas. In general, between twenty and seventy percent of reaction product produced in that portion of the vapor stream results in the deposition of soot on the substrate surface.
It is noted that essentially no soot is formed in region 46 of tube 10 upstream from hot zone 14. As burner 16 continues to move in the direction of arrow 18b, hot zone 14 moves downstream so that a part of sood buildup 44 extends into the hot zone and is consolidated thereby to form a unitary, homogeneous glassy layer 48. Such process parameters as temperatures, flow rates, reactants and the like are discussed in the publications J. B. MacChesney et al., Proceedings of the IEEE, 1280 (1974) and W. G. French et al., Applied Optics, 15 (1976). Reference is also made to the text Vapor Deposition Edited by C. F. Powell et al. John Wiley and Sons, Inc. (1966).
When burner 16 reaches the end of tube 10 adjacent to exhaust tube 12, the temperature of the flame is reduced and the burner returns in the direction of arrow 18a to the input end of tube 10. Thereafter, additional layers of glassy material are deposited within tube 10 in the manner described above. After suitable layers have been deposited to serve as the cladding and/or core material of the resultant optical waveguide filament, the temperature of the glass is increased to about 2200° C. for high silica content glass to cause tube 10 to collapse. This can be accomplished by reducing the rate of traverse of the hot zone. The resultant draw blank is then drawn in accordance with well-known techniques to form an optical waveguide filament having the desired diameter.
To optimize the process from the standpoint of reaction, high temperatures are utilized. For the usual silica based system, temperatures at the substrate wall are generally maintained between about 1400° and 1900° C. at the moving position corresponding with the hot zone. Indicated temperatures are those measured by a radiation pyrometer focused at the outer tube surface.
It is commonly known that one of the factors which limits deposition rate is the rate of sintering deposited soot to form a transparent glass layer. For a given composition of glass to be deposited, there is a maximum layer thickness of glass that can be sintered using the optimum combination of hot zone width, peak temperature of the hot zone and burner traverse rate. If the thickness of the sintered glass layer can be kept to the maximum value for different tube diameters, deposition rate increases proportionately with tube inside diameter because of increased surface area. However, because of the nature of flow dynamics of the reactant vapor stream and soot particle dynamics, the percentage of soot produced which deposits in the substrate tube decreases with increased tube diameter, thereby causing an effective decrease of deposition rate.
In accordance with the present invention means is provided for confining the flow of reactants to an annular channel adjacent the wall of the substrate tube in the hot zone. As shown in FIG. 3 a portion of gas conducting tube 50 extends into that end of substrate or bait tube 52 into which the reactants are introduced. That portion of tube 50 within tube 52 terminates just prior to the hot zone 54 created by moving heat source 56. Tube 50 is mechanically coupled by means represented by dashed line 58 to burner 56 to ensure that tube 50 is maintained the proper distance upstream of the hot zone 54. Alternatively, the heat source and gas feed tube may be kept stationary, and the rotating substrate tube may be traversed. The input end of tube 52 is connected to tube 50 by a collapsible member 60, a rotating seal 62 being disposed between member 60 and tube 52. As shown in FIG. 4, which is a cross-sectional view of the hot zone and adjacent regions of tube 52, gas emanating from tube 50 provides an effective mandrel or barrier to the reactants flowing in the direction of the arrows between tubes 50 and 52, thereby confining those reactants to an annular channel adjacent the wall of tube 52 in hot zone 54. For some distance downstream from hot zone 54, gas from tube 50 continues to act as a barrier to soot formed in the hot zone, thereby enhancing the probability that such soot will deposit on the wall of tube 52 as shown at 44'. Dashed line 66 of FIG. 5 represents the boundary between the gas emanating from tube 50 and the reactant vapor flowing in the hot zone 54.
The gas supplied to the hot zone by tube 50 may be any gas that does not detrimentally affect the resultant optical waveguide preform. Oxygen is preferred since it meets this requirement and is relatively inexpensive. Other gases such as argon, helium, nitrogen and the like may also be employed.
As shown in FIG. 4, the end of tube 50 is separated from the center of the hot zone by a distance x which must be great enough to prevent the deposition of soot on tube 50. The distance x will vary depending upon such parameters as the width of the burner and the temperature of the hot zone. The following findings were made for a deposition system wherein the outer diameters of tubes 50 and 52 were 20 and 38 mm, respectively, and the wall thicknesses thereof were 1.6 and 2 mm, respectively. The burner face orifices were located within a 45 mm diameter circle. In this system it was found that soot will deposit on tube 50 if the distance x is about 13 mm. Mixing of the reactant vapor stream with the gas flow through the baffle tube increases with the longitudinal distance from the baffle tube. The advantage derived by restricting reactant vapor to an annular region close to the wall of tube 52 may be obtained with a distance x up to about 15 cm. Best results are obtained when the distance x is within the range of 25-75 mm.
The size and shape of tube 50 should be such that a substantially laminar flow exists in the hot zone and in the region immediately downstream therefrom. Any turbulence which is introduced by tube 50 tends to pick up soot particles and carry them downstream to the exhaust tube.
In the prior art deposition process described in conjunction with FIGS. 1 and 2, deposition efficiency falls with an increase in tube diameter. An increase in deposition rate with increased tube diameter can be obtained by increasing tube diameter to about 30 mm. For tubes having diameters greater than 30 mm, deposition efficiency falls at a faster rate so that further increase in deposition rate is difficult to obtain. However, with the use of a baffle tube, the reactant vapor stream is restricted to a fixed distance from the inside surface of the bait tube that produces optimum deposition efficiency irrespective of bait tube diameter. The maximum size of the outer tube is limited by such considerations as that size tube for which the inner hole can be closed to form an optical waveguide preform. The wall thicknesses of the bait tube and the baffle tube are usually maintained relatively small, i.e., a few millimeters in thickness.
A cylindrically shaped baffle tube such as that illustrated in FIGS. 3 and 4 has been found to be easily constructed and to function satisfactorily to supply a mandrel of gas to the hot region of the bait tube without introducing an undue amount of turbulence. Other shapes such as that shown in FIG. 6 could also be employed to perform this function. The direction of gas flow from tube 70 is shown by arrow 72.
To illustrate the improvement in deposition rate and efficiency, a deposition system was operated both with and without a baffle tube 50 therein, all other process parameters remaining unchanged. Apparatus similar to that shown in FIG. 1 was employed to supply the reactant stream; however, only one reservoir 32 was employed. Oxygen was flowed through reservoir or bubbler 32 containing SiCl 4 maintained at 35° C. to provide a flow of about 2.5 g/m SiCl 4 . The flow rate of the BCl 3 was 92 sccm, and the flow of oxygen through flow meter 24 was 2.4 slm. The bait tube was a borosilicate glass tube having an outer diameter of 38 mm and a 2 mm wall thickness. A borosilicate glass having a composition of about 14 wt.% B 2 O 3 and 86 wt.% SiO 2 was deposited. From the flow rates of SiCl 4 and BCl 3 , the rate of oxide production was calculated to be 0.85 g/min SiO 2 and 0.29 g/min B 2 O 3 . The deposition rate was 0.251 g/min and the deposition efficiency was 26.2% when no baffle tube was employed. The system was then modified by adding a fused silica baffle tube having an outside diameter of 20 mm and a wall thickness of 1.6 mm. The end of the baffle tube was separated from the center of the hot zone by a distance of 50 mm. By employing the baffle tube, the deposition rate increased from 0.251 to 0.451 g/min and the efficiency increased from 26.2 to 43.2%.
Table I illustrates the effect of changing various of the process parameters on deposition rate and efficiency.
TABLE I______________________________________Oxide O.sub.2 Flow DepositionEx- Production (slm) Layer Effi-am- (g/min) By- Baf- Thickness Rate ciencyple SiO.sub.2 B.sub.2 O.sub.3 pass fle (mm) (g/min.) Percent______________________________________1 0.885 0.143 2.4 1.8 0.0196 0.461 44.12 1.48 0.234 2.4 1.8 0.0252 0.595 34.73 1.48 0.234 2.4 2.9 0.0231 0.545 31.84 1.48 0.234 2.4 1.05 0.0236 0.557 32.55 1.48 0.234 2.4 2.5 0.0300 0.691 40.36 1.48 0.234 2.0 2.2 0.0265 0.610 35.6______________________________________
In Examples 1 through 6 of this Table the bait tubes consisted of 38 mm OD borosilicate tubes having a 2 mm wall thickness and the baffle tubes consisted of 20 mm OD fused silica tubes having a 1.6 mm wall thickness. In the course of these experiments, a plurality of layers of glass were deposited within the bait tube in the manner described above. After 10 to 30 layers were deposited, the bait tubes were broken, and the thickness of each of the layers was measured under a microscope. The deposition rate was calculated from the layer thickness, and the deposition efficiency was defined as the deposition rate in g/min divided by the total mass flow of soot entering the tube, assuming a 100% conversion to oxides. The best results obtained were a deposition rate of 0.691 g/min, at 40.3% efficiency.
Based on the experiments reported above, it is obvious that improved deposition rates and deposition efficiencies can be realized during the manufacture of optical waveguide preforms. The following theoretical example is illustrative of the manner in which the apparatus of the present invention could be employed to manufacture such a perform.
A tube of commercial grade borosilicate glass having a 38 mm outside diameter and a 2 mm wall thickness is cleaned by sequential immersion in hydrofluoric acid, deionized water and alcohol. This bait tube, which is about 120 cm long, is attached to a 90 cm length of exhaust tube having a 65 mm outside diameter on one end and a 60 cm handle tube of the same size as the bait tube on the other end. This combination is inserted into a lathe such that the tubes are rotatably supported. The free end of the handle tube is provided with a rotatable seal through which a 180 cm long section of fused silica baffle tube having a 20 mm outside diameter and a 1.6 mm wall thickness is inserted. The baffle tube is supported at two different points along its length on a support which moves along with the burner. The burner traverses a 100 cm length of the bait tube at a rate of 25 cm/min. The burner is adjusted to provide a deposition temperature of 1800° C. at the outer surface of the bait tube. After the burner reaches the end of its traverse during which a layer of glass is deposited, it returns to its starting point at a rate of 100 cm/min.
Oxygen flows into the baffle tube at the rate of 2.5 slm. Three reservoirs are provided containing SiCl 4 , GeCl 4 and POCl 3 , respectively, these reservoirs being maintained at a temperature of 32° C. Oxygen flows through the first and third reservoirs at the rates of 0.3 lpm and 0.56 lpm, respectively, thereby delivering constant amounts of SiCl 4 and POCl 3 to the bait tube during the entire deposition process. The rate at which oxygen is supplied to the second container increases linearly from 0 to 0.7 lpm so that, during the first pass of the burner along the bait tube, no GeCl 4 is supplied to the bait tube, but the amount thereof is linearly increased during the remaining 49 passes of the burner. BCl 3 is supplied to the bait tube at the constant rate of 15 sccm, and bypass oxygen is supplied thereto at the rate of 2.4 slm.
After about 3 hours and 20 minutes, the time required for 50 burner passes, the rate of burner movement is decreased to 2.5 cm/min and the temperature increases to about 2200° C. at the outer surface of the bait tube. This causes the collapse of the bait tube into an optical waveguide preform having a solid cross-section. The usable length of this preform is about 84 cm.
The resulting preform or blank is then heated to a temperature at which the materials thereof have a low enough viscosity for drawing (approximately 2000° C.). This structure is then drawn to form about 25 km of optical waveguide filament having an outside diameter of about 110 μm. | A glass optical waveguide filament preform is prepared by chemical reaction of vapor ingredients within a glass bait tube. As the reactants flow through the bait tube, a hot zone traverses the tube to cause the deposition of sooty reaction products in the region immediately downstream of the hot zone. A baffle tube extends into that end of the bait tube into which the reactants flow. The baffle tube, which traverses the bait tube along with the burner, ends just short of the hot zone so that no soot is deposited thereon. A gas flowing from the baffle tube creates a gaseous mandrel which confines the flow of reactant vapors to an annular channel adjacent the bait tube wall in the hot zone, thereby increasing deposition rate and efficiency. | 2 |
FIELD OF THE INVENTION
[0001] This invention relates to a highly flame retardant, plasticized polyvinyl chloride (PVC) composition characterized by an absence of brittleness at low temperatures, substantial flexibility and low smoke properties. PVC formulations of the invention can be used for molding compositions, sheet materials, coating materials and electrical insulation materials. The composition of the invention is also suitable for PVC formed jackets, insulation for wire and cable products and roof sheathing.
BACKGROUND OF THE INVENTION
[0002] PVC compounds are a well known class of thermoplastic polymers which exhibit excellent chemical and corrosion resistance, physical and mechanical strength, and electrical insulative properties. Unplasticized versions of PVC are inherently flame resistant, and rigid PVC compounds require only additional antimony trioxide to achieve a high level of flame retardancy. When flexible forms of PVC are required, however, the addition of plasticizers to the formulation can increase its flammability. Conventional PVC is also apt to produce excessive smoke when exposed to ignition temperatures.
[0003] As is well known in the art, flame retardants must be in liquid form to plasticize PVC. See, Handbook of Polyvinyl Chloride Formulating, edited by Edward J. Wickson, 818-831, John Wiley & Sons (1993). The disclosure of this publication and all other publications and patents referred to herein are incorporated herein by reference.
[0004] Both triaryl and diaryl alkyl phosphate esters have been used to improve the flame retardancy of PVC. Nonetheless, continuing increases in demands in even better flame retardant properties for evermore stringent flexible PVC applications continue to challenge manufacturers.
[0005] The addition of dialkyl tetrahalophthalates such as dioctyl tetrabromophthalate or di-2-ethylhexyltetrabromophthalate has been able to achieve exceptional thermal stability and flame retardancy. The low temperature flexibility of PVC compounds is, however, compromised with the addition of such compounds.
[0006] There remains a continuing need in the art for even greater flexibility for PVC formulations and coatings.
[0007] When PVC burns, it gives off soot and suspended particles which are generally termed “smoke.” Although there is increasing demands for flexibility with thermal stability and flame retardancy, smoke generation is still an issue. As mentioned previously, the use of plasticizers necessary for flexibility and good processing properties generally increases the flammability of PVC compositions, especially if used at high levels. Although flame retardants are added to counteract the flammability of the plasticizers and reduce flammability of PVC compositions, they unfortunately increase smoke generation over the already considerable amount of smoke produced when PVC burns. In the case of plasticized PVC, the compounds forming the smoke can include not only the hydrocarbons, carbon oxides, and HCl from the PVC, but also the plasticizer compounds as well as their degradation products. The degradation products can also include aromatic and aliphatic hydrocarbons, carbon oxides, and hydrochloric acid. Smoke is particularly dangerous since it not only contains toxic by-products of combustion and thermal decomposition of the plastic. Smoke also restricts visibility and disorients potential victims, resulting in panic. Therefore, smoke suppressants, compounds which will inhibit the formation of smoke when the PVC composition burns, were developed.
[0008] The plastics industry has long recognized that the use of PVC in interior furnishings, building materials, and coverings for wire and cable presents the hazards of flame, toxic decomposition products, and smoke in the event of fire. It has therefore expended very considerable efforts to find additives for PVC which reduce smoke in the event that such PVC compositions are subjected to high temperatures or flame.
[0009] The most commercially recognized material for smoke suppression in PVC is ammonium octamolybdate (AOM). AOM is the premium material to make low smoke PVC compounds, particularly for plenum wire and cable applications. AOM is used in numerous PVC jacket formulations that pass the rigorous UL910 test for cables (copper conductor and fiber optic cables).
[0010] U.S. Pat. No. 4,153,792 discloses the production of amine molybdates as smoke suppressants, especially melamine molybdate by reacting an amine, such as melamine, with molybdenum trioxide in an aqueous acidic medium under reflux.
[0011] U.S. Pat. No. 4,217,292 also discloses the production of amine molybdates as smoke suppressants, preferably melamine molybdate by reacting an amine such as melamine with a stoichiometric quantity of molybdenum trioxide in an aqueous medium in the presence of an ammonium salt. The aqueous medium is essentially free of acid. The reaction may be conducted at temperatures within the range of 75-110° C.
[0012] Organic salts of divalent copper are also well known as smoke suppressants for polyvinyl chloride resins. Most studies were done using copper (II) acetate or copper (II) formate. These materials were designed to undergo decomposition to ground state copper (Cu°). This is referred to as a reductive coupling mechanism. Reductive coupling results in significant reduction of smoke upon ignition due to char formation. Copper in its ground state is active in reductive coupling of halogenated resins. The difficulty with copper (II) salts is two fold. The first difficulty is that the salts are blue or blue-green in color which also colors the resin systems. Secondly, the salts upon decomposition cause instability of the halogenated resin by dechlorination without reductive coupling. This dechlorination accelerates decomposition to olefinic species.
[0013] The use of melamine molybdate and copper compounds such as copper acetate, copper oxalate, and copper formate as smoke suppressants in halogenated resins, particularly PVC, is well known. This technology was never commercialized due to the technical failures of these systems. The pitfalls included blue to green discoloration of the resin systems, and poor thermal stability of the compounded resin systems, and loss of fire resistance characteristics due to the thermal instability of the compounded resin systems.
[0014] A variety of organic and inorganic compounds and salts have been proposed or used to reduce the smoke generation characteristics of rigid or plasticized PVC polymer compositions, but such agents have drawbacks such as not providing an improvement in smoke suppression for both rigid and plasticized PVC compositions, and unduly reducing the stability or processability of the polymer composition.
[0015] Another drawback with some agents employed to impart smoke suppression to PVC compositions unduly decrease the heat stability of the polymer compositions in which they are incorporated. In particular, some commercial smoke suppressant additives based on zinc compounds or combinations of zinc compounds with other compounds contain free zinc oxide, which can accelerate the degradation of PVC resins on exposure to temperatures above about 100° C.
[0016] In the area of PVC-based compositions for wire and cable covering applications, it is very desirable to have materials produce a minimum amount of smoke when burned, and produce light-colored smoke rather than dark smoke, while still possessing the good processing properties, mechanical toughness, and resistance to environmental stresses for which PVC compositions are known.
[0017] Accordingly, there is a continuing need for a PVC formulation having both high flexibility and very low smoke.
SUMMARY OF THE INVENTION
[0018] A feature of this invention is to provide low temperature flexibility of highly flame retardant plasticized PVC compounds by incorporating into PVC, according to the discovery of the invention, a mixture of a dialkyl or dialkylene tetrahalophthalate containing both tetrabromophthalates and tetrachlorophthalates and a brominated and/or chlorinated paraffin.
[0019] A further feature of this invention is to provide a PVC formulation that exhibits a decrease in smoke generation.
[0020] Another feature of the invention is to provide an improved PVC formulation for use in products such as molding compositions to form molded articles, sheet materials, roofing materials, insulation, jackets, coatings and articles of clothing.
[0021] A further feature of the invention is to provide a polyvinyl chloride composition containing a dialkyl tetrahalophthalate and a halogenated paraffin where the dialkyl tetrahalophthalate is included in an amount sufficient to inhibit separation of the liquid halogenated paraffin from the polyvinyl chloride composition and provide the desired flexible characteristics. The dialkyl tetrahalophthalate when used in combination with the halogenated paraffin enables the halogenated paraffin to be used in amounts greater than when the halogenated paraffin is used alone.
[0022] In the present invention, it has been discovered that the addition of a halogenated paraffin to a PVC flexibilizing formulation comprising one or more tetrahalophthalates further lowers smoke generation, improves flame retardancy and improves low temperature brittleness without adversely affecting PVC flexibility. Such formulations are useful as outer jackets and insulators for plenum wires and cables, wire coverings, articles of clothing including weatherproof apparel, flexible layers under roof sheathing, other roll and sheet based layers used in residential and commercial construction, shingles or other roof coverings, and flexible coatings applied to fabrics.
[0023] The various aspects of the invention are basically attained by providing a flexible PVC composition comprising a polyvinyl chloride resin, at least one tetrahalophthalate plasticizer in an amount sufficient to promote flexibility of the PVC composition, and a halogenated paraffin in an amount to provide flame and smoke retardant properties.
[0024] These and other aspects of the invention will become apparent from the following detailed description of the invention which discloses various embodiments of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention is directed to a polyvinyl chloride composition having flame retardant and smoke suppressing properties. The polyvinyl chloride compositions are suitable as molding compositions for forming molded articles, sheet goods such as roofing materials, coatings, coverings and insulation for wires and cables. The invention is further directed to a flame retardant and smoke suppressant agent that can be used in conjunction with a plasticizer for polyvinyl chloride resins. PVC containing at least one tetrahalophthalate, especially a mixture of tetrabromophthalate and tetrachlorophthalate, with a halogenated (especially brominated and/or chlorinated) paraffin show significant improvements in low temperature flexibility and decreased smoke generation potential. PVC compounds of the present invention also result in synergist improvements of flame retardancy with decreased smoke generation. The tetrahalophthalate is preferably a dialkyl or dialkenyl tetrahalophthalate.
[0026] PVC formulations according to one embodiment of the invention comprise: (A) a flexibilizing agent that includes one or more dialkyl or dialkenyl tetrahalophthalates, and (B) a smoke inhibitor that includes one or more halogenated alkyl hydrocarbons that are a liquid or solid form at 25° C. The halogenated alkyl hydrocarbons are preferably liquid halogenated paraffins. It has been found that the combination of the tetrahalophthalates and the halogenated paraffin provide improved flame and smoke retardancy than when the components are used individually in corresponding amounts without reducing the flexibility of the PVC composition.
[0027] The polyvinyl chloride composition of the invention preferably contains a mixture of at least one dialkyl or dialkenyl tetrahalophthalate and at least one halogenated paraffin where the various components do not separate from the PVC composition. The polyvinyl chloride composition in one embodiment includes at least 5 parts by weight and typically at least 10 parts by weight of the halogenated paraffin based on 100 parts by weight of the polyvinyl chloride resin. The dialkyl or dialkenyl tetrahalophthalate is included in an amount to provide the desired flexibility and to prevent the halogenated paraffin from separating or exuding from the polyvinyl chloride composition. It has been found that the halogenated paraffin can be added without reducing the flexibilizing properties of the tetrahalophthalate.
[0028] The dialkyl or dialkenyl tetrahalophthalate flexibilizing agents that can be used in the invention include one or more of fluoro-, chloro-, bromo-, and/or iodo-substituted dialkyl or dialkenyl tetrahalophthalates. Improved low temperature flexibility for PVC can be achieved with dialkyl tetrahalophthalate mixtures that are not adversely effected by the presence of the halogenated paraffin. Dialkyl tetrahalophthalates are disclosed in U.S. Pat. Nos. 6,534,575; 6,114,425 and 5,728,323, the disclosures of which are hereby incorporated by reference. Dialkyl or dialkenyl tetrahalophthalates useful in the present invention exhibit the following chemical structure:
[0000]
[0000] wherein:
[0029] R is an alkyl or alkenyl having 5-15 carbon atoms,
[0030] R′ is alkyl or alkenyl having 5-15 carbon atoms, and where R and R′ can be the same or different, and
[0031] X is independently F, Cl, Br or I.
[0032] In one preferred embodiment, R and R′ are independently a C 9 -C 11 alkyl or alkenyl.
[0033] The dialkyl or dialkenyl tetrahalophthalates used in the PVC compound of the present invention may be prepared using methods known in the art. Preferably, the dialkyl tetrahalophthalates used in the PVC compound of the present invention are prepared in accordance with the teachings in U.S. Pat. No. 6,114,425 to Day et al, the disclosure of which is hereby incorporated by reference.
[0034] The tetrahalophthalate compounds provide improved low temperature flexibility, increased flame retardancy and decreased smoke generation of polyvinyl chloride resins.
[0035] Dialkyl tetrahalophthalate compounds useful in the present invention are preferably included at a concentration within the range of about 0.01-25% by weight based on total weight of the PVC composition depending on the degree of flexibility desired for the final product and the PVC material.
[0036] In one embodiment of the invention, two or more dialkyl tetrahalophthalates are used in combination. The weight ratio of the two dialkyl tetrahalophthalate flexibilizing agents in the mixture can be within the range from about 1:50 to about 1:1. In another embodiment a dialkyl tetrachlorophthalate can be used in combination with a dialkyl tetrabromophthalate preferably within the range of 1:10 to about 1:8, and most preferably about 1:4 to about 1:3 dialkyl. In one embodiment of the invention, the dialkyl tetrahalophthalate includes a mixture of dialkyl tetrachlorophthalate and dialkyl tetrabromophthalate where the mixture includes the dialkyl tetrachlorophthalate in an amount of about 1 to 99 wt %, preferably about 1 to 50 wt %, and more preferably about 25 to 33 wt % based on the total weight of the mixture.
[0037] The halogenated alkyl hydrocarbon smoke suppressing agents used according to the invention preferably include brominated and/or chlorinated alkyl compounds, preferably in the form of halogenated paraffinic materials. The smoke suppressing agents are preferably paraffinic hydrocarbons having a halogen content of about 30 wt % to about 70 wt % based on the weight of the paraffin. In one embodiment, the paraffin is liquid at room temperature and about 10-30 carbon atoms.
[0038] The halogenated paraffin can be a brominated paraffin, a chlorinated paraffin, a bromochlorinated paraffin, and mixtures thereof produced from a straight chain C 10 to C 20 alkyl. In one embodiment, the smoke suppressing agent is a bromochlorinated liquid paraffin having substantially equal amounts of bromine and chlorine by weight based on the weight of the liquid paraffin. In an embodiment of the invention, the liquid paraffin can have a bromine content of about 15 wt % to about 35 wt % and a chlorine content of about 15 wt % to about 35 wt % based on the total weight of the paraffin. In another embodiment, the liquid paraffin can have a bromine content of about 30 wt % to about 35 wt % and a chlorine content of 30 wt % to 3 wt % based on the total weight of the liquid paraffin.
[0039] Examples of suitable halogenated paraffins useful in the invention include commercially available liquid halogenated materials sold under the trade name DOVERGUARD (Dover Chemical Corporation, Dover, Ohio). DOVERGUARD 9119 (Dover Chemical Corporation, Dover, Ohio) is an example of one preferred material having 33 wt % bromine and 33 wt % chlorine in an unspecified variety of olefins that exhibits a Gardner color of 1, a viscosity of 65 poise at 25° C., and a specific gravity of 1.58 at 50° C. Commercially available halogenated paraffins are a mixture or blend of halogenated straight chain C 10 -C 30 alkyls.
[0040] The halogenated paraffin can be used in an amount within the range of about 1-99% by weight based on the combined weight of the dialkyl tetrahalophthalate and halogenated paraffin mixture. In another embodiment, the halogenated paraffin is included in an amount of about 1 to 50 wt %, and more preferably 25 to 33 wt % based on the combined weight of the dialkyl tetrahalophthalate and halogenated paraffin mixture.
[0041] Mixtures of dialkyl tetrahalophthalate and halogenated paraffin can be prepared in any of a number of ways. For example, the dialkyl tetrahalophthalate flexibilizing agents can be mixed until homogeneous. The tetrahalophthalates can then be combined with the halogenated paraffin and added as a mixture to the PVC resin or the components can be added separately.
[0042] In one embodiment, the PVC formulation also includes a flame retardant synergist (e.g., antimony trioxide), a further plasticizer (e.g., trioctyl trimellitate), and/or a stabilizer (e.g., a calcium-zinc stabilizer).
[0043] The mixture or combination of the dialkyl tetrahalophthalate and halogenated paraffin are admixed with the polyvinyl chloride resin in an amount to provide the desired flexibility, flame and smoke retardancy. For example, the mixture or combined weight of the dialkyl tetrahalophthalate and halogenated paraffin can range from about 10 wt % to 25 wt %, and preferably about 15 wt % to 20 wt % based on the total weight of the polyvinyl chloride composition. In another embodiment, the combined weight of the dialkyl tetrahalophthalate and halogenated paraffin is about 20 parts by weight to about 40 parts by weight, and preferably about 25 parts by weight to 35 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. The dialkyl or dialkenyl tetrahalophthalate is typically included in an amount of about 15-25 parts by weight, and preferably about 18-22 parts by weight based on 100 parts by weight of the polyvinylchloride. The halogenated paraffin is typically included in an amount of about 5-15 parts by weight, and preferably about 8-12 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.
[0044] The finished polyvinyl chloride composition typically contains about 10 wt % to about 12 wt % dialkyl tetrahalophthalate and about 5 wt % to about 7 wt % halogenated paraffin based on the total weight of the polyvinyl chloride resin composition. In other embodiments, the polyvinyl chloride composition can include the dialkyl tetrahalophthalate in an amount of about 5-20 wt % and the halogenated paraffin in an amount of about 3-10 wt % based on the total weight of the polyvinyl chloride composition.
[0045] It has been found that the combination of the dialkyl tetrahalophthalate and the halogenated paraffin provide improved flexibility and flame and smoke retardancy that cannot be obtained by the component individually. In particular, it has been found that the halogenated paraffin by itself has limited dispersibility in the polyvinyl chloride resin. Amounts of the halogenated paraffin without the use of the dialkyl tetrahalophthalate in amounts greater than 5 parts by weight per 100 parts by weight of the polyvinyl chloride resin separate and exuded from the resin composition as a sticky oil. When used in combination with the dialkyl tetrahalophthalate, the amount of the halogenated paraffin can be incorporated in amounts of at least 10 parts and up to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.
EXAMPLES
[0046] For Examples 1-3, the base PVC polymer, plasticizer, stabilizer, flame retardant synergist, and the dialkyl tetrahalophthalate-brominated/chlorinated paraffin mixture were combined and thoroughly mixed. Initial mixing of the ingredients was carried out in a blender. The resulting charge was transferred to a 2 roll mill and preheated to 350° F. for fusion and further mixing. Rolling time was for 5 minutes under 1260 psi compression at 337° F. for compression molding of the mixture into test sheets.
[0047] The standard for PVC compression molding as known in the art is described in standardized test methods ASTM Designation: D-1928-90 and ASTM D-746, which are herein incorporated reference. Standardized test methods ASTM D-1928-90 and ASTM D-746 disclose the protocol for preparing compression molded polyethylene test sheets and PVC compression molding of the mixture into test specimens. In the present case, the specimens prepared according to these standards were subjected to physical, mechanical, and flame retardancy testing as described below.
[0048] Each example included tests to determine the tensile properties of the compressed PVC using standard dumbbell-shaped test specimens according to ASTM Designation D-638, published in 1995. In this test method, the test specimen is clamped by and between grips. The grips extend in opposed directions thereby stretching the test specimens until the specimen breaks. The test measures: (1) Tensile Modulus, which is the ratio of stress to corresponding strain below the proportional limit of a material and expressed in force per unit area (2) Tensile Strength at Break, which is the maximum tensile stress (tensile load per unit area of minimum original cross section) sustained by the specimen during a tension test at specimen break, and (3) Elongation, which is the elongation of a test specimen expressed as a percent of the gage length. An increase in these test factors indicates a more flexible test specimen.
[0049] Test specimen hardness was also measured. The standard hardness test method is found in the ASTM D-2240, published in 1995. This test results are based on the penetration of an indentor when forced into the test specimen.
[0050] Flame retardancy of the control and test formulations were determined by the Designation ASTM D-2863, published in 1995, to give oxygen index values. The oxygen index is equal to the minimum concentration of oxygen, expressed as volume percent, in a mixture of oxygen and nitrogen that will just support flaming combustion of a material initially at room temperature. A higher oxygen index indicates higher flame retardancy.
[0051] The test specimens were tested for the density of smoke generated by burning the test specimens in an NBS Smoke Chamber using the flaming mode in accordance with the ASTM E662-95 publication.
[0052] The test specimens were also tested for Brittleness Temperature. The brittleness of a test specimen is determined by immersing the specimen in a bath containing a heat transfer medium that is cooled. The specimens are struck at a striking element at a specified linear speed and then examined. The brittleness temperature is the temperature at which 50% of the specimens fail.
[0053] PVC resin (the base PVC resin used was GEON 30 from the Geon Corporation, now PolyOne Corporation) was compounded in a 2 roll mill in accordance with the procedures disclosed in ASTM D-1928 using the below mentioned Control and Test Formulations.
Examples 1-3
[0054] Examples 1-3 were prepared and tested according to the procedures discussed above. The proportions, components and test results are presented in Table 1.
[0000]
TABLE 1
Example 1
(CONTROL)
Example 2
Example 3
PVC Resin (Geon 30)
100
100
100
Trioctyl Trimellitate
34.3
34.3
34.3
(UNIPLEX 546-A)
Bis (2-Ethylhexyl
—
20
—
tetrachlorophthalate
Brominated/Chlorinated
—
10
10
Paraffin
(DOVERGUARD 9119)
Bis(2-Ethylhexyl
30
—
20
tetrabromophthalate)
(UNIPLEX FRP-45)
Antimony Oxide
5
5
5
Calcium-Zinc Stabilizer
5
5
5
Tensile Modulus at 100%
1760
2070
1900
Shore A Hardness (ASTM
88
88
90
D-224095, A Scale)
Tensile Strength at Break
2050
3480
3330
(ASTM D638-95)
Elongation (%)(ASTM
278
390
360
D638-95)
Oxygen Index (ASTM
33
37
41
D2863-95)
NBS Smoke(ASTM E662-
440
240
265
95)
Brittleness Temperature,
−12
−40
−32
° C. (ASTM D746-95)
[0055] The data in Table 1 shows that Examples 2 and 3 exhibited improved tensile modulus, tensile strength, elongation, oxygen index, smoke and brittleness relative to the control of Example 1. Both Examples 2 and 3, respectively, exhibited an 18% and 8% improvement in tensile modulus, 70% and 62% increase in tensile strength at break, 40% and 29% increase in tensile strength elongation, 12% and 24% increase in oxygen index, 45% and 40% decrease in NBS smoke and 233% and 167% increase in brittleness temperature.
[0056] The test data of Table 1 shows that the polyvinyl chloride resin composition that contain the halogenated paraffin exhibited an increase in tensile modulus, tensile strength, elongation, oxygen index, smoke and brittleness compared to Example 1 which contained only Bis-2-ethylhexyl-tetrabromophthalate. The differences between Examples 2 and 3 are due to the specific dialkyl tetrahalophthalate. Examples 2 and 3 which contained 10 parts by weight of the brominated/chlorinated paraffin exhibited no separation of the compound from the compositions. Previous samples prepared without the dialkyl tetrahalophthalate exhibit separation of the brominated/chlorinated paraffin when present in amounts greater than 5 parts by weight based on 100 parts by weight of the PVC resin.
[0057] While advantageous embodiments have been chosen to illustrate the invention, it will be understood by those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention as defined in the appended claims. | A highly flame retardant plasticized polyvinyl chloride composition includes a mixture of a dialkyl or dialkenyl tetrahalophthalate and a brominated/chlorinated paraffin. The composition exhibits an absence of brittleness, and substantial flexibility at low temperatures. The composition can be used to form sheet materials, molding compositions, roofing materials, PVC formed jackets and insulation for wire and cable products. | 2 |
SUMMARY OF THE INVENTION
The present invention relates to an external combustion engine for converting heat energy into rotational mechanical energy with improved power output in light of the heat input and engine weight and size. Furthermore, the operation of the engine is reversible so that it may be used as a highly efficient heat pump when the engine shaft is driven by an outside source of mechanical energy.
In a preferred embodiment, the rotary heat engine of the present invention comprises a ring-like stator having an elongated interior oval rotor chamber defined by a pair of adjoining lobes forming a high displacement high temperature fluid chamber and a low displacement low temperature fluid chamber, respectively. Each of the high and low temperature chambers includes an inlet port for admitting working fluid into the chamber, and an outlet port circumferentially spaced from the inlet port for exhausting working fluid.
A substantially cylindrical slotted rotor is rotatably and eccentrically mounted within the rotor chamber such that the high temperature chamber defines a greater volume than the low temperature chamber. The rotor contains a plurality of outwardly extending spring biased sliding vanes, the outer ends of which are in sliding engagement with the inner surface of the rotor chamber, and the sides of which are in sliding engagement with the inner surface of the end plates, to provide a sliding seal therealong.
A fluid heating path is formed between the outlet port of the low temperature fluid chamber and the inlet port of the high temperature fluid chamber, and includes a fluid heating device for heating the working fluid by combustion heat, waste heat, geothermal, solar, etc. A bypass path may also be provided around the fluid heater for regulating the amount of heat supplied to the working fluid, and consequently the power output from the heat engine rotor.
A fluid cooling path is similarly formed between the outlet port of the high temperature chamber and the inlet port of the low temperature chamber, and includes heat rejection means for removing heat energy from the working fluid. An economizer heat exchanger may also be provided between the cooling and heating paths for preheating fluid supplied to the fluid heater.
The heat engine of the present invention is designed to optimize operation of the engine with changes in varying temperatures, heat availability and mechanical load by modifying the eccentricity of the rotor within the rotor chamber to change the relative working volumes of the high temperature and low temperature fluid chambers. This operation is accomplished by varying the relative position of the cylindrical rotor with respect to the oval-shaped rotor chamber to modify the relative displacements of the high and low temperature chambers.
In another embodiment, the rotor shafts of similarly configured heat engines may be coupled with one engine working as a motor and the other as a heat pump to advantageously form an external combustion powered or heating unit. In this configuration, the outlet port of the low temperature chamber of a first heat engine, which serves as a motor, is coupled through a fluid heater to the inlet port of the high temperature chamber of the motor. The outlet port of the high temperature chamber of the motor is coupled through the heat rejecting part of a heat exchanger to the inlet port of the low temperature chamber of the motor. Fluid leaving the heat receiving part of the heat exchanger is admitted to the inlet port of the high temperature chamber of the second engine which serves as a heat pump where the fluid is heated further by compression. The hot fluid leaving the high temperature chamber of the second engine is routed through a heat rejection device where it gives its heat to a warm reservoir, and is then admitted to the low temperature chamber of the heat pump where it loses heat due to expansion. After leaving the low temperature chamber of the heat pump, the cold fluid is routed through a fluid heating device where it picks up heat from a cold reservoir. Subsequently, the fluid is routed through the heat receiving part of the heat exchanger where it picks up the waste heat from the first engine. Economizer means may also be provided between the heating and cooling fluid flow paths as required.
In another embodiment, the outlet port of the low temperature chamber of the first heat engine, which serves as a motor, is coupled through a fluid heater and the heat receiving part of a heat exchanger to the inlet port of the high temperature chamber, while the outlet port of the high temperature chamber of the motor is coupled to the inlet port of the low temperature chamber of the motor through a heat rejection device where the working fluid loses heat to a warm reservoir. A second heat engine is coupled to the first heat engine to serve as a heat pump. The outlet port of the low temperature chamber of the heat pump is coupled to the inlet port of the high temperature chamber of the heat pump through a fluid heating device where the working fluid receives heat from a cold reservoir. The output port of the high temperature chamber of heat pump is connected to the inlet port of the low temperature chamber of the heat pump through the heat rejection part of the heat exchanger where the working fluid loses heat to preheat the fluid serving the motor.
Further details of the invention will become apparent from the description which follows.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic diagram of the heat engine system of the present invention illustrating a side view, partially in cross section, of the rotary heat engine.
FIG. 2 is a front elevation view, partially in cross section, of the rotary heat engine of the present invention.
FIG. 3 is a front elevation view, partially in cross section, of the heat engine of the present invention with the rotor eccentrically displaced with respect to the stator from the position shown in FIG. 2.
FIG. 4 is a schematic view illustrating a first embodiment of a pair of mechanically coupled heat engines operating as an external combustion powered heating unit.
FIG. 5 is a schematic diagram of a second embodiment using a pair of mechanically coupled heat engines operating as an external combustion powered refrigeration unit.
DETAILED DESCRIPTION
The rotary heat engine system of the present invention is generally illustrated at 1 in FIG. 1-FIG. 3. Fundamentally, system 1 comprises a rotary heat engine 2 which produces rotational mechanical energy by means of a working fluid flowing in fluid heating loop 3 and fluid cooling loop 4. As will be explained in more detail hereinafter, the working fluid, such as hydrogen, helium, nitrogen, mercury vapor, tetrafluoromethane, etc., is heated in the heating loop 3, undergoes an expansion cycle in heat engine 2, is cooled in a cooling loop 4, and finally undergoes a compression cycle in engine 2. It will be noted that the working fluid flow is unidirectional, thereby avoiding considerable energy losses which have previously occurred with heat engines using reciprocating elements where masses of highly condensed gases must be alternately accelerated in opposite directions.
Rotary heat engine 2 generally includes an oval stator or cam ring 5. The interior of ring 5 forms an oval rotor chamber 6 defined by a pair of adjoining lobes forming a high temperature fluid chamber 7 and a low temperature fluid chamber 8. For purposes of an exemplary showing, ring 5 is constructed in two parts, an upper semi-cylindrical-like ring segment 5a, and a substantially identical lower semi-cylindrical-like ring segment 5b. Each ring segment comprises an outer curved portion terminating in a pair of spaced substantially parallel arm members. This construction results in a rotor chamber having substantially circular upper and lower surfaces 9 and 10, respectively, and intermediate plane parallel surfaces 11 and 12. In general, surfaces 11 and 12 will be of sufficient length to provide the desired range of adjustability between the rotor and stator as will be explained in more detail hereinafter. The ends of the arm portions adjacent surfaces 11 and 12 are substantially flat and parallel to facilitate joining the ring segments together by means of a pair of thin flat thermally insulating plates or gaskets 13 which prevent transfer of heat between ring segments 5 a and 5b. While for purposes of an exemplary showing, rotor chamber 6 has been described and illustrated as having rounded upper and lower surfaces, as well as intermediate substantially planar surfaces, it will be understood that other shapes may be utilized for the rotor chamber. Furthermore, ring 5 may be of unitary construction rather than made in separate parts.
Rotor chamber 6 is closed by means of a pair of substantially flat end plates 14 and 15 abuttingly and slidably engaging the end surfaces of stator ring 5. In general, end plates 14 and 15 will be urged firmly against the end surfaces of ring 5 by means not shown to insure a fluid tight seal therebetween. The sliding fit between these members permits adjustment of the engine characteristics as will be described in more detail below. As best shown in FIG. 1, upper ring segment 5a contains an orifice 16 extending therethrough adjacent surface 12 and forming an inlet port for admitting working fluid into high temperature chamber 7. As illustrated in FIG. 1, inlet port 16 extends obliquely through the wall of upper ring 5a so that working fluid is directed generally toward upper surface 9. A second orifice 17 spaced circumferentially from inlet port 16 adjacent surface 11 forms an outlet port for exhausting working fluid from high temperature chamber 7. In general, outlet port 17 will also extend obliquely through the wall of upper ring segment 5a so that the inlet end of port 17 is generally directed toward upper surface 9 of high temperature chamber 7. In general, this construction is similar to that commonly found in vane pumps.
Lower ring segment 5b is similarly configured and includes an orifice 18 extending obliquely through the wall of lower ring segment 5b adjacent surface 11 beneath outlet port 17. Orifice 18 forms an inlet port for delivering working fluid to low temperature chamber 8. Similarly, a second orifice 19 is circumferentially spaced from inlet port 18 underlying inlet port 16 to form an outlet port for exhausting working fluid from low temperature chamber 8.
As described and illustrated above, ports 16-19 extend through the walls of stator ring 5 as illustrated in FIG. 1, and by dashed lines in FIG. 2 and FIG. 3. However, the present invention contemplates an alternate arrangement where working fluid is introduced into and exhausted from rotor chamber 6 through appropriate orifice ports extending through one or both end plates 14 and 15. For example, the inlet port to high temperature chamber 7 may be formed by an orifice 20 extending through end plate 15 adjacent surface 12, while working fluid may be exhausted from high temperature chamber 7 by means of an outlet port formed by orifice 22 extending through end plate 14 adjacent surface 11. Similarly, working fluid may be introduced into low temperature chamber 8 by means of an inlet port formed by orifice 21 extending through end plate 15 adjacent surface 11, with working fluid being exhausted from low temperature chamber 8 by means of orifice 23 forming an outlet port extending through end plate 14 adjacent surface 12. As illustrated in FIG. 1, orifices 22 and 23 have been illustrated in dashed lines to illustrate their relative position on end plate 14.
A substantially cylindrical slotted rotor 24 is eccentrically disposed within rotor chamber 6 such that the volume defined by high temperature chamber 7 is greater than the volume defined by low temperature chamber 8. Consequently, the displacement of high temperature chamber 7 will be greater than the displacement of low temperature chamber 8. One end of rotor 24 terminates in a shaft 25 rotatably supported in ball bearing 26, for example. Similarly, the opposite end of rotor 24 may terminate in a similar shaft 27 rotatably supported by end plate 14. This construction permits rotor 24 to rotate freely about its axis, with mechanical energy being supplied to or removed from either of shafts 25 or 27. Alternatively, rotor 24 may be rotatably supported by a single shaft passing through either of end plates 14 or 15, as is well understood in the art.
Rotor 24 is supplied chordwise with four elongated slots 29 disposed around axis of rotation 30, such that adjacent slots 29 are substantially perpendicular to each other. As used herein, "chordwise" means that each slot extends from a point on the periphery of rotor 24 to a point spaced from the axis of rotation 30. For purposes of an exemplary showing, slots 29 are arranged to extend slightly beyond the axis of rotation 30, and are inclined in the direction of rotation of rotor 24 as depicted by directional arrow 31.
Each slot 29 slidably receives an elongated extensible vane 32 having a rounded outer tip 33 which slidably engages the inner surface of rotor chamber 6 to provide a sliding seal. Vanes 32 may be biased outwardly by means of one or more compression springs 34 positioned between the lower surface of slot 29 and the inner end of vane 32. This construction permits vane 32 to move from a fully retracted position when passing over surfaces 11 or 12, to a fully extended position when passing over surfaces 10 or 9 respectively. Furthermore, the vanes are inclined in the direction of rotor rotation to facilitate retraction.
The remaining elements of rotary heat engine system 1 are illustrated in FIG. 1. The outlet end 35 of a fluid heating means 36 is connected by means of fluid conduit 37 to inlet port 16 of high temperature chamber 7. Fluid heater 36 may include any type of heat source capable of elevating the temperature of the working fluid flowing through it, such as a fuel burner, waste heat exchanger, solar heater, geothermal heater, etc. The inlet end 38 of fluid heater 36 is connected by means of fluid conduit 40 to the heat receiving side 49 of economizing heat exchanger 41. The inlet end of heat exchanger 41 is connected by means of fluid conduit 42 to outlet port 19 of low temperature chamber 8 to complete fluid heating path 3. A fluid heater bypass channel 43 may also be provided around fluid heater 36 and optionally controlled by valve 39 to regulate the engine power throughout. This arrangement provides a convenient means for controlling the heat energy supplied to heat engine 2 without restricting the flow of the working fluid. The fuel supply (not shown) for heat source means 36 may be closely coupled to valve 39, or may be thermostatically controlled as a function of the fluid temperature at outlet end 35 of fluid heater 36, or both. In addition, means may be provided for preheating the combustion materials. For example, as illustrated in FIG. 1, air and fuel fed through conduits 36a to a fuel burner comprising fluid heater 36, may be preheated by heat exchange means 44a using waste heat from heat rejection means 44.
Fluid cooling path 4 is formed by heat rejection means 44, the outlet end of which is connected by means of fluid conduit 45 to inlet port 18 of low temperature chamber 8, and the inlet end of which is connected by means of fluid conduit 46 to the outlet end of the heat rejecting side 48 of economizer heat exchanger 41. The inlet end of the heat rejecting side of heat exchanger 41 is connected by means of fluid conduit 47 to outlet port 17 of high temperature chamber 7. Heat rejection means 44 may comprise any device for removing heat from the working fluid before it enters the low temperature chamber of heat engine 2 such as a cooling tower, heat exchanger communicating with a low temperature sink, heat radiator, etc. It will be understood that in the embodiment described, fluid heater 36, heat exchanger 41, and heat rejection means 44 may be separate devices, or constructed as integral parts of heat engine 2.
When heat engine 2 is operated as a motor, high temperature chamber 7 works as an expansion device for driving rotor 24, while low temperature chamber 8 serves as a compression device. With rotor 24 turning in the direction indicated by directional arrow 31, working fluid at a low temperature T c enters low temperature chamber 8 by way of inlet port 18 and exhausts low temperature chamber 8 through outlet port 19 into the heat receiving portion of heat exchanger 41 where the working fluid is economically preheated. The working fluid is then heated by fluid heater 36, emerging therefrom at a high temperature T h , and enters high temperature chamber 7 by way of inlet port 16. The working fluid is expanded in high temperature chamber 7, and exits by way of outlet port 17 to the heat rejecting side of heat exchanger 41 where it gives up a portion of its remaining heat energy to the cooler working fluid which has exited low temperature chamber 8. The working fluid then proceeds through heat rejection means 44 where it is cooled by low temperature T c . The simultaneous operating cycles result in a positive pressure differential between heating path 3 and cooling path 4. Since the vanes in chamber 7 expose a greater area to the pressurized working fluid than vanes in chamber 8, the summation of forces exerted on the vanes results in a net torque driving rotor 24 counterclockwise, thus perpetuating the rotation and maintaining the driving pressure differential.
In the application where heat engine 2 is operated as a heat pump for transferring heat from a cold reservoir to a warmer reservoir, high temperature chamber 7 operates as a compressor, while the less voluminous low temperature chamber 8 serves as an expansion device to recover mechanical energy. In this situation, an outside mechanical prime mover (not shown) turns rotor 24 in a clockwise direction, such that the preheated working fluid is compressed in high temperature chamber 7 and forced through loop 3 which now forms a heat rejection path. This compression raises the temperature of the fluid to T h making heat available at means 36, which now functions as a heat rejector, e.g. a radiator. Working fluid exhausted from heat rejector means 36 passes through the now heat rejecting side 49 of heat exchanger 41 where it is further cooled and serves to economically preheat fluid flowing through the opposite side of the heat exchanger. The cooled working fluid leaving heat exchanger 41 enters low temperature chamber 8 through port 19 which functions as an expansion device to return part of the mechanical energy used in compressing the fluid to drive shaft 25 or 27 of engine 2. This expansion process cools the working fluid to temperature T c which is less than the temperature of the cold reservoir. Therefore the fluid will pick up heat from the cold reservoir; i.e. the temperature of the fluid is raised by its passage through what is now the heat receiving device 44 of the system and further by passage through the heat receiving side 48 of heat exchanger 41 to complete the heat pumping cycle.
As described hereinabove, the operation of the rotary heat engine system 1 may be optimized for changes in varying temperatures, heat availability and mechanical load, either manually or automatically, by modifying the eccentricity of rotor 24 within rotor chamber 6 to change the relative working volumes or displacement of high temperature fluid chamber 7 and low temperature fluid chamber 8. For example, as illustrated in FIG. 2, stator ring 5 has been adjusted with respect to rotor 24 so that the volume of high temperature chamber 7 is significantly greater than the volume of low temperature chamber 8 to accommodate a particular set of working conditions. However, in FIG. 3, stator ring 5 has been adjusted downwardly as shown by directional arrows 50 so that the volume of high temperature chamber 7 is only slightly greater than the volume of low temperature chamber 8 to accommodate a different set of operating conditions.
In general, rotor 24 and rotor chamber 6 will be dimensioned to insure a fluid-tight seal between the ends of rotor 24 and the inner bearing surfaces of end plates 14 and 15, to prevent leakage of the working fluid between chamber 7 and chamber 8.
In an alternative embodiment, two heat engines 102 and 202, one operating as a motor and the other operating as a heat pump, may be coupled mechanically to form an external combustion powered air conditioning or refrigeration or heating unit, such as illustrated schematically in FIG. 4 and FIG. 5. In these figures, elements structurally similar to those appearing in FIG. 1-FIG. 3 have been similarly designated.
The arrangement of FIG. 4 finds utility as a heating device. The drive shaft 127 of a first heat engine 102 operating as a motor has been mechanically connected by means of a coupling or the like, designated schematically by dashed line 61 in FIG. 4, to the drive shaft 225 of a second heat engine 202 operating as a heat pump. Each heat engine is structurally similar to heat engine 2 described above. The outlet port 119 of the low temperature chamber of heat engine 102, which serves as a motor is coupled through a fluid heater 36 where heat Q 1 is added to the fluid, to the inlet port 116 of the high temperature chamber of the motor 102. The outlet port 117 of the high temperature chamber of motor 102 is coupled through the heat rejecting part 71 of a heat exchanger 70 to the inlet port 118 of the low temperature chamber of motor 102. Fluid leaving the heat receiving part 72 of heat exchanger 70 is admitted to the inlet port 216 of the high temperature chamber of the second heat engine 202, which serves as a heat pump, where the fluid is heated further by compression. The hot fluid leaving the high temperature chamber of the second engine 202 via port 217 is routed through a heat rejection device 44, where heat Q 2 is given up to a warm reservoir such as a room to be heated. The fluid then flows to the input port 218 of the low temperature chamber of heat pump 202 where it loses heat due to expansion. After leaving the low temperature chamber of heat pump 202 through port 219, the cold fluid is routed through a fluid heating device 73 where the fluid absorbs heat Q 13 from a cold reservoir, such as a body of water, for example. Subsequently, the fluid is routed through the heat receiving part 72 of heat exchanger 70 where it picks up waste heat from motor 102, thus completing the cycle.
The embodiment of FIG. 5 is useful for cooling purposes and includes similar heat engines 102 and 202 acting as motor and heat pump, respectively, which are connected by coupling 61. Heat Q 1 is added to the fluid in fluid heater 36. The outlet of fluid heater 36 is coupled to inlet port 116 of engine 102. Outlet port 117 of engine 102 is connected to port 118 through heat rejection device 44 which exhausts heat Q 2 to a warm reservoir. Port 119 is connected through the heat receiving part 80 of heat exchanger 81 to fluid heater 36 to preheat the fluid. The heat rejecting part 82 of heat exchanger 81 is connected between ports 217 and 218 of heat pump 202, while heat receiving means absorbing heat Q 3 from a cold reservoir is connected between ports 216 and 219 of heat pump 202.
In the embodiment of FIG. 4 and FIG. 5, the working fluid associated with heat engine 102 may be different from that used in heat engine 202. In addition, the relative sizes of the heat engines may be different to accommodate particular design requirements.
It will be understood that various changes in the details, materials, steps and arrangements of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. For example, multiple high and low temperature chambers may be distrubted circumferentially around the circumference of rotor chamber 6 to balance radial bearing strain on shaft bearings 26 and 28. | A rotary external combustion heat engine for furnishing mechanical energy from a source of heat. The engine includes a ring-like stator having an oval rotor chamber enclosing a cylindrical rotor eccentrically placed within the chamber to define a high displacement high temperature fluid chamber and a lower displacement low temperature fluid chamber. A plurality of extensible vanes extend outwardly from the rotor in sliding contact with the inner surface of the rotor chamber. A source of heat supplies thermal energy to fluid supplied to the high temperature chamber, while a heat sink cools fluid supplied to the low temperature chamber. An economizer heat exchanger is also provided for preheating the working fluid. The relative position of the rotor within the rotor chamber is adjustable for varying the relative displacement of the fluid chambers to control engine working parameters. In another embodiment, a first heat engine is utilized as a motor and is mechanically coupled to a second heat engine utilized as a heat pump for providing an external combustion heat pump or refrigeration unit. | 5 |
BACKGROUND OF THE INVENTION
[0001] Interconnect lines electrically connect devices within an integrated circuit (IC). IC devices may include one or more complimentary metal oxide semiconductor (CMOS) transistors having diffused source and drain regions separated by channel regions, and gates that are located over the channel regions. In practice, an IC may include thousands or millions of devices, such as CMOS transistors.
[0002] Interconnect lines of ICs generally take the form of patterned metallization layers. Interconnect lines may be formed one on top of another with an electrically insulating material therebetween. As will be more fully described below, one interconnect line may be formed under another interconnect line and electrically connected thereto by one or more tungsten plugs.
[0003] ICs are manufactured on silicon substrates using conventional photolithographic techniques. FIGS. 1-8 show a cross-sectional view of an IC during a portion of its manufacture. More particularly, FIG. 1 shows a first dielectric layer 12 , a first metallization layer 14 , and a photoresist layer 16 formed over substrate 10 . Layers 12 - 16 are formed using conventional techniques such as chemical vapor deposition, sputtering, or spin-on coating.
[0004] First matallization layer 14 can be formed into a first interconnect line. This first interconnect line can be formed by selectively exposing photoresist layer 16 to light passing through a patterned reticle (not shown). Photoresist areas of layer 16 exposed to light are subsequently removed using conventional development techniques. FIG. 2 shows the substrate 10 of FIG. 1 after development of photoresist layer 16 to form photoresist mask pattern 20 .
[0005] Once the photoresist mask pattern 20 is formed, a plasma etching operation is applied to the IC shown in FIG. 2 to remove portions of metallization layer 14 that are not covered by photoresist mask pattern 20 . FIG. 3 shows the IC of FIG. 2 after plasma etching thereof. The plasma etching operation results in first interconnect line 22 .
[0006] FIG. 4 shows the IC of FIG. 3 after a second dielectric layer 24 is deposited thereon. Although not shown, photoresist mask pattern 20 is removed prior to formation of second dielectric layer 24 . The second dielectric layer 24 and the first dielectric layer 12 may be formed from an insulating material such as silicon dioxide.
[0007] FIG. 5 shows the IC of FIG. 4 after a via 26 is formed within the second dielectric layer 24 . As is well known in the art, vias, such as via 26 , are formed by depositing a photoresist layer (not shown) over dielectric layer 24 , selectively exposing this photoresist layer to light passing through a patterned reticle having via hole patterns formed therein, developing and removing the exposed photoresist of form a photoresist via mask pattern, etching any dielectric layer 24 exposed through the photoresist via mask pattern, and removing the remaining photoresist via mask after etching dielectric layer 24 .
[0008] Once the vias are formed within the second dielectric layer 24 , the vias are filled with an electrically conductive material such as tungsten. As well is known in the art, vias, such as via 26 , are filled by depositing a barrier film by sputter or chemical vapor deposition, depositing a conductive film by sputter or chemical vapor deposition, and then removing the conductive film, and possibly removing the barrier film, over dielectric layer 24 , but not inside the via 26 . The barrier film is typically comprised of titanium, titanium nitride, or a titanium/titanium nitride stack. The conductive film is typically tungsten. The conductive film, and possibly the barrier film, is removed by plasma etching, chemical mechanical polishing, or wet etching. FIG. 6 shows via 26 of FIG. 5 filled with tungsten, thereby forming tungsten plug 30 .
[0009] After the tungsten plugs are formed, a second metallization layer is formed over dielectric layer 24 and the tungsten plugs, icluding tungsten plug 30 . This metallization layer is typically comprised of a metal stack that includes any combination of one or more the following: titanium, titanium nitride, aluminum, an aluminum copper alloy, or an aluminum silicon copper alloy. This metallization layer is then patterned using conventional photolithography and plasma etching to form an additional layer of interconnect lines. FIG. 7 shows the IC of FIG. 6 with a second interconnect line 32 formed thereon. The second interconnect line 32 is electrically coupled to the first interconnect line 22 via the tungsten plug 30 . First interconnect line 22 may be coupled at one end to a first device (i.e., a first CMOS transistor) The second interconnect line 32 may be coupled to a second device (i.e., a second CMOS transistor) or coupled to connections which lead to the outside of the chip package. Accordingly, the structure of the first interconnect line 22 , tungsten plug 30 , and second interconnect line 32 , function to interconnect the first and second IC devices or function to interconnect an IC device and external package connections.
[0010] As is well known in the art, conventional plasma etching to form interconnect lines (e.g., interconnect line 32 ) often leaves residual polymer (not shown) on the sides of the interconnect lines. To remove this residual polymer on the sides of the interconnect lines, a liquid cleaning solution is often used after plasma etch. Further, conventional plasma etching to form interconnect line 32 may leave a positive electrical charge interconnect line 32 , and thus, tungsten plug 30 and first interconnect line 22 . For purposes of explanation, it will be presumed that the structure consisting of first interconnect line 22 , tungsten plug 30 , and second interconnect line 32 is a floating structure such that both interconnect lines 22 and 30 and tungsten plug 30 will be positively charged before the polymer residue removal process.
[0011] After plasma etching, the IC shown in FIG. 7 is exposed to a cleaning solution to remove any polymer remaining after the plasma etching step. Typically this cleaning solution may be alkaline or basic in nature (i.e. pH is greater than 7), however, acidic solutions (i.e. pH is less than 7) can also be used. Although the cleaning solution works well in removing polymer residues, one, some, or all of the tungsten plugs that are exposed to the cleaning solution may dissolve or erode away during the polymer residue removal process. The cause is electrochemical corrosion caused by two dissimilar conductive materials being in contact, the interconnect line and the tungsten plug, while both conductive materials are simultaneously in contact with an electrolyte, the cleaning solution or rinsing solution, during the polymer removal process.
[0012] More and more devices are packed into smaller ICs. As such, the density of devices and interconnect lines in ICs has dramatically increased over the years. Unfortunately, this dense integration of devices and interconnect lines has the effect of pushing the limits of conventional photolithography patterning, which necessarily makes photolithography masks misalignments more likely to occur. An increase in misalignments will result in an increase of exposed tungsten plugs.
[0013] FIG. 7 illustrates the effects of misalignment of photolithography masks. More particularly, the misalignment of photolithography masks used to create second interconnect line 32 produces a misalignment of second interconnect line 32 with respect to tungsten plug 30 . As a result of this misalignment, tungsten plug 30 will be exposed to cleaning solution during the polymer residue removal step described above.
[0014] FIG. 8 illustrates how tungsten plug 30 could be corroded by the cleaning solution of the polymer residue removal process. As seen in FIG. 8 , a substantial portion of tungsten plug 30 , is removed by the aforementioned corrosion. Tungsten plug corrosion may have adverse effects on performance of the IC. For example, corrosion of tungsten plug 30 shown in FIG. 8 may be so extensive that first interconnect line 22 is no longer electrically coupled to second interconnect line 32 thereby creating an open circuit therebetween. IC devices coupled to second interconnect line 32 could be electrically isolated from IC devices coupled to first interconnect line 22 thereby resulting in an IC that fails to function for its intended purpose.
[0015] Clearly, there is a need to avoid tungsten plug corrosion in the manufacture of ICs. In 1998, a paper was published by S. Bothra, H. Sur, and V. Liang, entitled, “A New Failure Mechanism by Corrosion of Tungsten in a Tungsten Plug Process, ” IEEE Annual International Reliability Physics Symposium, pages 150-156. This paper, which is incorporated herein by reference in its entirety, describes some techniques for preventing tungsten plug corrosion. These techniques involve discharging the tungsten plugs prior to immersion in alkaline cleaning solution to remove polymer residue. In one technique described in the paper, tungsten plug discharge is accomplished by dipping ICs in an ionic solution prior to polymer residue removal. The paper describes that this ionic solution should have a pH near neutral (i.e. pH near 7). The paper describes deionized (DI) water as one form of ionic solution for discharging tungsten plugs. However, the paper found that a relatively long emersion time of several hours within the DI water was necessary to discharge exposed tungsten plugs, such as the exposed tungsten plug shown in FIG. 7 . The exposed tungsten plugs were found to remain in tact after subsequent emersion in the alkaline cleaning solution; however, noticeable corrosion of the interconnect lines, such as interconnect line 32 , was observed. Accordingly, this paper concluded that emersion in DI water of ICs for the purpose of discharging exposed tungsten plugs, was not a “practical” approach. It is noted that this paper should not be considered prior art to the invention claimed herein.
[0016] U.S. Pat. No. 6,277,742, describes another technique for preventing tungsten plug corrosion. In U.S. Pat. No. 6,277,742, an IC is dipped into an electrolyte solution sufficiently acid or alkaline. According to U.S. Pat. No. 6,277,742, charges accumulated can be discharged by dipping the IC into the electrolyte solution. Preferably, when an acid electrolyte solution is used, the pH value of the acid electrolyte solution is said to be less than 6.5. The acid electrolyte solution is said to include an oxy-acid aqueous solution such as acetic acid (CH 3 COOH), sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ). The acid electrolytic solution is said to include a hydrohalic acid like hydrofluoric acid (HF) or hydrochloric acid (HCL). An acid salt aqueous solution, for example, sodium hydrogen sulfate (NaHSO 4 ), ammonium chloride (NH 4 Cl) or ammonium nitride (NH 4 NO 3 ) is also said to be suitable. Preferably, when an alkaline electrolyte solution is used, the pH value of the alkaline electrolyte solution is greater than 7.5. The alkaline electrolyte solution is said to include either ammonium hydroxide (NH 4 OH) aqueous solution or metal hydroxide (M(OH) ) aqueous solution. The metal hydroxide aqueous solution includes sodium hydroxide (NaOH) or potassium hydroxide (KOH). An alkaline salt aqueous solution, for example, sodium acetate (CH 3 COONa) or sodium carbonate (Na 2 CO 3 ) is also said to be suitable. It is noted alkaline or acidic electrolytic solution may be environmentally hazardous or hazardous to those who are responsible for discharging ICs prior to polymer residue removal.
SUMMARY OF THE INVENTION
[0017] Disclosed herein is a method of making integrated circuits. In one embodiment the method includes forming tungsten plugs in the integrated circuit and forming electrically conductive interconnect lines in the integrated circuit after formation of the tungsten plugs. At least one tungsten plug is electrically connected to at least one electrically conductive interconnect line. Thereafter at least one electrically conductive interconnect line is contacted with water for a period of time less than 120 minutes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention may be better understood in its numerous objects, features, and advantages made apparent to those skilled in the art by referencing the accompanying drawings.
[0019] FIG. 1 is a cross-sectional view of a portion of a partially fabricated integrated circuit;
[0020] FIG. 2 shows the IC of FIG. 1 after patterning the photoresist layer to form photoresist mask pattern;
[0021] FIG. 3 shows the IC of FIG. 2 after etching the first metallization layer;
[0022] FIG. 4 illustrates the IC of FIG. 3 with a second dielectric layer formed thereon;
[0023] FIG. 5 illustrates the IC of FIG. 4 after formation of a via within the second dielectric layer;
[0024] FIG. 6 shows the IC of FIG. 5 with a tungsten plug formed therein;
[0025] FIG. 7 shows the IC of FIG. 6 after formation of a second interconnect line thereon;
[0026] FIG. 8 shows the IC of FIG. 7 after exposure to a cleaning solution to remove polymer residue;
[0027] FIG. 9 is a graph showing test results of an IC manufactured with and without use of one embodiment of the present invention to discharge tungsten plugs; and
[0028] FIG. 10 is another graph showing test results of an IC manufactured with and without use of one embodiment of the present invention to discharge tungsten plugs.
[0029] The use of the same reference symbols in different drawings indicates similar or identical items.
DETAILED DESCRIPTION
[0030] The present invention relates to a method of making ICs. In one embodiment the method includes forming a tungsten plug in a dielectric layer and forming an electrically conductive interconnect line partially or completely covering the after formation of the tungsten plug. FIG. 7 illustrates an exemplary, partially formed IC in which interconnect line 32 is formed after formation of dielectric layer 24 and tungsten plug 30 . The electrically conductive interconnect line 32 in FIG. 7 , may be formed from conductive materials such as a metal stack comprised of any combination of one or more of the following: titanium, titanium nitride, aluminum, an aluminum copper alloy, or an aluminum silicon copper alloy. The Tungsten plug 30 is electrically connected to conductive interconnect line 32 .
[0031] Formation of conductive line 32 may result in an unwanted polymer residue as described above. Moreover, formation of conductive line 32 may result in the accumulation of electrical charge on the conductive line 32 and the tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 . The polymer residue may be removed by a step or exposing the partially formed IC of FIG. 7 to a cleaning solution. Before the polymer residue removal step, but after the formation of the conductive interconnect line 32 , the partially formed IC is brought in contact with water for a period of time less than 120 minutes. More particularly interconnect line 32 connected to tungsten plug 30 (and tungsten plug 30 if not covered by interconnect 32 ), is contacted with water for a period of time less than 120 minutes. In one embodiment, contact is effected by dipping the partially formed IC into a bath of water. In another embodiment, the water is sprayed on the IC. In another embodiment, the water is dispensed on the IC by a nozzle. In a preferred embodiment, interconnect line 32 is contacted with water for a period of time equal to or less than 15 minutes.
[0032] The contact with the water fully or partially discharges conductive interconnect line 32 and tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 . It is noted that ICs may be created with more than two levels of interconnect lines. Interconnect lines 22 and 32 in FIG. 7 are lines in two separate levels. Ideally, each time a level of interconnect lines is formed, the newly formed interconnect lines should be contacted with water.
[0033] The water used to discharge conductive interconnect line 32 and/or tungsten plug 30 connected thereto and/or the underlying conductive line 22 connected to tungsten plug 30 , may have a pH at neutral or 7. It is noted that the pH of the water may be slightly higher or lower than neutral. In one embodiment, the water used is degasified. Degasified water can be formed during a distillation and/or filtration process which as much of the dissolved gases (i.e., nitrogen, oxygen, carbon dioxide, etc.) and microbubbles as possible are removed from water. In another embodiment, water that is not degasified and which has a pH at or near neutral, is used to discharge conductive interconnect line 32 and tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 . The water used to discharge conductive interconnect line 32 and tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 may be deionized (DI) water. DI water is water which has been “deionized” or has “no ions.” In a deionization process, water goes through an ion-exchange and/or reverse osmosis process in order to remove ions dissolved in the water (i.e. calcium, potassium, chlorine, fluorine, etc.) or other ionic impurities. This process may make the water purer and may control pH. In actuality, DI water still has ions because at all temperatures above absolute zero, water thermally dissociates into hydroxide ions and hydrogen ions (protons). In another embodiment, non-DI water is used to discharge conductive interconnect line 32 and tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 . In yet other embodiments, the water used to discharge conductive interconnect line 32 and tungsten plug 30 connected thereto and the underlying conductive line 22 connected to tungsten plug 30 may be: degasified and deionized; deionized but not degasified; degasified but not deionized; or neither degasified nor deionized.
[0034] FIGS. 9 and 10 graph the results of testing ICs during a 16 month period. The tested ICs are identical in design and were made with and without the step of dipping the ICs into a DI water bath for 120 minutes or less prior to exposure to an alkaline cleaning solution to remove polymer residue. ICs tested after month 13 were made using a 120 minute or less DI water-dip prior to polymer residue removal in accordance with one embodiment of the present invention, while ICs tested before month 13 were not made with the process step of dipping into DI water for 120 minutes or less prior to polymer residue removal. Except for the DI water dip step, the ICs tested were made using identical manufacturing tools and processes.
[0035] FIG. 9 shows that ICs (dies) made with the DI water dip step on average were less prone to failure as a result of tungsten plug corrosion when compared to ICs made without the DI water dip step. FIG. 10 shows that on average, the process yield (ICs that functioned properly versus ICs that failed to function properly) is higher when the DI water dip is used in the manufacturing process.
[0036] Although the present invention has been described in connection with several embodiments, the invention is not intended to be limited to the specific forms set forth herein. On the contrary, it is intended to cover such alternatives, modifications, and equivalents as can be reasonably included within the scope of the invention as defined by the appended claims. | Disclosed herein is a method of making integrated circuits. In one embodiment the method includes forming tungsten plugs in the integrated circuit and forming electrically conductive interconnect lines in the integrated circuit after formation of the tungsten plugs. At least one tungsten plug is electrically connected to at least one electrically conductive interconnect line. Thereafter at least one electrically conductive interconnect line is contacted with water for a period of time less than 120 minutes. | 7 |
This is a Continuation of U.S. patent application Ser. No. 09/234,485 filed Jan. 21, 1999, now U.S. Pat No. 6,879, 411. The entire disclosure of the prior application is hereby incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a facsimile system including a facsimile machine and a computer for controlling names of addressees, facsimile numbers, etc.
2. Description of the Related Art
In conventional facsimile machines, data of names of addressees to whom image data read from an original or manuscript and corresponding facsimile numbers as selected registration numbers (such as abbreviated numbers) is stored in a memory. When a registration number of an addressee is input upon transmission of image data of the original, the name of address and the facsimile number both corresponding to the input registration number are read and displayed on a liquid-crystal display section. When a user confirms the displayed contents and then depresses a transmission button, the original is read and the image data read from the original is transmitted to the displayed addressee.
In the above-described facsimile machines, however, keys and abbreviated dialing buttons depressed for input of a facsimile number also serve as character keys. Further, every one key is allotted to a plurality of characters so that characters can be input by use of a small number of keys. Moreover, the individual keys are small and the liquid-crystal display section displaying the input characters also has a small display area. The above-mentioned keys etc. need to be operated so that the characters are input when the names of addresses are registered. This registering work takes much time as compared with the case where a keyboard equipped in a computer or word processor is operated.
To solve the above-described problem, the prior art has proposed an arrangement in which a computer is connected to a facsimile machine. In this arrangement, data of information about the addressee such as the names of addressees and corresponding facsimile numbers is input into the computer. Thereafter, the data of information about the addressees is transferred to the facsimile machine and stored in a suitable memory. In the proposed arrangement, however, in the case where the user makes reference to the data of information about the addressee when the original is to be transmitted by the facsimile machine, the user needs to move from a location where the facsimile machine is equipped to a location where the computer is equipped, so that the user operates the computer in order that the data of information about the addressee may be displayed. Thus, the user cannot make reference to the data of information about the addressees at the facsimile machine side. This results in a troublesome operation.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a facsimile system in which the data of information about the addressees stored at the computer side can be referred to at the facsimile machine side.
The present invention relates a communication system comprising a communication terminal having a function of specifying an addressee from addressee identification information to communicate with the specified addressee; a computer transmitting addressee identification information to the communication terminal; a computer-side store unit provided at a computer side that stores the addressee identification information; a computer-side fetching unit provided at the computer side that fetches the addressee identification information from the computer-side store unit; a computer-side output unit that outputs the fetched addressee identification information to the communication terminal in case of communication so that the communication is executed according to a piece of addressee identification information selected from the fetched addressee identification information; a retrieval information input unit provided in the communication terminal and operated by an operator for input of retrieval information relating the addressee identification information; an instruction unit provided in the communication terminal so as to instruct the computer at the communication terminal side to retrieve via the computer-side fetching unit the addressee identification information stored in the computer-side store unit, the instruction unit instructing the computer to fetch the addressee identification information based on the retrieval information supplied by an operator; and a terminal side display that displays the addressee identification information outputted by the computer-side output unit so that the piece of addressee identification information is selected at the communication terminal side.
According to the above-described communication system, the computer-side fetching unit refers to and fetches the addressee identification information stored in the computer-side store unit when the instruction unit gives the computer an instruction to refer to the addressee identification information. As a result, for example, a facsimile machine can refer to the addressee identification information. Accordingly, when addressee identification information which cannot be stored at the facsimile machine side is stored in the computer-side store unit, the addressee identification information stored in the computer-side store unit can freely be referred to by the instruction unit at the facsimile machine side. Consequently, a quantity of substantially storable addressee identification information can be increased to a large degree.
The invention further provides a communication system comprising a communication terminal having a function of specifying an addressee from addressee identification information to communicate with the specified addressee; a computer transmitting addressee identification information to the communication terminal; a computer-side store unit provided at a computer side that stores the addressee identification information; a computer-side fetching unit provided at the computer side that fetches the addressee identification information from the computer-side store unit; a computer-side output unit that outputs the fetched addressee identification information to the communication terminal in case of registration in the communication terminal of the addressee identification information used for communication so that the communication is executed according to a piece of addressee identification information selected from the fetched addressee identification information; a retrieval information input unit operated by an operator for input of retrieval information relating the addressee identification information; an instruction unit provided in the communication terminal so as to instruct the computer at the communication terminal side to retrieve via the computer-side fetching unit the addressee identification information stored in the computer-side store unit, the instruction unit instructing the computer to fetch the addressee identification information based on the retrieval information supplied by an operator; and a terminal side display that displays the addressee identification information outputted by the computer-side output unit so that the piece of addressee identification information is selected at the communication terminal side, wherein the communication terminal includes a terminal-side input unit provided so that the addressee identification information output is received in the communication terminal, and a terminal-side store unit that stores the addressee identification information supplied to the terminal-side input unit.
In another preferred form, the facsimile machine includes facsimile-side registering means for registering the data of addressee identification information in the facsimile-side storage means and facsimile-side output means for outputting the data of addressee identification information registered in the facsimile-side storage means by the facsimile-side registering means. In this preferred form, the computer includes computer-side input means for receiving the data of addressee identification information output from the facsimile-side storage means by the facsimile-side output means, and the computer-side storage means stores the data of addressee identification information received by the computer-side input means.
In further another preferred form, the facsimile machine is capable of executing facsimile transmission via an internet to an addressee, and the facsimile machine includes reading means for reading data of address information registered on the basis of an electronic mail application program which is already in operation and designating means for designating the data of address information read by the reading means as data of address information for the facsimile transmission via the internet. In this arrangement, the facsimile machine preferably includes address information storage means for storing the data of address information designated by the designating means as an addressee address for the facsimile transmission via the internet and address selecting means for selecting a desired address from the address information storage means.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the present invention will become clear upon reviewing the following description of the preferred embodiments made with reference to the accompanying drawings, in which:
FIG. 1 is a block diagram of a communication line to which a facsimile system of one embodiment in accordance with the present invention is connected;
FIG. 2 is a perspective view of a personal computer and a facsimile machine both constituting the facsimile system;
FIG. 3 is a perspective view of the facsimile machine;
FIG. 4 is a block diagram showing an electrical arrangement of the personal computer shown in FIG. 2 ;
FIG. 5 is a block diagram showing an electrical arrangement of the facsimile machine shown in FIG. 2 ;
FIG. 6 illustrates the contents of a telephone directory 28 c;
FIGS. 7A and 7B are flowcharts showing the contents of main processes carried out by a CPUs 30 and 25 respectively;
FIGS. 8A and 8B are flowcharts showing the contents of a registering process the CPU 30 carries out at step 100 in FIG. 7A and the contents of a synchronous registering process the CPU 25 carries out at step 200 in FIG. 7A respectively;
FIGS. 9A and 9B are flowcharts showing the contents of a retrieval requiring process the CPU 30 carries out at step 120 in FIG. 7A and a retrieving process the CPU 25 carries out at step 220 in FIG. 7B respectively;
FIG. 10 is a flowchart showing the contents of a transmission process the CPU 30 carries out at step 140 in FIG. 7A ;
FIG. 11 is a block diagram of an internet facsimile machine of another embodiment in accordance with the present invention;
FIG. 12 is a schematic block diagram of a communication network to which the internet facsimile machine is connected; and
FIG. 13 is a flowchart showing processes for diverting, to the use with an internet facsimile application, address information registered by an electronic mail application which is stalled in a personal computer and is already in operation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
One embodiment of the present invention will be described with reference to FIGS. 1 to 10 . Referring to FIG. 1 , a communication line to which a facsimile system 1 in accordance with the present invention is connected is shown. The facsimile system 1 comprises a facsimile machine 3 and a personal computer (hereinafter, “PC”) 2 connected to the facsimile machine 3 by a connecting cable 4 . The facsimile machine 3 is connected to a telephone exchanger 6 by a telephone line 5 . The telephone exchanger 6 is connected via a post office protocol server (POPS) 11 and a simple mail transfer protocol server (SMTP) 7 to an internet A. The internet A is connected to an SMTP 8 further connected via a POPS 12 and a telephone exchanger 9 to a facsimile machine 10 owned by an addressee. The telephone exchangers 6 and 9 are connected via a public communication exchange network B to each other. The facsimile machine 10 of the addressee has functions of transmitting and receiving data via the internet A or the public communication exchange network B.
An arrangement of the PC 2 will be described with reference to FIG. 2 . The PC 2 comprises a computer body 21 incorporated with a CPU, a keyboard 22 , a mouse 23 , and a CRT monitor 24 . The facsimile machine 3 is connected via the connecting cable 4 to the computer body 21 . The keyboard 22 is used to input data of addressee identification information such as a name, a facsimile number or a mail address of an addressee. The computer body 21 is provided with an FD drive 26 for driving a 3.5-inch floppy disk (hereinafter, “FD”) and a CD-ROM drive 27 for driving a CD-ROM. The FD drive 26 or the CD-ROM drive 27 is used to install an application program for controlling the data of addressee identification information. The CRT monitor 24 constitutes computer-side display means in the invention.
An electrical arrangement of the PC 2 will now be described with reference to FIG. 4 . The computer body 21 includes a CPU 25 carrying out programs of an operating system and an application program for controlling a telephone directory (data file) in which data of addressee identification information including names, facsimile numbers and mail addresses of addressees to whom image data is transmitted from the facsimile machine 3 . A ROM 21 a , a RAM 21 b , a hard disk drive (hereinafter, “HDD”) 28 are connected to the CPU 25 . An interface (IF) 29 is also connected to the CPU 25 for receiving via the connecting cable 4 various commands transmitted from the facsimile machine 3 . An operating system 28 a , various application programs 28 b and a telephone directory 28 c are stored in the HDD 28 .
The telephone directory 28 c will be described with reference to FIG. 6 . For example, the telephone directory 28 c is designed to be able to register one hundred sets of telephone directory data (Nos. 1 to 100 ). In each set, data of the name of an addressee, the corresponding facsimile number and mail address is registered. The HDD 28 constitutes computer-side storage means in the invention.
The facsimile machine 3 will be described with reference to FIG. 3 . The facsimile machine 3 is of a multi-function type provided with a plurality of functions of facsimile, image scanning, printing and copying. A facsimile machine with only the facsimile function or with the facsimile function and one or more of the above-mentioned functions may be used, instead.
The facsimile machine 3 comprises a generally box-shaped housing 3 j . An operation panel 3 a is provided on a forward portion of the top of the housing 3 j . The operation panel 3 a comprises numeric keys 3 b of “0” to “9” for input of a facsimile number of an addressee, a start button 3 c for instruction to start reading an original etc., a stop button 3 d for instruction to interrupt transmission of image data, abbreviated dialing buttons 3 e for transmission of image data by use of an abbreviated facsimile number, a retrieval button 3 f operated so that the CPU 25 of the PC 2 carries out retrieval of the telephone directory 28 c stored in the HDD 28 , and a registration button 3 g operated for determining registration of addressee information input with the numeric keys 3 b . The numeric keys 3 b are adapted for entry of characters and symbols and accordingly, can be used for input of the name of addressee and mail address of an electronic mail.
A liquid-crystal display (LCD) 3 h is provided in the rear of the operation panel 3 g on the top of the housing 3 j . The LCD 3 h displays the name, facsimile number and mail address of an addressee, and an operating state of the facsimile machine 3 . An original setting section 3 i is provided in the rear of the LCD 3 h for setting an original or manuscript carrying information to be transmitted or copied. The original set in the original setting section 3 i is carried into the housing 3 j by a paper feeding mechanism (not shown) provided in the housing 3 j . An image scanner (shown by reference numeral 38 in FIG. 5 ) is provided for reading image information on the carried original. The original whose image information has been read by the image scanner is discharged onto a tray 3 m through an original outlet 3 k provided below the operation panel 3 a , being stacked.
A recording paper setting section 3 n is provided in the original setting section 3 m . Sheets of recording paper for recording received image information or print data are set in the recording paper setting section 3 n . A recording paper cassette (not shown) accommodating a plurality of sheets of recording paper in a stacked state is detachably attached to the recording paper setting section 3 n . The recording paper accommodated in the cassette is carried into the housing 3 j by the above-mentioned paper feeding mechanism. The image information or print data is recorded on the carried recording paper by a printer (shown by reference numeral 49 in FIG. 5 ). The recording paper on which the image information or print data has been recorded is discharged through a recording paper outlet 3 p provided below the tray 3 .
A video signal input terminal 3 q is provided on a lower right-hand portion of a front of the housing 3 a as viewed in FIG. 3 . A video camera (not shown) connected to the terminal 3 q delivers video signals to the facsimile machine 3 , so that image information is printed by the printer on the basis of the video signals. A communication terminal (not shown) connected to a telephone line 5 and a terminal (not shown) connected to the connecting cable 4 for connection to the PC 2 are provided on a rear of the housing 3 a . A telephone receiver (not shown) is provided on a left-hand side of the housing 3 for the purpose of contact with an addressee. The retrieval button 3 f constitutes instruction means and the LCD 3 h constitutes facsimile-side display means in the invention.
An electrical arrangement of the facsimile machine 3 will now be described with reference to FIG. 5 . The facsimile machine 3 is provided with a facsimile unit FU and a printer unit PU. Both units are connected via an interface 42 to each other. The facsimile unit FU includes a CPU 30 for-controlling the image scanner 38 , transmission and receiving of image information, and input and output of various commands and addressee information from and to the PC 2 . The CPU 30 is connected to a facsimile control circuit 41 . The ROM 31 , the RAM 32 and the EEPROM 33 are connected to the facsimile control circuit 41 . The ROM 31 stores a control program 31 a on the basis of which the CPU 30 executes the above-mentioned controls. The RAM 32 temporarily stores image information read from the original by the image scanner 38 . The EEPROM 33 erasably stores a telephone directory having the same arrangement as the telephone directory 28 c stored in the HDD 28 of the PC 2 . The abbreviated dialing buttons 3 e correspond to registration numbers 1 to 12 respectively. Each of the registration numbers is accessible from the EEPROM 33 by operation of the corresponding abbreviated dialing button 3 e . Regarding the other registration numbers, the numeric keys 3 b are operated so that the desired registration number is accessible from the EEPROM 33 when the registration number is directly input.
Further, a PC interface 39 , an NCU 34 , a modem 35 and an original sensor 40 for detecting the setting of an original are connected to the facsimile control circuit 41 . An encoder 36 and a decoder 37 are further connected to the facsimile control circuit 41 . The encoder 36 encodes data of image information obtained by the image scanner 38 scanning an original to compressed data. The decoder 37 decodes encoded data of received image information.
On the other hand, the printer unit PU is provided with a printer control circuit 43 for controlling a printer 49 . A CPU 44 executing a program for controlling the printer 49 is connected to the printer control circuit 43 . A ROM 45 , a RAM 46 , a PC interface 47 , a character generator (CG) 48 and the printer 49 are further connected to the printer control circuit 43 . The ROM 45 stores the program executed by the CPU 44 and the like. The RAM 46 includes a work memory used when the CPU 44 executes the program and a print memory storing print data etc. The PC 2 is connected to the PC interface 47 . The character generator 48 stores data of vector font of printing characters.
In the embodiment, the PC interface 39 is a parallel interface in conformity to the Centronics Standards. The facsimile machine 3 transmits and receives data to and from the PC 2 via the cable 4 connected to the PC interface 39 . The EEPROM 33 constitutes facsimile-side storage means in the invention.
The control contents of the CPUs 30 and 25 will be described with reference to FIGS. 7A to 10 . These control contents start with a process for referring to the telephone directory stored in the HDD 28 of the PC 2 and ends with a process for transmitting an electronic mail from the facsimile machine 3 . First, FIGS. 7A and 7B show the contents of main processes executed by each CPU. The CPU 30 of the facsimile machine 3 carries out a registering process (step 100 ), a retrieval requiring process (step 120 ) and a transmission process (step 140 ) in this sequence as shown in FIG. 7A . In the registering process, addressee information is registered in the telephone directory stored in the EEPROM 33 . The CPU 30 requires the PC 2 to retrieve the addressee identification information in the retrieval requiring process. In the transmission process, data of image information the image scanner 38 has scanned from the original is transmitted, accompanied with an electronic mail. Alternatively, the data is transmitted via a public telephone line to a facsimile machine of the addressee.
The CPU 25 of the PC 2 carries out a synchronous registering process (step 200 ) and a retrieving process (step 220 ) sequentially as shown in FIG. 7B . In the synchronous registering process, the CPU 25 registers the telephone directory having the same contents as the telephone directory stored in the facsimile machine 3 in synchronization with build-up of power supply to the facsimile machine 3 and registration of addressee identification information. In the retrieving process, the CPU 25 retrieves the data of addressee identification information in response to the retrieval requirement from the CPU 30 of the facsimile machine 3 .
The registering process the CPU 30 executes at step 100 and the synchronous registering process the CPU 25 executes at step 200 will now be described in detail with reference to FIGS. 8A and 8B . First, the CPU 30 detects power-on of the facsimile machine 3 (YES at step 102 ) and then reads the data of telephone directory stored in the EEPROM 33 (step 104 ). The CPU 30 delivers the read data of telephone directory via the PC interface 39 to the PC 2 (step 106 ).
On the other hand, the CPU 25 of the PC 2 inputs the output data of telephone directory (step 202 ), registering the input data in the telephone directory 28 c of the HDD 28 thereof (step 204 ). In this case, a previous data of the telephone directory 28 c of the HDD 28 is renewed by a new one.
The CPU 30 then judges whether the facsimile machine 3 is in a mode for registration of the data of addressee identification information (step 108 ). When the facsimile machine 3 is in the mode (YES at step 108 ), the CPU 30 inputs the data of addressee identification information the user has supplied by operation of the numeric keys 3 b (step 110 ). Upon detection of the ON state of the registration button 3 g for determining registration of the input data of addressee identification information (YES at step 112 ), the CPU 30 registers in the EEPROM 33 the data of addressee identification information input at step 110 (step 114 ). The CPU 30 then delivers the same data of addressee identification information as the registered one to the PC 2 (step 116 ). The CPU 25 of the PC 2 inputs and registers the output data of the addressee identification information in the telephone directory 28 c of the HDD 28 (steps 206 and 208 ). The renewed contents of the telephone directory are displayed on the CRT monitor 24 (step 210 ).
In the above-described facsimile system 1 , the telephone directory having the same contents as that stored in the facsimile machine 3 is automatically stored in the PC 2 . The user can view the telephone directory having the same contents when operating either the facsimile machine 3 or the PC 2 . This is convenient for the user.
The retrieval requiring process the CPU 30 executes at step 120 and the retrieving process the CPU 25 executes at step 220 will now be described in detail with reference to FIG. 9 . First, the CPU 30 detects input of retrieved characters, namely, the initials of the addressee or characters indicative of part of the name of addressee with the numeric keys 3 b (YES at step 122 ). Upon detection of the ON state of the retrieving button 3 f (YES at step 124 ), the CPU 30 delivers to the PC 2 a retrieval requiring command (retrieving command) indicative of requirement of retrieval of the addressee identification information containing the retrieved characters (step 126 ).
On the other hand, when detecting input of the retrieval requiring command (YES at step 222 ), the CPU 25 of the PC 2 retrieves the data of addressee identification information containing the retrieved characters indicated by the retrieval requiring command in the telephone directory 28 c of the HDD 28 thereof, extracting the data (step 224 ). The CPU 25 then delivers the results of extraction to the facsimile machine 3 (step 226 ).
The CPU 30 inputs the output results of extraction (step 128 ), displaying them on the LCD 3 h (step 130 ). When a plurality of results of extraction are present, one of the data of addressee identification information is selected with the numeric keys 3 b (step 132 ). Thereafter, upon detection of the ON state of the registration button 3 g (YES at step 134 ), the CPU 30 registers the selected addressee identification information in the telephone directory of the EEPROM 33 (step 136 ).
In the above-described facsimile system 1 , the data of telephone directory stored in the PC 2 can be retrieved at the facsimile machine 3 side, which side is away more or less from the PC 2 . Consequently, the user need not move from the location of the facsimile machine 3 to the location of the PC 2 every time of retrieval.
The transmission process the CPU 30 of the facsimile machine 3 executes at step 140 in FIG. 7A will be described with reference to FIG. 10 . In the following description, the user of the facsimile machine 3 transmits an electronic mail accompanying the data of image information to an addressee registered as No. 1 (see FIG. 6 ). The CPU 30 detects selection of the registration No. 1 addressee on the basis of operation of the abbreviated dialing button 3 e (YES at step 142 ). The CPU 30 then judges whether a mail address of the selected addressee is registered (step 144 ). Since the mail address of the selected addressee No. 1 has been registered (YES at step 144 ), the CPU 30 starts up a software for electronic mail transmission (step 146 ).
The CPU 30 then makes an electronic mail (step 152 ) when detecting the ON state of the transmission button 3 c (YES at step 148 ) and then the setting of an original on the basis of the output signal from the original sensor 40 (YES at step 150 ). The CPU 30 then starts the scan of the original by the image scanner 38 (step 154 ). Upon detection of completion of the scan (YES at step 156 ), the CPU 30 dials to the SMTP 7 (step 158 ). Upon detection of connection to the SMTP 7 (YES at step 160 ), the CPU 30 transmits the electronic mail accompanying the image data obtained from the original by the scanning (step 162 ).
The electronic mail is transmitted from the SMTP 7 via the internet A and the SMTP 8 to the POPS 12 . The addressee accesses at the facsimile machine 10 to the POPS 12 so that the electronic mail stored in the POPS 12 is received by the facsimile machine 10 of the addressee.
When judging that the mail address of the selected addressee is not registered (NO at step 144 ), the CPU 30 detects the ON state of the transmission button 3 c (YES at step 164 ). Further, when detecting the setting of the original on the basis of the output signal of the original sensor 40 (YES at step 166 ), the CPU 30 starts the scan of the original by the image scanner 38 (step 168 ). Upon detection of completion of the scan (YES at step 170 ), the CPU 30 dials to the telephone exchanger 6 (step 172 ). Upon detection of connection to the telephone exchanger 6 (YES at step 174 ), the CPU 30 transmits the image data obtained from the original by the scanning (step 176 ).
According to the above-described facsimile system 1 , when the mail address of the selected addressee has been registered, a communication channel via the internet A is automatically selected so that the data of image information can be transmitted with the electronic mail. This can save a time for switching the communication channel depending upon presence or absence of a mail address of the selected addressee.
In the foregoing embodiment, the communication channel can manually be switched from that via the internet A to the public communication exchange network B which is not via the internet A when a facsimile number of the selected addressee has been registered. For example, the operation for selecting the public communication exchange network B may be executed before the transmission button 3 c is turned on or subsequently to the operation for selecting an addressee.
In the foregoing embodiment, the data of telephone directory stored at the computer side is retrieved and extracted to thereby be registered at the facsimile machine side by the processes shown in FIG. 9B . The data of telephone directory registered at the facsimile machine side is designated and the data of image information is transmitted by the processes shown in FIG. 10 . For example, however, the data of telephone directory extracted at the computer side may temporarily be stored in a suitable memory area such as a RAM without being registered in the EEPROM 33 , and the data of image information may be transmitted to an addressee indicated by the temporarily stored data. In this case, data of one or more of the addressees is not stored at the facsimile side. When the user operates the facsimile machine so that the addressee is retrieved on the basis of a character string of the addressee, the data of telephone directory in the computer is retrieved, the corresponding data of telephone directory is automatically taken into the facsimile machine to be stored in the temporal storage area. Further, the retrieved data of telephone directory is displayed on a display, for example. Confirming the displayed contents, the user depresses the transmission button when they are right, so that the data of image information can be transmitted to a desired addressee. Thus, the user can transmit the data of image information to the addressee registered in the telephone directory at the computer side only by the operation at the facsimile machine side.
On the other hand, when part of the extracted data of telephone directory cannot be displayed on the display of the facsimile machine upon retrieval of the telephone directory at the computer side, all the data of telephone directory may once be displayed on the display at the computer side. The user may select a desired data of telephone directory, which may be taken into the facsimile machine side on the basis of the selection.
Step 224 executed by the CPU 25 of the PC 2 functions as computer-side referring means in the invention. Step 126 executed by the CPU 30 of the facsimile machine 3 functions as instruction means. Step 226 executed by the CPU 25 functions as computer-side output means. Step 128 executed by the CPU 30 functions as facsimile-side input means. Step 114 executed by the CPU 30 functions as facsimile-side registering means. Step 116 executed by the CPU 30 functions as facsimile-side output means. Step 206 executed by the CPU 25 functions as computer-side input means. Step 130 executed by the CPU 30 functions as facsimile-side display means. Step 210 executed by the CPU 25 functions as computer-side display means. Step 142 executed by the CPU 30 functions as selecting means. Step 162 executed by the CPU 30 functions as transmission means.
According to the above-described embodiment, when the instruction means of the facsimile machine 3 gives the PC 2 an instruction to refer to the addressee identification information, the computer-side referring means of the PC 2 refers to the data of addressee identification information stored in the storage means (the HDD 28 ) and the data of addressee identification information referred to by the computer-side referring means can also be referred to by the facsimile machine 3 . Accordingly, part of the data of the addressee identification information that cannot be stored at the facsimile machine 3 side can freely be referred to by the instruction means at the facsimile machine 3 side when stored in the computer-side storage means of the PC 2 . Consequently, a quantity of substantially storable data of addressee identification information can be increased to a large degree.
Particularly in the foregoing embodiment, the data of addressee identification information stored in the computer-side storage means (the HDD 28 ) can be taken into the facsimile-side storage means (the EEPROM 33 ). Accordingly, for example, when desired data of addressee identification information is stored in the computer-side storage means, the information can be referred to and taken into the facsimile machine 3 side to thereby be stored. As a result, data of image information can readily be transmitted to a desired addressee on the basis of the stored information.
Further, the date of addressee identification information registered at the facsimile machine 3 side can also be registered in the PC 2 side. Accordingly, since the same data of addressee identification information can be controlled both by the facsimile machine 3 and by the PC 2 , the data of addressee identification information having a low frequency of use can be reserved in the computer-side storage means even when deleted from the facsimile-side storage means. Consequently, the facsimile-side storage means can efficiently be used. Further, information which has been deleted once can readily be recovered in the facsimile-side storage means.
Further, the facsimile machine 3 side can give the PC 2 side an instruction to retrieve the data of addressee identification information. Further, the results of retrieval are displayed at the facsimile machine 3 side such that the contents thereof can be confirmed. This can save a time required for displaying the results of retrieval on the display at the PC 2 side and thereafter re-inputting the data of addressee identification information at the facsimile machine 3 side. Further, the computer-side display means can display a larger quantity of data of the results of extraction than the facsimile-side display means. Accordingly, when the results of extraction by the computer-side referring means has a quantity of information that cannot partially be displayed on the display means provided in the facsimile machine 3 , the destination of the information can be switched to the computer-side display means. For example, when a list of addressees having the same initials is displayed, the list can contain a larger number of addressees when displayed on the computer-side display means than when displayed on the facsimile-side display means. Consequently, a target name of addressee can quickly be found.
Further, the facsimile machine 3 is provided with the selecting means which can select either the data of addressee identification information stored in the storage means at the facsimile machine 3 side or that stored in the storage means at the PC 2 side. Further, the image information can be transmitted to the addressee indicated by the selected data of addressee identification information via or not via the internet. For example, even when desired data of addressee identification information is stored in the computer-side storage means, the data can be referred to by an instruction at the facsimile machine 3 side. Further, when selected by the selecting means, necessary data of addressee identification information is automatically taken into the facsimile machine 3 side so that the data of image information can be transmitted to a desired addressee on the basis of the data of address identification information. At this time, the user can perform all the operations necessary for the transmission only at the facsimile machine 3 side. Particularly when the selected data of addressee identification information contains the mail address, the communication channel via the internet can automatically be selected for transmission of the data of image information. This can save a time required for switching the communication channel depending on the contents of the selected data of addressee identification information.
Further, a mail address is generally composed of a plurality of characters and/or symbols. When such a mail address is registered with input keys (unsuitable for input of characters) of a conventional facsimile machine and a small-sized liquid crystal display, the registration takes much time and accordingly reduces the working efficiency. In the foregoing embodiment, however, the character input work can be done with the keyboard and the large-sized display at the PC 2 side. Consequently, the working efficiency can be improved to a large degree. Further, the data of addressee identification information input as described above can readily be referred to at the facsimile machine 3 side. Further, if the displayed data is a necessary one, it can readily be taken into the facsimile machine 3 side by the operation thereat. This is effective for equipment provided with a function of transmitting data of image information via the internet.
In the above-described facsimile system, an application program for execution of internet facsimile (hereinafter, “application”) is carried out in the PC 2 so that address information of addressees is registered and a desired addressee is selected from the registered addresses, whereby the address can readily be ascertained without input of the characters of the address one by one.
On the other hand, the PC 2 can also operate an application for execution of electronic mail. According to the application, address information of addressees is registered so that the address of a desired addressee can readily be ascertained without input of the characters of the address one by one when the address is selected from the registered addressees. However, the address information registered on the electronic mail application cannot be used on the internet facsimile application since these are independent applications.
A second embodiment of the invention is directed to a solution of the above-described problem. The second embodiment will now be described with reference to FIGS. 11 to 13 . Referring to FIG. 11 , the arrangement of an internet facsimile machine 310 in accordance with the invention is schematically shown. The internet facsimile machine 310 comprises an image processing section 320 and a PC 330 . The image processing section 320 includes a scanner 321 for reading images, a printer 322 for printing the images, an information expansion/compression section 323 for expanding received image information and compressing image information to be transmitted, an image memory 324 for storing image information compressed by the information expansion/compression section 323 , and a PC interface section 325 rendering information exchange between the image processing section 320 and the PC 330 possible. A general type of facsimile machine or the multifunction type facsimile machine as described in the foregoing embodiment may be used as the image processing section 320 . The image processing section 320 is connected via the PC interface section 325 to the PC 330 or, more specifically, to an I/O port 331 thereof.
The PC 330 comprises a CPU 332 , a memory 333 , a line control section 334 , and a modem 335 for modulating and demodulating signals. The memory 333 of the PC 330 stores an application for execution of electronic mail and an internet facsimile application for execution of internet facsimile transmission. The memory 333 comprises a ROM, a RAM or a hard disk.
The application for execution of electronic mail is well known in the art. For example, an address of the addressee is stored in a predetermined area of the memory 333 of the PC 330 so as to correspond to the name of the addressee, whereby the address of the addressee is registered. Thereafter, when the user inputs the name of the addressee on the PC 330 using keys, an electronic mail can automatically be transmitted to the addressee without input of the address.
In the internet facsimile application, data of image information read by the scanner 321 is compressed by the information expansion/compression section 323 , and the compressed data is stored in the image memory 324 . The data of image information is converted so as to have a format transmittable on the internet. Further, the data of image information is transmitted via the internet to an address input on the PC 330 . In the internet facsimile application, furthermore, the data of image information received via the internet is converted to a format suitable for the subsequent processes and then stored in the image memory 324 . The data is expanded by the information expansion/compression section 323 and then printed by the printer 322 .
The memory 333 of the PC 330 is provided with an internet facsimile address registration area 333 B for storing address information used in the internet facsimile application.
FIG. 12 schematically illustrates a communication network to which the internet facsimile machine 310 is connected. The machine 310 is connected to a LAN 350 and further via a public communication line 360 and an internet 370 to a facsimile machine 380 of an addressee.
The electronic mail application is installed in the PC 330 of the internet facsimile machine 310 and is already in operation. FIG. 13 shows processes for diverting address information having registered by the above-mentioned electronic mail application to a purpose of use in the internet facsimile application. First, the electronic mail application is started up (step S 10 ). Address information is already registered in the electronic mail application. The address information contains addresses of addressees, words identifying the respective addressees, for example, the respective names of the addressees. The internet facsimile application is then started up (step S 20 ). A process for copying address information by the internet facsimile application is then started (step S 30 ). In this process, address information is made by the electronic mail application and stored in the electronic mail address registration area 333 A is retrieved (step S 40 ) and the data structure of the information is analyzed (step S 50 ). Various types of electronic mail applications employ particular manners for storing the address information. The above-mentioned analysis of the data structure is carried out in order that the storing manner of actually stored address information may be found.
The address information is then read on the basis of the results of analysis of the data structure (step S 60 ). The read address information is displayed on a display of the PC 330 (step S 70 ). Thereafter, data of information such as the address, telephone number, etc. is added to the address information on display, if necessary (step S 80 ). The data of information is stored in the internet facsimile address registration area 333 B according to a storing format by the internet facsimile application so that the data is rendered usable on the internet facsimile application (S 90 ). The process is then completed.
The address information registered in the internet facsimile as described above is read out by the internet facsimile application in the same manner as address information registered on the internet facsimile application.
The same addressee is common to the electronic mail address and the internet facsimile address in the embodiment. However, even when both addresses differ from each other, each address can be registered as that for the internet facsimile depending on the aspect of the analysis. For example, when a plurality of addresses correspond to one addressee, the first address may be defined as the electronic mail address, whereas the second address may be defined as the internet facsimile address. As a result, the address of the same addressee can be prevented from duplicate.
The address information having already registered on the basis of the electronic mail application can be diverted to the purpose of use on the internet facsimile application as the result of execution of the above-described processes. Accordingly, the same address need not be registered individually on the electronic mail application and on the internet facsimile application. Consequently, the user can save the time.
In a modified form of the second embodiment, display of the address information at step S 70 in FIG. 13 , addition of information at step S 80 , and start-up of the electronic mail application at step S 10 may be eliminated. Further, both of the electronic mail application and the internet facsimile application are installed in the same personal computer in the second embodiment. However, the applications may be installed in the different personal computers respectively so that the electronic mail application is used by communication between the personal computers.
The internet facsimile machine 310 comprises the image processing section 320 (the facsimile machine) and the PC 330 (personal computer) in the second embodiment. However, for example, the internet facsimile machine may comprise a personal computer to which a scanner, a printer, a modem, etc. are connected. Further, the programs including various applications and OS for operating the facsimile machine and the personal computer are stored in the ROM and HDD in the foregoing embodiments. However, these programs may be stored in a CD-ROM or FD, instead.
The foregoing description and drawings are merely illustrative of the principles of the present invention and are not to be construed in a limiting sense. Various changes and modifications will become apparent to those of ordinary skill in the art. All such changes and modifications are seen to fall within the scope of the invention as defined by the appended claims. | A communication system includes a communication terminal, a computer transmitting addressee identification information to the communication terminal, a computer-side fetching unit fetching the addressee identification information from a computer-side store unit, a computer-side output unit that outputs the fetched addressee identification information to the terminal in case of communication, a retrieval information input unit located in the terminal and operated for input of retrieval information relating the addressee identification information, an instruction unit located in the terminal to instruct the computer to retrieve the addressee identification information, the instruction unit instructing the computer to fetch the addressee identification information based on the retrieval information supplied by an operator, and a terminal side display that displays the outputted data so that the desired addressee identification information is selected at the terminal side. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims benefit of U.S. Provisional Patent Application No. 61/427,714, filed Dec. 28, 2010, entitled Gas Turbine Engine and Airfoil, which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to gas turbine engines, and more particularly, to airfoils for gas turbine engines.
BACKGROUND
[0003] Gas turbine engine airfoils, particularly those that require cooling, remain an area of interest. Some existing systems have various shortcomings, drawbacks, and disadvantages relative to certain applications. Accordingly, there remains a need for further contributions in this area of technology.
SUMMARY
[0004] One embodiment of the present invention is a unique gas turbine engine. Another embodiment is a unique turbine engine airfoil. Other embodiments include apparatuses, systems, devices, hardware, methods, and combinations for gas turbine engines and airfoils. Further embodiments, forms, features, aspects, benefits, and advantages of the present application will become apparent from the description and figures provided herewith.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The description herein makes reference to the accompanying drawings wherein like reference numerals refer to like parts throughout the several views, and wherein:
[0006] FIG. 1 schematically illustrates some aspects of a non-limiting example of a gas turbine engine in accordance with an embodiment of the present invention.
[0007] FIG. 2 illustrates some aspects of a non-limiting example of an airfoil in accordance with an embodiment of the present invention.
[0008] FIG. 3 illustrates some aspects of a non-limiting example of a cross section of the airfoil of FIG. 2 .
[0009] FIG. 4 illustrates some aspects of a non-limiting example of a cross section of the airfoil of FIG. 2 .
[0010] FIGS. 5A-5E illustrate some aspects of a non-exhaustive group of non-limiting examples of different rib designs in accordance with embodiments of the present invention.
DETAILED DESCRIPTION
[0011] For purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nonetheless be understood that no limitation of the scope of the invention is intended by the illustration and description of certain embodiments of the invention. In addition, any alterations and/or modifications of the illustrated and/or described embodiment(s) are contemplated as being within the scope of the present invention. Further, any other applications of the principles of the invention, as illustrated and/or described herein, as would normally occur to one skilled in the art to which the invention pertains, are contemplated as being within the scope of the present invention.
[0012] Referring to the drawings, and in particular FIG. 1 , a non-limiting example of some aspects of a gas turbine engine 10 in accordance with an embodiment of the present invention is schematically depicted. In one form, gas turbine engine 10 is an aircraft propulsion power plant. In other embodiments, gas turbine engine 10 may be a land-based or marine engine. In one form, gas turbine engine 10 is a multi-spool turbofan engine. In other embodiments, gas turbine engine 10 may take other forms, and may be, for example, a turboshaft engine, a turbojet engine, a turboprop engine, or a combined cycle engine.
[0013] As a turbofan engine, gas turbine engine 10 includes a fan system 12 , a bypass duct 14 , a compressor system 16 , a diffuser 18 , a combustion system 20 , a turbine system 22 , a discharge duct 26 and a nozzle 28 . Bypass duct 14 and compressor system 16 are in fluid communication with fan system 12 . Diffuser 18 is in fluid communication with compressor system 16 . Combustion system 20 is fluidly disposed between compressor system 16 and turbine system 22 . In one form, combustion system 20 includes a combustion liner (not shown) that contains a continuous combustion process. In other embodiments, combustion system 20 may take other forms, and may be, for example, a wave rotor combustion system, a rotary valve combustion system, or a slinger combustion system, and may employ deflagration and/or detonation combustion processes.
[0014] Fan system 12 includes a fan rotor system 30 . In various embodiments, fan rotor system 30 includes one or more rotors (not shown) that are powered by turbine system 22 . Bypass duct 14 is operative to transmit a bypass flow generated by fan system 12 to nozzle 28 . Compressor system 16 includes a compressor rotor system 32 . In various embodiments, compressor rotor system 32 includes one or more rotors (not shown) that are powered by turbine system 22 . Each compressor rotor includes a plurality of compressor blades (not shown). Turbine system 22 includes a turbine rotor system 34 . In various embodiments, turbine rotor system 34 includes one or more rotors (not shown) operative to drive fan rotor system 30 and compressor rotor system 32 . Each turbine rotor includes a plurality of turbine blades (not shown) Turbine rotor system 34 is drivingly coupled to compressor rotor system 32 and fan rotor system 30 via a shafting system 36 . In various embodiments, shafting system 36 includes a plurality of shafts that may rotate at the same or different speeds and directions. In some embodiments, only a single shaft may be employed. Turbine system 22 is operative to discharge an engine 10 core flow to nozzle 28 . In one form, fan rotor system 30 , compressor rotor system 32 , turbine rotor system 34 and shafting system 36 rotate about an engine centerline 48 . In other embodiments, all or parts of fan rotor system 30 , compressor rotor system 32 , turbine rotor system 34 and shafting system 36 may rotate about one or more other axes of rotation in addition to or in place of engine centerline 48 .
[0015] Discharge duct 26 extends between a discharge portion 40 of turbine system 22 and engine nozzle 28 . Discharge duct 26 is operative to direct bypass flow and core flow from a bypass duct discharge portion 38 and turbine discharge portion 40 , respectively, into nozzle system 28 . In some embodiments, discharge duct 26 may be considered a part of nozzle 28 . Nozzle 28 in fluid communication with fan system 12 and turbine system 22 . Nozzle 28 is operative to receive the bypass flow from fan system 12 via bypass duct 14 , and to receive the core flow from turbine system 22 , and to discharge both as an engine exhaust flow, e.g., a thrust-producing flow.
[0016] During the operation of gas turbine engine 10 , air is drawn into the inlet of fan 12 and pressurized by fan 12 . Some of the air pressurized by fan 12 is directed into compressor system 16 as core flow, and some of the pressurized air is directed into bypass duct 14 as bypass flow, and is discharged into nozzle 28 via discharge duct 26 . Compressor system 16 further pressurizes the portion of the air received therein from fan 12 , which is then discharged into diffuser 18 . Diffuser 18 reduces the velocity of the pressurized air, and directs the diffused core airflow into combustion system 20 . Fuel is mixed with the pressurized air in combustion system 20 , which is then combusted. The hot gases exiting combustor 20 are directed into turbine system 22 , which extracts energy in the form of mechanical shaft power sufficient to drive fan system 12 and compressor system 16 via shafting system 36 . The core flow exiting turbine system 22 is directed along an engine tail cone 42 and into discharge duct 26 , along with the bypass flow from bypass duct 14 . Discharge duct 26 is configured to receive the bypass flow and the core flow, and to discharge both as an engine exhaust flow, e.g., for providing thrust, such as for aircraft propulsion.
[0017] Compressor rotor system 32 includes a plurality of blades and vanes (not shown) employed to add energy to the gases prior to combustion. Turbine rotor system 34 includes a plurality of blades and vanes (not shown) employed to extract energy from the high temperature high pressure gases in the flowpath. It is desirable to maintain the temperature of blades and vanes within certain temperature limits, e.g., based on the materials and coatings employed in the blades and vanes. In many cases, blades and vanes are cooled by injecting cooling air into the blade or vane. The blades rotate with the corresponding rotor during the operation of engine 10 , which may increase the degree of difficulty in cooling the blade because the cooling air tends to migrate radially outward due to centrifugal force. Embodiments of the present invention includes an airfoil configured to mitigate and/or prevent the migration of cooling air due to centrifugal loading.
[0018] Referring to FIGS. 2-4 , a non-limiting example of some aspects of an airfoil 50 in accordance with an embodiment of the present invention is depicted. In one form, airfoil 50 is a turbine blade. In other embodiments, airfoil 50 may be a compressor blade. In still other embodiments, airfoil 50 may be a turbine or compressor vane. In one form, airfoil 50 is a dual wall airfoil. In other embodiments, airfoil 50 may be a single wall airfoil or an airfoil having more than two walls. Airfoil 50 includes a spar 52 and an outer skin 54 . In one form, airfoil 50 is formed of a conventional aerospace material, such as CMSX-4, available from Cannon Muskegon Corporation of Muskegon, Mich., USA. In other embodiments, other materials, conventional or otherwise, may be employed.
[0019] In one form, spar 52 is hollow, having an internal volume that forms a cooling air supply passage 56 . In other embodiments, one or more other cooling air supply passages may be employed in addition to or in place of cooling air supply passage 56 . In other embodiments, cooling air supply passage 56 may be positioned adjacent to an inner wall other than spar 52 . Spar 52 includes a plurality of cooling air inlet openings 58 extending through the wall of spar 52 . Cooling air supply passage 56 is in fluid communication with cooling air inlet openings 58 . Cooling air supply passage 56 is operative to supply cooling air to cooling air inlet openings 58 .
[0020] Outer skin 54 forms an outer wall for airfoil 50 on both the pressure side and the suction side of airfoil 50 . In one form, outer skin 54 extends around both the pressure side and the suction side. In other embodiments, outer skin 54 may be in the form of individual sheets, e.g., one outer wall for each of the pressure side and the suction side of airfoil 50 , e.g., illustrated in FIG. 3 as an outer wall 54 A for the pressure side, and an outer wall 54 B for the suction side. Similarly, in one form, spar 52 extends around both the pressure side and the suction side. In other embodiments, spar 52 may be in the form of individual structures, e.g., one inner wall for each of the pressure side and the suction side of airfoil 50 , e.g., illustrated in FIG. 3 as an inner wall 52 A for the pressure side, and an inner wall 52 B for the suction side.
[0021] Outer skin 54 includes a plurality of cooling air exit openings 60 . Spar 52 forms an inner wall for airfoil 50 on both the pressure side and the suction side of airfoil 50 . Outer skin 54 and spar 52 are spaced apart from each other by a plurality of ribs 62 . In one form, ribs 62 extend between the outer wall formed by outer skin 54 and the inner wall formed by spar 52 . In other embodiments, ribs 62 may extend between other walls in addition to or in place of outer skin 54 and spar 52 . In one form, ribs 62 form a plurality of flow migration dams configured to reduce or prevent cooling air flow migration in a radially outward direction, e.g., due to centrifugal force during the rotation of airfoil 50 in the form of a turbine engine blade. In one form, ribs 62 are oriented horizontally in airfoil 50 . In other embodiments, ribs 62 may be oriented in other directions in addition to or in place of horizontal. In one form, airfoil 50 may have an attachment feature 64 configured to mechanically couple airfoil 50 to engine 10 . In one form, attachment feature 64 is operative to deliver cooling air to cooling air supply passage 56 .
[0022] Each adjacent pair of ribs 62 form therebetween a cooling passage 66 . In one form, ribs 52 and cooling passages 66 are formed on both the pressure side and the suction side of airfoil 50 . In other embodiments, ribs 52 and cooling passages 66 may be formed only on either the pressure side or the suction side of airfoil 50 . In some embodiments, cooling passages 66 may also be formed between ribs 62 and end structures of airfoil 50 , e.g., at the root and tip of airfoil 50 (not shown). In one form, cooling passages 66 are bound by adjacent pairs of ribs 62 and by outer skin 54 and spar 52 . In other embodiments, cooling passages 66 may be bound by other walls in addition to ribs 62 . Cooling passages 66 are in fluid communication with cooling air inlet openings 58 and with cooling air exit openings 60 . In one form, each cooling passage 66 is in fluid communication with cooling air inlet openings 58 at one end, and with cooling air exit openings 60 at the opposite end. In other embodiments, cooling passages 66 , cooling air inlet openings 58 and cooling air exit openings 60 may be arranged otherwise. In one form, each cooling passage 66 adjacent to and in fluid communication with a single cooling air inlet opening 58 and with a single cooling air exit opening 60 and operative to receive cooling air from the single cooling air inlet opening 58 and the single cooling air exit opening 60 . In other embodiments, each cooling passage 66 may be adjacent to and in fluid communication with a plurality of cooling air inlet openings 58 and/or a plurality of cooling air exit openings 60 .
[0023] During engine 10 operation, cooling air is delivered from cooling air supply passage 56 to cooling passages 66 via cooling air inlet openings 58 . The cooling air exits cooling passages 66 via cooling air exit openings 60 . In one form, cooling passages 66 are operative to flow cooling air to remove heat from outer skin 54 and spar 52 . In one form, cooling passages 66 extend continuously between the leading edge portion 68 of airfoil 50 and the trailing edge portion 70 of airfoil 50 . In other embodiments, cooling passages 66 may not extend continuously between leading edge portion 68 and trailing edge portion 70 .
[0024] In one form, ribs 62 are configured to form vortexes 72 in cooling passages 66 . In a particular form, ribs 62 are configured to form a series of vortexes 72 in cooling passages 66 . In one form, ribs 62 are configured to form vortexes on each side of cooling passages 66 . e.g., the top and bottom of each cooling passage 66 . In other embodiments, ribs 62 may not be configured to form vortexes in cooling passages 66 . In one form, ribs 62 include a plurality of trip strips (turbulators) 74 extending from ribs 62 into cooling passages 66 . Trip strips 74 are configured to generate vortexes in the cooling air passing through cooling passages 66 . In other embodiments, trip strips 74 may not extend from ribs 62 , e.g., may be otherwise formed or extend within cooling passages 66 .
[0025] In other embodiments, ribs 62 may be configured to form vortexes by virtue of having a particular shape, e.g., yielding a tortuous flowpath shape of cooling passages 66 , non-limiting examples of which are illustrated in FIGS. 5A-5E . Other shapes may be employed in other embodiments.
[0026] Embodiments of the present invention include an airfoil for a gas turbine engine, comprising: an outer wall having a plurality cooling air exit openings; an inner wall spaced apart from the outer wall, wherein the inner wall has a plurality of cooling air inlet openings; a plurality of flow migration dams, wherein the flow migration dams extend between the inner wall and the outer wall, the plurality of flow migration dams forming therebetween a plurality of cooling passages, wherein the cooling passages are in fluid communication with the cooling air inlet openings and with the cooling air exit openings; and a cooling air supply passage in fluid communication with the cooling air inlet openings, wherein the cooling air supply passage is operative to supply cooling air to the cooling air inlet openings.
[0027] In a refinement, the airfoil further comprises a one or more trip strips in one or more cooling passages configured to generate one or more vortexes.
[0028] In another refinement, the one or more trip strips extend from the flow migration dams.
[0029] In yet another refinement, the one or more trip strips include a series of trip strips in each cooling passage, wherein the series of trip strips is configured to generate a series of vortexes in each cooling passage.
[0030] In still another refinement, the one or more trip strips extend from the flow migration dams.
[0031] In yet still another refinement, the migration dams are oriented horizontally.
[0032] In a further refinement, the cooling passages each have a first end and a second end opposite the first end, and wherein the cooling passages are in fluid communication with the cooling air inlet openings at the first ends, and in fluid communication with the cooling air exit openings at the second ends.
[0033] In a yet further refinement, the flow migration dams are configured to reduce cooling air flow migration in a radially outward direction due to centrifugal force.
[0034] In a still further refinement, the cooling air supply passage is disposed adjacent to the inner wall.
[0035] In a yet still further refinement, the inner wall forms a spar for the airfoil.
[0036] In an additional refinement, the airfoil is configured as a dual wall airfoil.
[0037] In another additional refinement, the outer wall and the inner wall are disposed on a pressure side of the airfoil, further comprising: a second outer wall disposed on a suction side of the airfoil, the second outer wall having a second plurality cooling air exit openings; a second inner wall disposed on a suction side of the airfoil and spaced apart from the second outer wall, wherein the second inner wall has a second plurality of cooling air inlet openings; a second plurality of flow migration dams, wherein the flow migration dams extend between the second inner wall and the second outer wall, the second plurality of flow migration dams forming therebetween a second plurality of cooling passages, wherein the second cooling passages are in fluid communication with the second cooling air inlet openings and with the second cooling air exit openings, wherein the cooling air supply passage is disposed between the inner wall and the second inner wall, and is in fluid communication with the second cooling air inlet openings, wherein the cooling air supply passage is operative to supply cooling air to the second cooling air inlet openings.
[0038] In yet another additional refinement, the airfoil has a leading edge portion and a trailing edge portion; and wherein the flow migration dams extend continuously between the leading edge portion and the trailing edge portion.
[0039] Embodiments include a turbine engine, comprising: an airfoil, the airfoil including: a hollow spar structure having a plurality of cooling air inlet openings, wherein an internal volume in the hollow spar structure forms a cooling air supply passage operative to deliver cooling air to the cooling air inlet openings; an outer skin spaced apart from the hollow spar structure by a plurality of ribs, wherein the plurality of ribs form a plurality of cooling passages, each cooling passage being defined between an adjacent pair of ribs, wherein the cooling air inlet openings are in fluid communication with the cooling passages; and wherein the outer skin includes a plurality of cooling air exit openings in fluid communication with the plurality of cooling passages.
[0040] In a refinement, the ribs are configured to form vortexes in the cooling passages.
[0041] In another refinement, the ribs are configured to form a series of vortexes in each cooling passage.
[0042] In yet another refinement, the ribs are configured to form vortexes on each side of the cooling passages.
[0043] In still another refinement, one or more ribs include one or more trip strips extending from the one or more ribs, and wherein the one or more trip strips are configured to generate one or more vortexes.
[0044] In a further refinement, the ribs are configured to prevent a migration of flow of cooling air between the hollow spar structure and the outer skin in a radial direction.
[0045] Embodiments of the present invention include an airfoil for a turbine engine, comprising: an outer wall having a plurality cooling air exit openings; an inner wall spaced apart from the outer wall, wherein the inner wall has a plurality of cooling air inlet openings; a cooling air supply passage in fluid communication with the cooling air inlet openings, wherein the cooling air supply passage is operative to supply cooling air to the cooling air inlet openings, and means for cooling the outer wall without allowing flow migration in a radially outward direction, wherein the means for cooling is in fluid communication with both the cooling air inlet openings and the cooling air exit openings.
[0046] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment(s), but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as permitted under the law. Furthermore it should be understood that while the use of the word preferable, preferably, or preferred in the description above indicates that feature so described may be more desirable, it nonetheless may not be necessary and any embodiment lacking the same may be contemplated as within the scope of the invention, that scope being defined by the claims that follow. In reading the claims it is intended that when words such as “a,” “an,” “at least one” and “at least a portion” are used, there is no intention to limit the claim to only one item unless specifically stated to the contrary in the claim. Further, when the language “at least a portion” and/or “a portion” is used the item may include a portion and/or the entire item unless specifically stated to the contrary. | One embodiment of the present invention is a unique gas turbine engine. Another embodiment is a unique turbine engine airfoil. Other embodiments include apparatuses, systems, devices, hardware, methods, and combinations for gas turbine engines and airfoils. Further embodiments, forms, features, aspects, benefits, and advantages of the present application will become apparent from the description and figures provided herewith. | 8 |
BACKGROUND
[0001] This disclosure relates to the production of a media suitable for electret treatment.
[0002] Media that have been given electret treatment may be used as filters to remove contaminants from air as well as being used as dirt and dust particle collectors in other forms, such as mops. The media for these applications is often polyolefin nonwoven fabrics, particularly meltblown fabrics. The polyolefinic fabric media is designed to be hydrophobic in its base (untreated) state in an effort to resist moisture, since moisture is known to degrade the filtration efficiency due to electret fouling. It would be useful to have hydrophilic electret filtration media for specific applications, such as a mop designed to collect dust and dirt particles while also being able to remove liquid spills.
SUMMARY
[0003] This disclosure describes hydrophilic electret fabrics that provide exceptional filtration and dust and dirt collection properties. There is a surfactant treatment for a polyolefinic nonwoven fabric that may be used as a filtration medium or for collecting dust and dirt, e.g. as a mop, a wipe for surface cleaning or similar device. The base polyolefinic nonwoven fabric is hydrophobic and is treated prior to electret treatment with a surfactant that consists essentially of carbon, hydrogen and oxygen atoms.
[0004] This disclosure also describes a nonwoven fabric that has the dried residue of an aqueously applied surfactant treatment prior to electret treatment. The surfactant treatment is essentially free of silicon, potassium, phosphorus and sulfur.
[0005] The fabrics treated as disclosed herein may be used in dust and dirt collection devices and as filter material.
DETAILED DESCRIPTION
[0006] It is to be understood that the following description is only exemplary of the principles of the present disclosure, and should not be viewed as narrowing the pending claims. Those skilled in the art will appreciate that aspects of the various embodiments discussed may be interchanged and modified without departing from the scope and spirit of the disclosure.
[0007] As used herein the term “nonwoven fabric or web” means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric. Nonwoven fabrics or webs have been formed from many processes such as for example, meltblowing processes, spunbonding processes, and bonded carded web processes. The basis weight of nonwoven fabrics is usually expressed in ounces of material per square yard (osy) or grams per square meter (gsm) and the fiber diameters useful are usually expressed in microns. (Note that to convert from osy to gsm, multiply osy by 33.91).
[0008] As used herein the term “spunbonded fibers” refers to small diameter fibers which are formed by extruding molten thermoplastic material as filaments from a plurality of fine, usually circular capillaries of a spinneret with the diameter of the extruded filaments then being rapidly reduced as by, for example, in U.S. Pat. No. 4,340,563 to Appel et al., and U.S. Pat. No. 3,692,618 to Dorschner et al., U.S. Pat. No. 3,802,817 to Matsuki et al., U.S. Pat. Nos. 3,338,992 and 3,341,394 to Kinney, U.S. Pat. No. 3,502,763 to Hartman, and U.S. Pat. No. 3,542,615 to Dobo et al. Spunbond fibers are generally not tacky when they are deposited onto a collecting sheet. Spunbond fibers are generally continuous and have average diameters (from a sample of at least 10) larger than 7 microns, more particularly, between about 10 and 20 microns. The fibers may also have shapes such as those described in U.S. Pat. No. 5,277,976 to Hogle et al., U.S. Pat. No. 5,466,410 to Hills and U.S. Pat. Nos. 5,069,970 and 5,057,368 to Largman et al., which describe fibers with unconventional shapes.
[0009] As used herein the term “meltblown fibers” means fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity, usually hot, gas (e.g. air) streams which attenuate the filaments of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting sheet to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Butin et al. Meltblown fibers are microfibers which may be continuous or discontinuous, are generally smaller than 10 microns in average diameter, and are generally tacky when deposited onto a collecting sheet.
[0010] The permeability of a nonwoven material may range from 25 to about 500 cubic feet per minute (CFM) as characterized in terms of Frazier permeability. For example, the permeability of the nonwoven material may range from 50 to about 400 cubic feet per minute. As yet another example, the permeability of the nonwoven material may range from 100 to about 300 cubic feet per minute. The Frazier permeability, which expresses the permeability of a material in terms of cubic feet per minute of air through a square foot of area of a surface of the material at a pressure drop of 0.5 inch of water (or 125 Pa), was determined utilizing a Frazier Air Permeability Tester available from the Frazier Precision Instrument Company and measured in accordance with Federal Test Method 5450, Standard No. 191A. When the nonwoven material contains SMS material(s) having basis weights ranging from about 1 osy (33 gsm) to about 2.6 osy (87 gsm), the permeability of the nonwoven material may range from about 20 cubic feet per minute to about 75 cubic feet per minute when determined generally in accordance with ISO 9237:1995 (measured with an automated air permeability machine using a 38 cm 2 head at a test pressure of 125 Pa,—exemplary air permeability machine is TEXTEST FX 3300 available from TEXTEST AG, Switzerland). If multiple plies or layers of SMS material are used to provide basis weights ranging from about 2 osy (67 gsm) to about 5 osy (167 gsm), the permeability of the nonwoven material may range from about 10 cubic feet per minute to about 30 cubic feet per minute when determined generally in accordance with ISO 9237:1995.
[0011] There are a number of methods of characterizing the air filtration efficiencies of nonwoven webs. One method uses a TSI, Inc. (St. Paul, Minn.) Model 8130 Automated Filter Tester (AFT). This test (the TSI test) is less expensive than the BFE test, and while less accurate, gives directional and relative indications of filtration efficiency. The Model 8130 AFT measures pressure drop and particle filtration characteristics for air filtration media. The AFT utilizes a compressed air nebulizer to generate a sub-micron aerosol of sodium chloride particles which serves as the challenge aerosol for measuring filter performance. The characteristic size of the particles used in these measurements was 0.1 micrometer. Typical air flow rates were between 31 liter per minute and 85 liters per minute. The AFT test was performed on a sample area of 140 square cm. The performance or efficiency of a filter medium is expressed as the percentage of sodium chloride particles which penetrate the filter. Penetration is defined as transmission of a particle through the filter medium. The transmitted particles were detected downstream from the filter. The percent penetration (% P) reflects the ratio of the downstream particle count to the upstream particle count. Light scattering was used for the detection and counting of the sodium chloride particles.
[0012] Bacterial filtration efficiency (BFE) employs a test where samples are challenged with a biological aerosol of Staphylococcus aureus and the results employ a ratio of the bacterial challenge counts to sample effluent counts, to determine percent bacterial filtration efficiency (% BFE). For the tests herein, a suspension of S. aureus was aerosolized using a nebulizer and delivered to the test article at a constant flow rate. The aerosol droplets were drawn through a six-stage, viable particle Andersen sampler for collection. This test procedure allows a reproducible bacterial challenge to be delivered to the nonwoven material and complies with ATSM F2101 (Nelson Lab #373162). The testing herein was performed by Nelson Laboratories, Inc., Salt Lake City, Utah, according to “Bacterial Filtration Efficiency,” Procedure No. SOP/ARO/007L.1.
[0013] The Andersen sampler is known in the art and is used to collect viable samples of airborne bacteria and fungal spores. The samples can act as a measure of the number of bacteria or fungal spores in the air at a specific location and time. The sampler works through impaction in which air is drawn through a sampling head with 400 small holes at constant rate (in this case 28.3 L/min or 1 cubic foot per minute) for a known period of time. Before sampling a media plate is placed inside the sampling head and as air is pulled through the holes heavier particles such as bacteria and fungal spore's impact on the agar surface and stick there. The air continues through the sampler and into the pump. After sampling the plate can be removed for culturing.
[0014] It has been found that electret treatment increases the BFE of a fabric. Electret treatment is described, for example, in U.S. Pat. No. 5,592,357. Electret treatment is used to produce an intense corona current at reduced voltages to help reduce the potential for arcing and provide a more efficient, stable discharge at atmospheric pressure, for electrostatically charging an advancing web or film. Once ionization occurs, excess charged particles cannot be lost until they collide with a solid body, preferably the remaining electrode, achieving the desired result. It has been found that this applies to both AC and DC voltages.
[0015] Placement of a thin non-electron absorbing gas layer in the vicinity of an electrode is advantageously accomplished by various means. For example, the charging bar can be replaced with a longitudinally extending tube having spaced apertures for delivering a gas to the discharge-forming elements of the electrode. These discharge-forming elements can include either a series of pins which extend through the spaced apertures of the tube, or a series of nozzles which project from the surface of the tube. In either case, this places the gas in the vicinity of the pins, or the nozzles, which in turn receive appropriate biasing voltages for developing the electric field which is to produce the improved discharge. Alternatively, the charging shell can be replaced with a hollow body which similarly incorporates a series of apertures, and a cooperating series of pins or nozzles, to achieve a similar result.
[0016] Surfactant treatments for the nonwoven material were investigated to produce a hydrophilic electret material. The material used was a 2.57 osy (87 gsm) SMS except for Sample 1 which was a 1.85 osy (62.7 gsm) SMS. The surfactant treatment was applied to the material by a dip and squeeze (saturation) process, using an aqueous formulation containing the surfactant. The amount of surfactant treatment in weight percent is indicated in the Sample descriptions below for the treated and dried material. The material having the dried surfactant treatment residue was subjected to electret treatment as indicated in the Table. TSI and BFE were tested according to the procedures above. The wettability to water was assessed for the samples by placing drops of distilled water on the fabric surface. The amount of surfactant used for the samples was adjusted to give uniform and complete wet out by the drops of water. A sample determined to be wettable to water is considered to be hydrophilic.
[0017] Samples with treatments investigated include the following:
1. Quadrastat® PIBK at 0.8% add on: Quadrastat® PIBK is the tradename for an aqueous formulation that contains 50% of potassium isobutyl phosphate available from Manufacturers Chemical, LLC, of Cleveland, Tenn. The data in the table is based on five samples. 2. Quadrastat® PIBK at 3.0% add on. The data in the table is based on five samples. 3. Masil® SF-19 at 0.8% add on: MASIL® SF 19 is a low toxicity silicone surfactant with high thermal stability combining the advantages of dimethyl silicone fluids with conventional, nonionic surfactants. This product has a polydimethyl-siloxane backbone modified via the chemical attachment of polyoxyalkylene chains. MASIL® SF 19 provides reduced surface tension in aqueous and non-aqueous systems, lubricity, and flow and leveling in a variety of coatings, textile, plastic and personal care applications. The data in the table is based on four samples. 4. DOSS 70D at 0.7% add on. Doss 70D is a dialkyl sulfosuccinate anionic surfactant available from Manufacturers Chemicals LLC. The data in the table is based on four samples. 5. Cirrasol® PP862 at 1.0% add on: Cirrasol® PP862 is a non-ionic surfactant that is a blend of hydrogenated ethoxylated castor oil and sorbitan monooleate and is available from Croda International PLC of East Yorkshire, England. The data in the table is based on five samples. 6. Pluronic® P123 at 0.34% add on: Pluronic® P-123 is the tradename for a triblock copolymer manufactured by the BASF Corporation. The nominal chemical formula is HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 2 O) 20 H, which corresponds to a molecular weight of around 5800 Da. Triblock copolymers based on poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) are known generically as poloxamer, and similar materials are manufactured by other companies. The data in the table is based on five samples. 7. Pluronic® P123 at 0.6% add on. The data in the table is based on five samples. 8. Pluronic® P123 at 1.8% add on. The data in the table is based on five samples. 9. Pluraflo® L1060 at 0.5% add on: Pluraflo® L1060 is a non-ionic dispersant (i.e. surfactant) of an ethylene oxide propylene oxide block co-polymer and is available from the BASF Corporation of Florham Park, N.Y. The data in the table is based on four samples. 10. No treatment: No surfactant treatment is added to the base fabric prior to electret treatment. The data in the table is based on five samples.
[0000] Sample number, Post from Electret Pre-elec. Post-elec. electret Wettability above conditions TSI TSI BFE to water? 1 D 20.1 ± 0.9 20.4 ± 0.7 NO 2 C 17.0 ± 0.2 16.4 ± 0.4 90 YES 3 E 20.4 ± 1.0 35.0 ± 21.1 YES 4 B 20.9 ± 0.4 21.7 ± 0.7 YES 5 A 18.8 ± 0.9 73.2 ± 1.1 YES 6 F 21.9 ± 0.7 59.2 ± 0.8 99.1 YES 7 F 21.7 ± 0.6 59.1 ± 1.3 99.9 YES 8 F 35.9 ± 12.2 54.0 ± 1.5 YES 9 A 36.9 ± 8.5 60.9 ± 3.5 YES 10 A 41.2 ± 1.5 68.1 ± 1.4 99.9 NO
Electret conditions:
A—13.75 kV, 1.0 mA B—15 kV, 1.5 mA C—Average of 13 kV, 1 mA and 12.5 kV, 0.7 mA D—12 kV, 0.7 mA E—12 kV, 1.0 mA F—13.75 kV, 11.25 mA
[0034] As can be seen from the results, the first four samples, containing elements other than simply carbon, hydrogen and oxygen, had a very small increase in TSI after electret treatment. This indicates that the BFE results would likely also be poor as shown by sample 2. BFE was not run for the other samples that showed poor TSI results due to the high cost for this test. Beginning with sample 5, however, the difference between the pre- and post-electret TSI was significant. The BFE data that was collected also showed good results, post-electret treatment.
[0035] Electret treatment is used, as discussed above, to increase the BFE of a fabric. This treatment also increases the TSI. It is not believed that differing electret treatment conditions had a great effect on these result and is reported merely for thoroughness. The data shows that the treatments containing other than carbon, hydrogen and oxygen (C—H—O) atoms do not show an appreciable increase in TSI after electret treatment, indicating that they do not allow the fabric to hold a charge and are therefore unsuitable for electret charging. Samples 1, 2 and 4 have little or no positive change in TSI after electret treatment. Note that sample three does show an average increase in TSI but the range of results is extremely wide, leading to questions about repeatability and the value of such results. The successful candidates display large increases in TSI after electret treatment, showing that they allow the web to absorb the charge needed to increase the barrier to microbial infiltration.
[0036] Regardless of the mechanism of operation, it is clear that the treatments for Samples 5-9 that are surfactants containing only carbon, hydrogen and oxygen (C—H—O) atoms are superior to other treatments containing silicon, phosphorus, sulfur and the like, though amounts above 1.5 appear to be less promising. Treatments that are C—H—O surfactants that are essentially free of silicon, potassium, phosphorus and sulfur provide superior TSI NaCl filtration compared to the other treatments 1-4. The preferred amount of surfactant add on is between a positive amount and 1 weight percent or at most 1.5% but must also make the material hydrophilic.
[0037] As used herein and in the claims, the term “comprising” is inclusive or open-ended and does not exclude additional unrecited elements, compositional components, or procedure steps.
[0038] While various patents have been incorporated herein by reference, to the extent there is any inconsistency between incorporated material and that of the written specification, the written specification shall control. In addition, while the disclosure has been described in detail with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various alterations, modifications and other changes may be made to the disclosure without departing from the spirit and scope of the present disclosure. It is therefore intended that the claims cover all such modifications, alterations and other changes encompassed by the appended claims. | The present disclosure describes a surfactant treatment for a polyolefinic nonwoven fabric used as a filtration medium or for collecting dust and dirt, e.g. as a mop or similar device. The surfactant treatment consists essentially of carbon, hydrogen and oxygen atoms. The surfactant treated material has a BFE after electret treatment of at least 97 percent and is hydrophilic. | 3 |
BACKGROUND
[0001] Applicant is not aware of any system capable of telescopically extending and retracting an outrigger shoe for construction equipment, such as, backhoe loaders.
OBJECTS AND FEATURES
[0002] A primary object and feature of the present invention is to provide a system for providing a range of ground positions to position the shoe of an outrigger so that the operator of the construction equipment can select the preferred ground position.
[0003] It is a further object and feature of the present invention to provide lateral movement of construction equipment where the outriggers are in the stabilizing position.
[0004] A further primary object and feature of the present invention is to provide such a system that is safe, efficient, trustworthy, inexpensive and handy. Other objects and features of this invention will become apparent with reference to the following descriptions.
CROSS REFERENCE TO RELATED APPLICATIONS
[0005] Not applicable.
SUMMARY
[0006] Disclosed is a system to stabilize a construction vehicle having a frame and a pair of stabilizing legs with ground-engaging shoes at the ends of the legs. The stabilizing legs pivotally connect to the frame on substantially opposing sides, so that the stabilizing legs pivot upwards to a stowed position and pivot downwards to a stabilizing position where the shoe engages the ground. Further, the stabilizing legs telescope between a retracted position and an extended position. The retracted position locates the shoe closer to the vehicle and the extended position locates the shoe further from the vehicle. A pair of hydraulic cylinders connect to the respective stabilizing legs to power the telescopic movement of the stabilizing legs between the retracted position and extended position.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows a perspective view that illustrates a backhoe loader with an outrigger engaged with the ground after being extended to a location further from the vehicle.
[0008] FIG. 2 shows a top, diagrammatic view that illustrates a backhoe loader positioned near a ditch requiring extension of an outrigger to cross the ditch.
[0009] FIG. 3 shows a top, diagrammatic view that illustrates a backhoe loader positioned near a ditch after translating the backhoe over the ditch by retracting the extended outrigger and extending the retracted outrigger.
[0010] FIG. 4 shows a cross-sectional side view that illustrates the outrigger in the stowed, retracted position.
[0011] FIG. 5 shows a cross-sectional side view that illustrates the outrigger in the stowed, extended position.
[0012] FIG. 6 shows a cross-sectional side view that illustrates the outrigger in the stabilizing, retracted position.
[0013] FIG. 7 shows a cross-sectional side view that illustrates the outrigger in the stabilized, extended position.
[0014] FIG. 8 shows a schematic view that illustrates a hydraulic circuit to retrofit pre-existing construction equipment with the telescoping outrigger.
DETAILED DESCRIPTION
[0015] The present Telescoping Outrigger Systems will now be discussed in detail with regard to the attached drawing figures, which were briefly described above. In the following description, numerous specific details are set forth illustrating the Applicant's best mode for practicing the Telescoping Outrigger Systems and enabling one of ordinary skill in the art to make and use the Telescoping Outrigger Systems. It will be obvious, however, to one skilled in the art that the present Telescoping Outrigger Systems may be practiced without many of these specific details. In other instances, well-known manufacturing methods, mechanical engineering considerations, hydraulic circuit considerations, fluid dynamics principals and other details have not been described in particular detail in order to avoid unnecessarily obscuring this disclosure.
[0016] FIG. 1 shows a perspective view that illustrates backhoe loader 110 with stabilization leg 120 engaged with ground 130 after being extended to a location further from backhoe loader 110 across ditch 140 . System 100 shows how outriggers on backhoe loaders can extend and retract hydraulically. That is, system 100 shows how outriggers can telescope their length to provide positioning of shoe 125 across a range of ground locations to permit the operator to place shoe 125 on stable ground. Hydraulically telescoping outriggers can be helpful when shoe 125 would otherwise be positioned inside or along the edge of the ditch that the backhoe loader digs.
[0017] For example, as shown in FIG. 1 , backhoe loader 110 uses the bucket 150 to dig a ditch 140 in the ground 130 between building 160 and a terminus, (which is not shown), such as the street, or utility connection. It is desirable to dig ditch 140 to extend close to both building 160 and the terminus using backhoe loader 110 (and not digging manually, for example, using shovels). One way to dig ditch 140 using backhoe loader 110 would be to begin digging at the terminus and proceed toward building 160 . As the ditch approaches building 160 , backhoe loader 110 would be turned around to complete the ditch (and to avoid running into the building) by digging outwardly from the building back toward the ditch 140 .
[0018] Without telescoping outriggers, backhoe loader would likely place the outrigger inside the ditch (that is, not properly engaged with ground), or, immediately next to the ditch where the ground may not be stable. Without telescoping outriggers, the backhoe loader operator might need to re-position or repeatedly re-position the backhoe loader to avoid an undesirable placement of the outrigger shoe. Without the telescoping outriggers, the backhoe loader might be required to refill a portion of the ditch in order to place the outrigger stably.
[0019] As shown, backhoe loader 110 could avoid these problems. Backhoe loader 110 shows outrigger 120 extended beyond ditch 140 to place shoe 125 beyond ditch 140 . Without extending, outrigger 120 might be placed in ditch 140 . This shoe 125 placement relieves the need to reposition backhoe loader 110 , which may improve efficiency, for example, because the time spent repositioning the backhoe loader could be saved. This shoe 125 placement relieves the need to partially fill in ditch 140 , which may save time and improve safety, for example, because the time spent partially filling in the ditch could be saved and because more stable ground could be selected for placement of the shoe of the outrigger.
[0020] By allowing a wider range of placements of the shoe 125 , safety can be improved, for example, because a more stable location for placing the shoe 125 may be selected by the operator. The telescoping outrigger maintains many of the existing benefits of backhoe outriggers generally. For example, the outriggers remain stowable for easy transportation of the backhoe rigger.
[0021] Further, when the backhoe loader is used on uneven ground, the use of telescoping outriggers can provide additional positioning of the backhoe loader and placement of the shoe of the outrigger.
[0022] As shown in the exploded portion A of FIG. 1 , the outrigger 120 can be telescoped (that is, extend or retract along a range of ground positions) and moved between stowed/stabilized positions using hydraulic cylinders. Hydraulic cylinder 127 moves outrigger 120 between a stowed position and a stabilizing position. Hydraulic cylinder 129 is shown positioned inside outrigger 120 . Hydraulic cylinder 129 extends or retracts the length of outrigger 129 , because outrigger 120 has two mating portions that slide along the long axis.
[0023] Backhoe loader 110 has a bucket 150 for digging and excavating on one end. Backhoe loader 110 has a loader 170 on the other end for conveying materials into transportation trucks. Backhoe loader 110 prepares for excavation by lowering loader 170 and both of its outriggers 120 , as shown, to stabilize the backhoe loader 110 while the bucket 150 moves, swings, and scoops during excavation. If necessary outriggers 120 may be telescoped to select a desirable or stable ground position for shoe 125 . Backhoe loader 110 excavates by swinging bucket 150 out to engage the ground by extending the stick and boom 190 , and scooping up earth, which can be picked up and placed into piles of dirt 180 , as shown.
[0024] The construction vehicle may be any suitable mechanical excavator with bucket and hinged boom, such as, the bucket loader (or front-end loader) shown in FIG. 1 , for backhoe loader 110 . Alternately, construction vehicle may be an excavator with features like removable buckets, removable loaders, etc. The stabilizing leg may be any suitable stabilizing beam such as rigger shown in FIG. 1 , for outrigger 120 . The frame may be any suitable vehicle chassis, such as the body of the backhoe loader shown in FIG. 1 . The tractor may be any suitable prime mover, such as the engine enclosed in the backhoe loader shown in in FIG. 1 .
[0025] The backhoe bucket may be any suitable excavating-scoop such as the shovel-scoop shown in FIG. 1 , for bucket 150 . The loader bucket may be any suitable bucket conveyor for loading materials, such as the wide scoop shown in in FIG. 1 as loader 170 . The shoe may be any suitable ground-engaging member, such as the friction gripper shown in FIG. 1 for shoe 125 . The stick and boom may be any suitable hinged boom, such as the pivoting, two-beam hydraulically controlled boom shown in FIG. 1 as stick and boom 190 .
[0026] The hydraulic cylinder may be any suitable linear hydraulic motor, such as the mechanical actuator that provides a unidirectional force with a unidirectional stroke, shown in FIG. 1 for hydraulic cylinder 127 and hydraulic cylinder 129 .
[0027] FIG. 2 shows a top, diagrammatic view that illustrates backhoe loader 110 positioned near ditch 140 requiring extension of an outrigger to cross ditch 140 . FIG. 3 shows a top, diagrammatic view that illustrates backhoe loader 110 positioned near ditch after translating the backhoe over ditch 140 by retracting extended outrigger 122 and extending retracted outrigger 121 .
[0028] Now turning to FIGS. 2 3 together, these figures show that the operator of backhoe loader 110 may translate backhoe loader 110 from side to side by simultaneous extending one outrigger and retracting the other outrigger, as shown. FIG. 2 shows outrigger 121 ′ in the retracted position and outrigger 122 ′ in the extended position. In both FIG. 2 and FIG. 3 , loader 160 may be lowered to the ground position and is providing a third point of stabilization with the ground. This arrangement may be desirable because it would position the ground engaging end of outrigger 122 beyond ditch 140 . Between the positions of the backhoe loader 110 shown in FIG. 2 and FIG. 3 , operator would simultaneously extend outrigger 121 and retract outrigger 122 . FIG. 3 shows the outrigger 121 ″ in the extended position and outrigger 122 ″ in the retracted position.
[0029] The result is that backhoe loader has moved predominately sideways, which can be seen by the movement of pivot 155 . Bucket 150 is attached to the stick and boom which is attached to backhoe loader 110 at pivot 155 . Pivot 155 allows bucket 150 to swing from side to side. In FIG. 2 , pivot 155 ′ is positioned well to one side of ditch 140 , as shown. In FIG. 3 , pivot 155 ″ is positioned substantially over top of ditch 140 , as shown. Further, FIG. 3 shows that the wheels of backhoe loader may be positioned over ditch 140 , as well. That is, the lateral translation of the backhoe loader may allow the backhoe loader to reach positions and placements that may not be reached by driving on backhoe loader's wheels. This arrangement may have the further advantage of saving time by aligning the in-and-out scooping motion of bucket 150 (along the hinged stick and boom) with ditch 140 , as shown in FIG. 3 , which may aid in efficiency of excavation, ease of operation, or provide other advantages.
[0030] Loader 160 may rotate over (or slide across) the ground to accommodate the predominately sideways motion of the backhoe loader 110 . This can be seen by the change in angle of the loader 160 relative to ditch 140 , as shown between FIGS. 2 3 .
[0031] FIG. 4 shows a cross-sectional, side view that illustrates outrigger 200 in the stowed, retracted position. FIG. 5 shows a cross-sectional side view that illustrates outrigger 200 in the stowed, extended position. FIG. 6 shows a cross-sectional side view that illustrates outrigger 200 in the stabilizing, retracted position. FIG. 7 shows a cross-sectional side view that illustrates outrigger 200 in the stabilized, extended position.
[0032] Now, considering FIGS. 4 , 5 , 6 , 7 together, the various extreme (that is, fully-extended or fully-contracted) positions of outrigger 200 can be seen. Outrigger 200 connects to frame 210 , as shown. The medial end of outrigger 200 pivotal connects to frame 210 at joint 292 , as shown. The medial end of hydraulic cylinder 270 pivotally connects to frame 210 at joint 294 , as shown. The distal end of hydraulic cylinder 270 pivotally connects to outrigger 200 at joint 298 , as shown. This arrangement of joints 292 , 294 , and 298 with outrigger 200 and hydraulic cylinder 270 allows outrigger 200 to rotate between at stowage position and a stabilization position. These pivoting connections may be made by pins.
[0033] Outrigger 200 pivotally connects to shoe 230 at joint 296 , as shown, which allows shoe 230 to engage the ground at a varying angle. This pivoting connections may be made by a pin. Alternately, the shoe may be fixedly connected to the outrigger.
[0034] Outrigger 200 includes external member 250 and internal member 240 , as shown. External member 250 may be disposed around internal member 240 to allow internal member to slide in and out along the long axis. Hydraulic cylinder 260 may be disposed inside of internal member 240 and fixedly connected to the distal end, as shown. Hydraulic cylinder 260 may be disposed inside of external member 250 and fixedly connected to the medial end, as shown. This arrangement of external member 250 , internal member 240 and hydraulic cylinder 260 allows outrigger 200 to extend and retract, that is, it allows telescoping along the long axis of outrigger 200 . The external member 250 , internal member 240 and hydraulic cylinder 260 may be designed to be sufficient to overcome the forces generated during swinging, scooping and otherwise operating the bucket on the stick and boom, for example, selection of the materials and design may include factors such as modeling of mechanical forces, advances in materials technology, advances in hydraulics or fluid dynamics, economic considerations, etc.
[0035] The beams may be any type of slidably-mating beams, such as the mating cylinders shown in FIGS. 4 , 5 , 6 , 7 for external member 250 and internal member 240 .
[0036] Alternately, the external member and internal member may be reversed, with the internal member connected to the frame and the external member connected to the shoe. Further alternately, the hydraulic cylinder may be disposed along the outside of the outrigger. Yet further alternately, the members may be inter-mating in any fashion that allows sliding or extension/contraction along the long axis. In some embodiments, the joint between the stowage/stabilization cylinder and the outrigger may be desirable on the portion/beam/member that is immediately pivotally connected to the frame.
[0037] FIG. 8 shows a schematic view that illustrates hydraulic circuit 300 to retrofit pre-existing construction equipment with a pair of telescoping outriggers. For pre-existing construction equipment, a kit may be provided to retrofit with telescoping outriggers. This kit would include two telescoping outriggers, of the type shown in FIGS. 4 , 5 , 6 , 7 . The kit could also include sufficient controls to operate the two new hydraulic cylinders, that is, control valve, lines, and manual valves for the placement in cab. The kit would also include installation instructions (to describe the installation steps) and an operating manual (to describe operation of the telescoping outrigger after installation).
[0038] This kit would be sold as an aftermarket solution. Kits would be assembled using parts with appropriate dimensions for the make, model, and/or year of construction equipment. The outrigger would mount to the pre-existing machine frame pin bores. The outrigger arm would house a separate control valve, which would allow the telescoping circuit to be operated by the pre-existing stow/stabilize hydraulic circuit.
[0039] Installation would begin by removal of the original (non-telescoping) outrigger. The hydraulic cylinder (for stow/stabilize hydraulic circuit) would be left attached to the construction equipment. Next, the new telescoping outrigger would be attached to the frame of the construction equipment, which includes a hydraulic cylinder for extend/retract hydraulic circuit. Finally, the extend/retract cylinder would be connected to the existing hydraulic circuit by modifying the circuit to function as shown in FIG. 8 .
[0040] FIG. 8 shows a hydraulic circuit that permits use of the existing (stow/stabilize) hydraulic controls to alternate between controlling the pair of hydraulic cylinders that stow/stabilize and controlling the pair of hydraulic cylinders that extend/retract (telescope). The original hydraulic lines from head end 310 and rod end 315 of the stow/stabilize hydraulic circuit may be connected into the diverter valve 320 , which may be the diverter valve provided with the telescoping outrigger as part of a kit.
[0041] Hydraulic oil may flow into diverter valve 320 from the head end 310 and rod end 315 , as shown. Diverter valve 320 contains control spools 321 , double check valves 327 , and pressure reducing valve 325 , as shown. Upon activation of the hydraulic circuit, pilot oil would be produced through pressure reducing valve 325 , as shown. This pilot oil would flow to control valves 330 located in cab 340 . Hydraulic fluid may be any suitable incompressible fluid, such as hydraulic oil.
[0042] Control valves 330 are detented. When control valves 330 are in a normal position, control valves 330 would block oil and allow only operation of the stow/stabilize hydraulic circuit of the stow/stabilize hydraulic cylinder 350 . This allows moving the telescoping outrigger between the stowed position and the stabilizing position.
[0043] When the operator would like to operate the telescoping hydraulic circuit, the operator would change the position of the detented control valves 330 . The pilot oil from the control valves 330 would then travel back to diverter valve 320 allowing the position of spools 321 to re-direct the pump flow to the extend/retract hydraulic circuit of the telescoping cylinder 360 .
[0044] In some embodiments, diverter valve 320 may be mounted within or upon the telescoping outrigger. In some embodiments, it may be preferable to provide quad check valves or multiple check valves to prevent movement of the stow/stabilize cylinder while the extend/retract hydraulic circuit is in use.
[0045] The hydraulic controller may be any suitable mechanical, pilot, or electro-hydraulic controls, such as the diverter valves shown in FIG. 8 as diverter valve 320 .
[0046] For installations into new construction equipment, the original equipment manufacturer may include a control circuit as part of the original construction equipment. This control circuit would be operated from the cab by the operator and allow extension and retraction of the telescoping outriggers, either independently, or simultaneous (as desirable to create side-to-side movement described in FIGS. 2 3 , above). These controls may be mechanical, pilot, or electro-hydraulic controls, or other types of controls.
[0047] Although Applicant has described Applicant's preferred embodiments of this invention, it will be understood that the broadest scope of this invention includes modifications and implementations apparent to those skilled in the art after reading the above specification and the below claims. Such scope is limited only by the below claims as read in connection with the above specification. Further, many other advantages of Applicant's invention will be apparent to those skilled in the art from the above descriptions and the below claims. | A system to stabilize a construction vehicle having a frame and a pair of stabilizing legs with ground-engaging shoes at the ends of the legs. The stabilizing legs pivotally connect to the frame on substantially opposing sides, so that the stabilizing legs pivot upwards to a stowed position and pivot downwards to a stabilizing position where the shoe engages the ground. Further, the stabilizing legs telescope between a retracted position and an extended position. The retracted position locates the shoe closer to the vehicle and the extended position locates the shoe further from the vehicle. A pair of hydraulic cylinders connect to the respective stabilizing legs to power the telescopic movement of the stabilizing legs between the retracted position and extended position. | 4 |
[0001] This application claims the benefit of Provisional Patent Application No. 61/784,150, filed Mar. 14, 2013.
FIELD OF THE INVENTION
[0002] The invention relates to the inhibition of hypoxia-inducible factor activity.
BACKGROUND OF THE INVENTION
[0003] The use of plant extracts in Traditional Chinese Medicine (TCM) can be traced back to 6000 years ago (Solecki and Shanidar, 1975). In recent years, there has been a burgeoning use of plant extracts in TCM for modern drug discovery (Graziose et al., 2010). These plant extracts are used for a variety of purposes including health improvement, beauty, and nutritional supplementation, as well as prevention and treatment of diseases, including diabetes and cancer (Graziose et al. 2010).
[0004] Carica papaya is one of the candidate plants. It has been reported to have medicinal properties towards various diseases including dengue fever (Ahmad et al., 2011), wound healing (Mahmood et al., 2005) and asthma (Canini et al., 2007). Extracts from Carica papaya also claimed to have anti-cancer properties (Morimoto et al., US Patent Application No. 20080069907). These investigators, however, did not indicate the specific mechanisms that were involved in the anti-cancer effects, nor did they indicate that the age of the plant could have any effect on the efficacy of the treatment.
[0005] Oxygen homeostasis is a critical element for physiological well-being of the human body. Limited oxygen supply, termed hypoxia, plays a major role in the pathobiology of solid tumors. Hypoxia and oxidative stress pathways are associated with various human disorders, including inflammatory diseases, vascular diseases, cancer and infectious diseases. Cells in hypoxic regions of tumors are more resistant to radiation and chemotherapy (Brown. 2000). They are also more resistant to cell death signaling (Seol et al., 2009). Master regulators of cell survival under hypoxia are the hypoxia-inducible factors (HIFs), HIF-1 and HIF-2. These transcription factors regulate several processes vital for the cells to survive the hypoxic conditions (Semenza, 2011; Miyara et al. 2011). Since these cancer cells have altered metabolic mechanisms for survival under hypoxia, we conjectured that their responses to plant extracts also will be different from normoxic cancer cells. Even though HIF-inhibitory drugs have been approved by the US-FDA for clinical use (Xia et al., 2012), their undesirable side effects are still problematic (Sanchez et al., 2012; Yamaguchi et al., 2012). Due to the limited number of drug candidates in the pipeline and the adverse side effects of the approved ones, identification and development of candidate drug inhibitors that target the HIF-1 pathway are urgently needed.
BRIEF SUMMARY OF THE INVENTION
[0006] We have discovered that methanolic extracts of certain Carica papaya leaves have a potent inhibitory effect on HIF. The Carica papaya leaves effective in this invention are “young” leaves, which in this invention is defined as obtained from a plant of age six months and younger from the date of germination of the seed, i.e., six months and younger from the date the plant seed sprouts. Cytotoxicity analyses showed that such young Carica papaya extracts caused high toxicity towards hypoxic cells but not normoxic cells. This specificity is crucial when one targets to eliminate only the hypoxic cells. Based on this specificity, adverse side effects of the extracts and their general toxicity on non-target cells will potentially be eliminated. Therefore, in accordance with this invention, an extract of young Carica papaya leaves is used as an inhibitor of HIF to effectively block hypoxia-inducible factor (HIF) function and methods of use thereof. More specifically it relates to the use of such young Carica papaya plant extract to eliminate unwanted cells by inhibiting HIF. The compounds and compositions of the present invention are useful in the prevention and treatment of hypoxia-related conditions and diseases such as inflammatory diseases, vascular diseases, cancer and infectious diseases.
[0007] In a particular embodiment, a method is provided for treating a solid hypoxic tumor in a patient, comprising the steps of identifying a patient having a solid hypoxic tumor, and administering to the patient an extract of young Carica papaya leaves. The extract can be administered to the patient as a therapeutically acceptable amount of a pharmacon comprising the extract in a pharmaceutically acceptable carrier wherein the patient is not otherwise indicated for treatment with the extract of Carica papaya leaves. The pharmacon can be formulated as a liposome, incorporated into a polymer release system, or suspended in a liquid in a dissolved form or as a colloidal form.
[0008] In another embodiment, the extract is administered in combination with a chemotherapeutic agent, such as cisplatin or chetomin.
[0009] In another embodiment of the invention, we provide as a composition of matter an alcohol extraction from young Carica papaya leaves.
[0010] In another embodiment of the invention, we provide an article of manufacture comprising a vessel containing an extract of young Carica papaya leaves and instructions for use of the extract for the treatment of a solid hypoxic tumor in a method comprising identifying a patient having a solid hypoxic tumor, and administering to the patient an effective amount of an extract of young Carica papaya leaves. An effective amount of a composition for treating a cancer will be that amount necessary to inhibit mammalian cancer cell proliferation in situ. Those of ordinary skill in the art are well-schooled in the art of evaluating effective amounts of anti-cancer agents.
[0011] In another embodiment of the invention, we provide an article of manufacture comprising packaging material and contained within the packaging material, an extract of young Carica papaya leaves wherein the packaging material comprises a label that indicates that the extract can be used for treating a solid hypoxic tumor
[0012] In a further embodiment of the invention, the young Carica papaya leaves are extracted with an alcohol, which can be monohydric, polyhydric, unsaturated aliphatic, or alicyclic
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which:
[0014] FIG. 1A shows the effects of methanolic plant extracts on Saos-2 cells in normoxia and hypoxia with dose response curves from an MTT assay and where cisplatin and chetomin were used as positive controls.
[0015] FIG. 1B shows a compilation of the IC 50 's of the extracts and experimental control drugs in which data are shown as mean±S.E.M. of triplicates from a representative of three independent experiments, and in which the asterisk (*) represents a significant difference (P<0.05) among the IC 50 in normoxia and hypoxia.
[0016] FIG. 2 shows the effects of plant extract treatment on HIF activities in hypoxic Saos-2 cells where a hypoxia driven firefly luciferase reporter assay was used to measure HIF activity in the cells and positive values indicate increased HIF inhibition while negative values showed HIF activation.
[0017] FIG. 3 shows the effects of Carica papaya extract treatment on HIF-driven reporter gene expression in which the HRE-luc Saos2 cells (Malaysian patent filing #: PI 2012003492) were treated with different concentrations of Carica papaya extract and incubated in either normoxic or hypoxic conditions, and in which Luciferase signal intensities were measured after 24 hours.
[0018] FIG. 4 shows the percent HIF inhibition in the plant extract or drug-treated hypoxic HRE-luc Saos2 cells where Carica papaya and control extract concentrations were 0.1 mg/ml, cisplatin concentration was 0.1 mM. The percent HIF inhibition was calculated as a ratio of the difference between untreated and treated sample to the untreated sample, and a positive value indicates HIF inhibition, while a negative value denotes HIF activation.
[0019] FIG. 5 shows the percent of HIF inhibition for leave crude extracts obtained from plants of age either six months or younger or older than six months, where negative inhibition value indicates activation of HIF, the symbol “*” denotes statistically significant difference (P<0.05) compared to the untreated control, B=Batch number, and R=Replicate.
[0020] FIG. 6 shows the percentage of HIF inhibition with brew samples using prior art extraction procedures described in Morimoto et al. US patent Application No. 20080069907 on leaves obtained from plants older than 10 months from the date of germination of the seed, where negative inhibition value indicates activation of HIF, B=Batch number, and R=Replicate.
DETAILED DESCRIPTION OF THE INVENTION
[0021] The discovery of the unique properties of the extract of young Carica papaya leaves arose from an investigation of the effects of the extracts of various plants on HIF activity, and the effect of the age of the Carica papaya leaves on HIF inhibitory activities. Descriptions of those experiments will be given followed by specific investigations of extracts from Carica papaya leaves.
The Effects of the Extracts of Various Plants on HIF Activity
Cell Line and Culture Conditions
[0022] A human osteosarcoma cell line, Saos-2 stably expressing four copies of the erythropoietin hypoxia response elements (HRE-luc Saos2; Shafee et al., Malaysian Patent Application 14: PI 2012003492), was cultured in DMEM medium (PAA, USA) supplemented with 10% (v/v) fetal bovine serum (FBS; PAA, USA) and 1% (v/v) antibiotic-antimycotic (PAA, USA) in a humidified incubator supplied with ambient oxygen and 5% CO 2 at 37° C. An hypoxic gaseous environment was created by incubating cells in a ProOx in vitro chamber (BioSpherix), controlled by ProOx model 110 (BioSpherix). The cells were supplied 0.5% O 2 , 94.5% N 2 and 5% CO 2 at 37° C.
Plant Materials, Cell Culture Treatment and Viability Assay
[0023] Nine types of plants with known medicinal properties were tested in this study, and are described in Table 1:
[0000]
TABLE 1
Plants used in the study and their medicinal uses.
Plant name
Medicinal use and references
Melastomataceae
Anti diarrhoeal (Sunilson et al., 2009), antimicrobial (Thatoi et
Melastoma
al., 2008), cytotoxicity, antiviral (Lohezic Le Devehat et al.,
malabathricum
2002), anticoagulant (Manicam et al., 2010), antipyretic,
L.
anti-inflammatory, antinociceptive (Zakaria et al., 2006),
antioxidant, free radical scavenging activity and anticancer
(Susanti et al., 2007).
Acanthaceae
Antidiabetic, diuretic, antilytic, laxative (Sunarto, 1977),
Strobilanthes
anticancer (Yaacob et al., 2010), anti-AIDS, antihypertensive
crispa
(Liza et al, 2010), antioxidant (Abu et al., 2007),
T. Anderson
antihyperglycemic and antilipidemic (Fadzelly et al., 2006)
Cactaceae
Antitumour, anti-rheumatic, antiulcer, anti-inflammatory
Pereskia
(Goh, 2000), relief of headache, gastric pain, hemorrhoids,
grandifolia
atopic dermatitis, body revitalization (Goh, 2002; Rahmat,
Haw.
2004; Tan et al., 2005), reduce swelling (Sahu et al., 1974;
Anon, 1969) and antioxidant (Sim et al., 2010).
Compositae
Eruptive fever, rash, kidney disease, migraines, constipation,
Gynura
hypertension, diabetes mellitus, cancer (Perry, 1980),
procumbens
anti-herpes simplex virus, antidiabetic, urinary infection,
(Lour.) Merr.
antiallergic, reduce cholesterol and high blood pressure
(Jiratchariyakul et al., 2000), antihyperglycaemic (Akowuah et
al., 2001; Akowuah et al., 2002; Hassan et al., 2010),
anti-inflammatory (Iskander et al., 2002; Jiratchariyakul et al.,
2000), anti-hyperlipidaemic (Zhang and Tan, 2000),
hypertension (Lam et al., 1998; Kim et al., 2006), wound
healing (Zahra et al., 2011) and antiulcer (Mahmood et al.,
2010), antioxidant and antitumour (Maw et al., 2011)
Umbelliferae
Cancer (Yu et al., 2007; Huang et al., 2008), fever
Hydrocotyle
(Manandhar, 1993; Pfoze et al., 2012), edema, detoxication,
sibthorpioides
throat pain, diuretic, psoriasis (Li, 1986), rheumatalgia,
Lam.
dysentery, whooping cough, jaundice (Srivastava et al., 2012),
viral infection (Li, 2000; Wang 2000; Yu et al., 2007).
Caricaceae
Anti-tumor (Otsuki et al., 2010), anti-Dengue fever (Ahmad
Carica
et al., 2011), antisickling (Imaga et al., 2009), vasodilatatory,
papaya
antioxidant, reduction of cardiovascular risks (Runnie et al.,
L.
2004), wound healing (Mahmood et al., 2005), asthma
relieving, vermifuge, treatment of gastric problems, fever,
amoebic dysentery (Canini et al., 2007).
Labiatae
Antioxidant (Hsu et al., 2010), anti-inflammatory (Hsu et al.,
Orthosiphon
2010); Nadia et al., 2012), kidney stones (Hsu et al., 2010),
aristatus
dysuria (Premgamone et al., 2008), hypertension (Matsubara
(Blume) Miq.
et al., 1999; Ohashi et al., 2000).
Cactaceae
Anticancer (Malek et al., 2009; Tan et al., 2005), antitumour,
Pereskia
anti-rheumatic, antiulcer, anti-inflammatory, antidiabetic and
bleo
hypertension (Goh, 2000), antiproliferative and mutagenic (Er
DC.
at al., 2007), relief of headache, gastric pain, hemorrhoids,
atopic dermatitis, body revitalization (Goh, 2002; Rahmat,
2004; Tan et al., 2005).
Acanthaceae
Skin rashes, insect and snake-bite, analgesic, anti-
Clinacanthus
inflammatory (Satayavivadetal., 1996; Wanikiat et al., 2008),
nutans
anti-HSV and anti-VZS (Jayavasu et al, 1992; Thawaranantha
(Burm. f.) Lindau
et al., 1992), bladder activity (Low et al., 2011).
[0024] The voucher specimens were deposited in the Herbarium of Institute of Biosciences, Universiti Putra Malaysia. Leaves of these plants were subjected to methanolic extraction as described in Hsu et al. 2010. The leaves were washed with distilled water and left to air-dry at room temperature or in an oven at 40° C. until a constant weight was obtained. Dried leaves were then blended into a powder form, soaked and extracted in methanol at a 1:3 ratio (w/v) for three days at room temperature. Extracts were filtered by Whatman No. 1 filter paper with the aid of a vacuum pump. The residues were re-extracted twice using the same methanolic method. Filtrates were then concentrated by rotary evaporator at a maximum of 40° C. Concentrated extracts were collected in glass vials with push-in caps and dried in an oven at 40° C. until a constant weight was obtained. All of the crude extracts were stored −80° C. Prior to use, the extracts were prepared at the required concentrations by dissolving them in serum-free DMEM media with a final DMSO concentration of less than 0.5% (v/v), centrifuged at 1000×g and filtered through 0.22 μM filters. Overnight cultures of cells, initially seeded at 1.5×10 4 cells per well in a 96-well plate, were treated with selected concentrations of plant extracts and incubated in normoxic or hypoxic conditions. After 24 h of incubation, an MTT assay (Jamal et al. 2012) was employed to determine cell viability following treatment of cultured cells with selected concentrations of the crude plant extract. These concentrations were determined empirically and selected to cover a range of effects, ranging from no effect to significant cytotoxicity. Initially, cells were seeded at 1.5×10 4 cells per well in a 96-well plate for 24 h. The cells were treated with selected concentrations of the extract and incubated in normoxic or hypoxic conditions. After 24 h of treatment, spent culture medium was replaced with fresh serum-free DMEM containing 0.5 mg/ml MTT. After a further 4 h of incubation in 5% CO 2 at 37° C., formazan precipitates that formed were dissolved with 100 μl of DMSO and the reaction was read in a microplate reader (Model 550. BioRad, Hercules, Calif.) at 570 nm absorbance and 630 nm as the reference wavelength.
HIF Reporter Assay
[0025] Cells were co-transfected with a hypoxia-driven firefly luciferase reporter plasmid construct containing four copies of the erythropoietin (EPO) hypoxia response elements (HRE) and a pRL-CMV expressing Renilla luciferase as described previously (Kaluz et al., 2008, Shafee et al., 2009, Shafee et al. Malaysian Patent Application No. PI 2012003492). Transfected cells were treated with appropriate concentrations of plant extracts and incubated in either normoxic or hypoxic conditions. After 24 h, firefly and Renilla luciferase signal intensities were measured (Kaluz et al. 2008. Shafee et al. 2009). Percent HIF inhibition was calculated as a ratio of the difference between untreated and plant extract-treated sample to the untreated sample. A positive value indicates HIF inhibition, while a negative value denotes HIF activation.
Statistical Analysis
[0026] The Student t-test was used to analyze the experimental data in this study. Results were expressed as mean±standard error of the mean (SEM). A p value of <0.05 was considered significant.
Results and Discussion
[0027] To investigate whether hypoxia affects cellular responses to plant extract treatment, cells were treated with selected concentrations of each extract, and their viability was determined. As positive controls for inhibition of HIF activity, we included cisplatin (Duyndam et al., 2007), and Chetomin (Tan et al. 2005). Different patterns of cytotoxicity were observed when the cells were treated in normoxic versus hypoxic conditions. As expected (Song et al., 2006), the IC 50 value for cisplatin in hypoxia is significantly higher than in normoxia ( FIG. 1A ). For the first time, we show that the IC 50 of chetomin also increased in hypoxia.
[0028] Melastoma malabathricum, Strobilanthes crispus and Pereskia grandifolia , showed no drastic differences in cytotoxicity when lower concentrations (<50 μg/ml) of extracts were used ( FIG. 1A ). However, at concentrations higher than 150 μg/ml, cytotoxicity to Melastoma malabathricum became more evident in the hypoxic compared to the normoxic cultures. Cytotoxic and antiproliferative activities of methanolic extracts of Melastoma malabathricum have been previously reported (Devehat et al. 2002). Their studies, which were done under normoxia, showed that the IC 50 values of the extract ranges from 19 to >400 μg/ml depending on the cell line tested. Results in the present study showed that hypoxic cancer cells are more susceptible to Melastoma malabathricum cytotoxicity when the concentrations used are above 150 μg/ml. Therefore, it is likely that the IC 50 of the extracts will be lower in hypoxic cancer cells. For Strobilanthes crispus the difference in cytotoxicity began to be seen as early as 100 μg/ml. Beginning at this concentration, cells in the hypoxic environment showed a higher rate of cell death compared to the cells in the normoxic environment. The opposite situation was observed in the cells treated with Pereskia grandifolia . Cytotoxicity of the cells was observed to be higher in the normoxic condition instead, even though cytotoxicity was seen earlier, at 25 μg/ml.
[0029] Gynura procumbens, Hydrocotyle sibthorpioides and Carica papaya extracts showed different cytotoxicities in normoxia and hypoxia at all concentrations used. Gynura procumbent and Hydrocotyle sibthorpioides were found to induce cell proliferation at concentrations lower than 150 μg/ml. No induction was seen for Carica papaya extract. Interestingly, in hypoxia, all these extracts induced higher cell proliferation than in normoxia. To the best of our knowledge, this is the first report to show induction of cell proliferation in cancer cells by these three plant extracts. Gynura procumbens has been shown to contribute towards the wound healing process (Zahra et al. 2011). Our findings of increased cell proliferation, albeit in cancer cells, may help contribute towards further understanding of mechanisms involve in the process of wound healing. Similar to our findings in the normoxic condition, the inefficiency of Hydrocotyle sibthorpioides extracts in cell killing was also reported previously (Huang et al., 2008). They showed that the IC 50 of Hydrocotyle sibthorpioides ethanolic extracts in cancer cells was >2000 μg/mL. For Carica papaya , we observed a minimal stimulatory effect in hypoxia at concentrations lower than 250 μg/ml. However, above this concentration, its cytotoxicity increased tremendously. In normoxia, on the other hand, the extract showed a gradual increase in cytotoxicity with increasing concentrations of extracts. This result is supported by Otsuki et al. (2010) which reported anti-proliferative responses of various tumor cell lines in normoxic conditions towards Carica papaya extracts.
[0030] Orthosiphon aristatus, Pereskia bleo and Clinacanthus nutans extracts showed minimal cytotoxicity in both normoxic and hypoxic conditions. Orthosiphon aristatus extract, which was previously shown to have antioxidant and anti-inflammatory effects (Hsu et al., 2010), showed a gradual reduction of cell viability with increasing amounts of extract used in the normoxic condition. But in the hypoxic condition, no statistically significant difference in cytotoxicity was observed until 500 μg/ml were used, when a sharp drop in cell viability was observed in both normoxic and hypoxic conditions, indicating a general cytotoxity. For Pereskia bleo and Clinacanthus nutans extracts, no significant cytotoxicity was seen until at the highest concentrations tested under normoxic conditions. This finding is in agreement with a study by Er et al. (2007) which also failed to observe any notable anti-proliferative effect of Pereskia bleo methanolic extract in 4T1 and NIH/3T3 cell lines. In contrast, Malek et al. (2009) reported cytotoxicity effects of Pereskia bleo methanolic extract in several cancer cell lines. Besides the different types of cancer cells used, another possible explanation for these inconsistencies is the gaseous conditions used in their studies. In our study, we found that hypoxic environment led to growth stimulatory response by Pereskia bleo but not for Clinacanthus nutans . This result strongly suggests that microenvironmental conditions contribute towards cellular responses to plant extract treatments.
[0000] Specific Investigation of Extracts from Carica papaya Leaves.
[0031] The following describes the specific investigation of whether HIF is affected by Carica papaya plant extract treatment, HRE-luc Saos2 cells were treated with selected concentrations of the extract, and their HIF-responsive luciferase signal was determined. The untreated samples showed the expected response pattern, where the signal was only increased in hypoxia but not normoxia ( FIG. 3 ). The high hypoxic signal was dramatically reduced in cells treated with various concentrations of Carica papaya extracts. At the lowest concentration tested (0.1 mg/ml) the signal was reduced by almost 40%. As the concentration of the extract increased, the signal also decreased. However, due to the possibility of general cytotoxicity of the extracts on the cells, the reduced signals need to be further studied. Prior to performing further investigation, we compared the inhibitory properties of the Carica papaya against cisplatin, a known inhibitor of HIF (Duyndam et al., 2007).
[0032] At 0.1 mg/ml concentration, Carica papaya extract reproducibly inhibits HIF signals by approximately 40% ( FIG. 4 ). This inhibition was comparable to cisplatin, where the inhibition was around 60%. To confirm that the signal inhibition was not due to a general effect of extract treatment on the HRE-luc Saos2 cells, another plant extract was used as a control. Treatment of this extract at a similar concentration to Carica papaya extract, did not result in any HIF inhibitory signal. Instead, a slight increase was observed. This increase was expected since HIF is also a stress-response signal (Semenza, 2011; Miyata et al., 2011). Therefore, cells which undergo stress, in this case perhaps by the presence of the extract, will display a slight increase in HIF activity. These data clearly demonstrate the specificity of Carica papaya extract on HIF inhibition.
[0033] To verify that the reduced HIF signals were not due to cytotoxicity effects of the Carica papaya extract on the cells, we performed an MTT assay on the treated cells. At 0.1 mg/ml concentration, where HIF signal was suppressed by as much as 40%, the cells appeared to be viable ( FIG. 1A ). In fact, the cell number was slightly increased in the hypoxic condition, suggesting a minimal effect of the Carica papaya extract on the general properties of the cells. At higher concentrations, the extract began to affect cell viability, particularly in the hypoxic condition. This interesting observation suggests that hypoxic cells are more susceptible to Carica papaya -induced cytotoxicity compared to normoxic cells. Therefore, Carica papaya is an ideal candidate to eliminate unwanted hypoxic cells. To observe the pattern of HRE-luc Saos2 cell killing by HIF-inhibitors in normoxic and hypoxic conditions, cisplatin was used. Additionally, another specific inhibitor of HIF, chetomin (Tan et al., 2005), was also used. This was a proof-of-concept study to confirm the results observed in the Carica papaya extract-treated samples. Referring to the respective plots for Carica papaya , cisplatin, and chetomin in FIG. 1A , a different pattern of cytotoxicity was observed when the cells were treated with these drugs in normoxic versus hypoxic conditions. As expected, the IC 50 value for cisplatin in hypoxia is significantly higher than in normoxia. Hypoxia-induced resistance to cisplatin treatment was previously reported (Song et al., 2006). For the first time, we have shown in this study that the IC 50 of chetomin also increased in hypoxia.
Overall
[0034] Our data demonstrate that methanolic Carica papaya plant extracts showed different IC 50 values in hypoxic versus normoxic conditions ( FIG. 4 ). This is not entirely unexpected, since cellular responses and adaptations to the hypoxic environment are complex and play important roles in normal cellular physiology. Hypoxic tumor cells are known to be more resistant to certain drugs (Reviewed in Brown, 2000). We found that the IC 50 of Carica papaya extract in hypoxia was reduced by almost 3-fold when compared to normoxia. This finding demonstrates Carica papaya as a candidate for the elimination of unwanted hypoxic cells. To investigate the effects of a combination treatment, using Carica papaya with either cisplatin or chetomin, we performed experiments using IC 50 concentrations of each material. Results obtained showed that the combination treatment led to an increase in cytotoxicity compared to individual treatments. In this combination treatment, the killing effect improved by 4-fold in both conditions tested. This observation suggests that Carica papaya is a good candidate, as individual or combination treatment for drug resistant cells, particularly with respect to targeting hypoxic cells.
[0035] Since HIF is known to be a master regulator of cellular responses to low oxygen conditions (Semenza. 2011), it is likely that the variation in cellular responses to plant extracts in hypoxic versus normoxic conditions was due to differences in their HIF activities. To investigate this possibility, a hypoxia-driven reporter assay (Kaluz et al., 2008) was performed in samples treated with the lowest concentrations of each plant extract. Signal intensity of this assay is directly proportional to HIF activity. These lowest concentrations were chosen since they provide the least effects on the general properties of the cells. Treatment of cells with plant extracts did not show any significant variation in the normoxic basal level of HIF activities (data not shown). Varying responses, however, were observed in the hypoxic samples ( FIG. 2 ). Treatment with all of the plant extracts, except for Carica papaya , resulted in further activation of HIF activity, as evidenced from the negative values of the HIF inhibition. The level of activation however, varied among the different plant extracts. These variations did not show any obvious correlation to their viability at the low concentrations tested ( FIG. 1A ). Interestingly, the only candidate HIF inhibitor found in this study, which was the Carica papaya extract, led to an almost 40% inhibition of HIF activity. This inhibition was almost comparable to cisplatin treatment, a known HIF inhibitor (Duyndam et al., 2007). This novel finding indicates the potential of Carica papaya extract as an agent to kill hypoxic cancer cells through inhibition of HIF activity.
[0036] Data presented in the foregoing study show specific cytotoxic effects of Carica papaya extract under hypoxic conditions as evidenced from a 3-fold reduction in IC 50 of hypoxic versus normoxic cells. This reduced IC 50 was achieved through specific inhibition of HIF activities.
[0037] Having established the effectiveness of Carica papaya extract to inhibit HIF activity, experiments were performed to determine the effect the age of the Carica papaya leaves on HIF inhibition. Leaves of the C. papaya were subjected to the methanolic extraction method to obtain crude leave extracts. Several batches of leave samples were originally obtained from different ages of plants from a farm that cultivates specific C. papaya varieties. The extracts were used in a HIF inhibition assay using the cell-based HIF assay system described above.
[0038] HHIF inhibitory activities were found to be dependent on the age of the plant from where the leaves were originally harvested. Referring to FIG. 5 , statistically significant, replicable inhibition was seen in crude extract of leaves from plants ages 6 months and younger. An opposite effect, statistically significant activation of HIF, was noted when samples were obtained from plants that were older than 6 months of age.
[0039] To compare the invention to the disclosure in prior art Morimoto et al. US patent Application No. 20080069907, HIF assays were performed using extraction procedures detailed in their patent application with plants that were older than 10 month. Referring to FIG. 6 , results showed that a replicable inhibition of HIF was not seen. The HIF activity was instead increased, as evident from the negative values of HIF inhibition (the y-axis).
[0040] The alcohol used to extract the Carica papaya leaves was methanol. In general, one can use any of the monohydric, polyhydric, unsaturated aliphatic, or alicyclic alcohols, exemplified by methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentan-1-ol, 3-methylbutan-1-ol, 2-methylbutan-1-ol, 2,2-dimethylpropan-2-ol, pentan-3-ol, pentan-2-ol, 3-methylbutan-2-ol, 2-methylbutan-2-ol, ethane-1,2-diol, propane-1,2-diol, propane-1,2,3-triol, butane-1,2,3,4-tetraol, or pentane-1,2,3,4,5-pentol. The alcohol is preferably an acyclic alcohol having from 1 to five carbon atoms, most preferably methanol.
[0041] As described above, performed experiments using combinations of Carica papaya and cisplatin or chetomin led to an increase in cytotoxicity by 4-fold. Other chemotherapeutic agents can be used. More particularly, one can use in combination with the Carica papaya extract a chemotherapeutic agent selected from the group consisting of cisplatin, chetomin, methotrexate, trimetrexate, adriamycin, taxotere, 5-fluorouracil, vincristine, vinblastine, pamidronate disodium, anastrozole, exemestane, cyclophosphamide, epirubicin, toremifene, letrozole, trastuzumab, megestrol, tamoxifen, paclitaxel, docetaxel, capecitabine, goserelin acetate, 0-epi-1,25 dihydroxyvitamin D3,4-ipomeanol, 5-ethynyluracil, 9-dihydrotaxol, abiraterone, acivicin, aclarubicin, acodazole hydrochloride, acronine, acylfulvene, adecypenol, adozelesin, aldesleukin, all-tk antagonists, altretamine, ambamustine, ambomycin, ametantrone acetate, amidox, amifostine, aminoglutethimide, aminolevulinic acid, amrubicin, amsacrine, anagrelide, andrographolide, angiogenesis inhibitors, antagonist D, antagonist G, antarelix, anthramycin, anti-dorsalizing morphogenetic protein-1, antiestrogen, antineoplaston, antisense oligonucleotides, aphidicolin glycinate, apoptosis gene modulators, apoptosis regulators, apurinic acid, ARA-CDP-DL-PTBA, arginine deaminase, asparaginase, asperlin, amsacrine, atamestane, atrimustine, axinastatin 1, axinastatin 2, axinastatin 3, azacitidine, azasetron, azatoxin, azatyrosine, azetepa, azotomycin, baccatin III derivatives, balanol, batimastat, benzochlorins, benzodepa, benzoylstaurosporine, beta lactam derivatives, beta-alethine, betaclamycin B, betulinic acid, BFGF inhibitor, bicalutamide, bisantrene, bisantrene hydrochloride, bisaziridinylspermine, bisnafide, bisnafide dimesylate, bistratene A, bizelesin, bleomycin, bleomycin sulfate, BRC/ABL, antagonists, breflate, brequinar sodium, bropirimine, budotitane, busulfan, buthionine sulfoximine, cactinomycin, calcipotriol, calphostin C, calusterone, camptothecin derivatives, canarypox IL-2, caracemide, carbetimer, carboplatin, carboxamide-amino-triazole, carboxyamidotriazole, carest M3, carmustine, cam 700, cartilage derived inhibitor, carubicin hydrochloride, carzelesin, casein kinase inhibitors, castanospermine, cecropin B, cedefingol, cetrorelix, chlorambucil, chlorins, chloroquinoxaline sulfonamide, cicaprost, cirolemycin, cis-porphyrin, cladribine, clomifene analogs, clotrimazole, collismycin A, collismycin B, combretastatin A4, combretastatin analog, conagenin, crambescidin 816, crisnatol, crisnatol mesylate, cryptophycin 8, cryptophycin A derivatives, curacin A, cyclopentanthraquinones, cycloplatam, cypemycin, cytarabine, cytarabine ocfosfate, cytolytic factor, cytostatin, dacarbazine, dacliximab, dactinomycin, daunorubicin hydrochloride, decitabine, dehydrodidemnin B, deslorelin, dexifosfamide, dexormaplatin, dexrazoxane, dexverapamil, dezaguanine, dezaguanine mesylate, diaziquone, didemnin B, didox, diethylnorspermnine, dihydro-5-azacytidine, dioxamycin, diphenyl spiromustine, docosanol, dolasetron, doxifluridine, doxorubicin hydrochloride, droloxifene, droloxifene citrate, dromostanolone propionate, dronabinol, duazomycin, duocarmycin SA, ebselen, ecomustine, edatrexate, edelfosine, edrecolomab, eflomithine, eflornithine hydrochloride, elemene, elsamitrucin, emitefur, enloplatin, enpromate, epipropidine, epirubicin hydrochloride, epristeride, erbulozole, erythrocyte gene therapy vector system, esorubicin hydrochloride, estramustine, estramustine analog, estramustine phosphate sodium, estrogen agonists, estrogen antagonists, etanidazole, etoposide, etoposide phosphate, etoprine, fadrozole, fadrozole hydrochloride, fazarabine, fenretinide, filgrastim, finasteride, flavopiridol, flezelastine, floxuridine, fluasterone, fludarabine, fludarabine phosphate, fluorodaunorunicin hydrochloride, flurocitabine, forfenimex, formestane, fosquidone, fostriecin, fostriecin sodium, fotemustine, gadolinium texaphyrin, gallium nitrate, galocitabine, ganirelix, gelatinase inhibitors, gemcitabine, gemcitabine hydrochloride, glutathione inhibitors, hepsulfam, heregulin, hexamethylene bisacetamide, hydroxyurea, hypericin, ibandronic acid, idarubicin, idarubicin hydrochloride, idoxifene, idramantone, ifosfamide, ilmofosine, ilomastat, imidazoacridones, imiquimod, immunostimulant peptides, insulin-like growth factor-1 receptor inhibitor, interferon agonists, interferon alpha-2A, interferon alpha-2B, interferon alpha-N1, interferon alpha-N3, interferon beta-IA, interferon gamma-IB, interferons, interleukins, iobenguane, iododoxorubicin, iproplatin, irinotecan, irinotecan hydrochloride, iroplact, irsogladine, isobengazole, isohomohalicondrin B, itasetron, jasplakinolide, kahalalide F, lamellarin-N triacetate, lanreotide, lanreotide acetate, leinamycin, lenograstim, lentinan sulfate, leptolstatin, leukemia inhibiting factor, leukocyte alpha interferon, leuprolide acetate, leuprolide/estrogen/progesterone, leuprorelin, levamisole, liarozole, liarozole hydrochloride, linear polyamine analog, lipophilic disaccharide peptide, lipophilic platinum compounds, lissoclinamide 7, lobaplatin, lombricine, lometrexol, lometrexol sodium, lomustine, lonidamine, losoxantrone, losoxantrone hydrochloride, lovastatin, loxoribine, lurtotecan, lutetium texaphyrin, lisofylline, lytic peptides, maitansine, mannostatin A, marimastat, masoprocol, maspin, matrilysin inhibitors, matrix metalloproteinase inhibitors, maytansine, mechlorethamine hydrochloride, megestrol acetate, melengestrol acetate, melphalan, menogaril, merbarone, mercaptopurine, meterelin, methioninase, methotrexate sodium, metoclopramide, metoprine, meturedepa, microalgal protein kinase C inhibitors, MIF inhibitor, mifepristone, miltefosine, mirimostim, mismatched double stranded RNA, mitindomide, mitocarcin, mitocromin, mitogillin, mitoguazone, mitolactol, mitomalcin, mitomycin, mitomycin analogs, mitonafide, mitosper, mitotane, mitotoxin fibroblast growth factor-saporin, mitoxantrone, mitoxantrone hydrochloride, mofarotene, molgramostim, monoclonal antibody, human chorionic gonadotrophin, monophosphoryl lipid a/myobacterium cell wall SK, mopidamol, multiple drug resistance gene inhibitor, multiple tumor suppressor 1-based therapy, mustard anticancer agent, mycaperoxide B, mycobacterial cell wall extract, mycophenolic acid, myriaporone, n-acetyldinaline, nafarelin, nagrestip, naloxone/pentazocine, napavin, naphterpin, nartograstim, nedaplatin, nemorubicin, neridronic acid, neutral endopeptidase, nilutamide, nisamycin, nitric oxide modulators, nitroxide antioxidant, nitrullyn, nocodazole, nogalamycin, n-substituted benzamides, 06-benzylguanine, octreotide, okicenone, oligonucleotides, onapristone, ondansetron, oracin, oral cytokine inducer, ormaplatin, osaterone, oxaliplatin, oxaunomycin, oxisuran, paclitaxel analogs, paclitaxel derivatives, palauamine, palmitoylrhizoxin, pamidronic acid, panaxytriol, panomifene, parabactin, pazelliptine, pegaspargase, peldesine, peliomycin, pentamustine, pentosan polysulfate sodium, pentostatin, pentrozole, peplomycin sulfate, perflubron, perfosfamide, perillyl alcohol, phenazinomycin, phenylacetate, phosphatase inhibitors, picibanil, pilocarpine hydrochloride, pipobroman, piposulfan, pirarubicin, piritrexim, piroxantrone hydrochloride, placetin A, placetin B, plasminogen activator inhibitor, platinum complex, platinum compounds, platinum-triamine complex, plicamycin, plomestane, porfimer sodium, porfiromycin, prednimustine, procarbazine hydrochloride, propyl bis-acridone, prostaglandin J2, prostatic carcinoma antiandrogen, proteasome inhibitors, protein A-based immune modulator, protein kinase C inhibitor, protein tyrosine phosphatase inhibitors, purine nucleoside phosphorylase inhibitors, puromycin, puromycin hydrochloride, purpurins, pyrazofurin, pyrazoloacridine, pyridoxylated hemoglobin polyoxyethylene conjugate, RAF antagonists, raltitrexed, ramosetron, RAS farnesyl protein transferase inhibitors, RAS inhibitors, RAS-GAP inhibitor, retelliptine demethylated, rhenium RE 186 etidronate, rhizoxin, riboprine, ribozymes, RII retinamide, RNAi, rogletimide, rohitukine, romurtide, roquinimex, rubiginone B1, ruboxyl, safingol, safingol hydrochloride, saintopin, sarcnu, sarcophytol A, sargramostim, SDI1 mimetics, semustine, senescence derived inhibitor 1, sense oligonucleotides, signal transduction inhibitors, signal transduction modulators, simtrazene, single chain antigen binding protein, sizofuran, sobuzoxane, sodium borocaptate, sodium phenylacetate, solverol, somatomedin binding protein, sonermin, sparfosate sodium, sparfosic acid, sparsomycin, spicamycin D, spirogermanium hydrochloride, spiromustine, spiroplatin, splenopentin, spongistatin 1, squalamine, stem cell inhibitor, stem-cell division inhibitors, stipiamide, streptonigrin, streptozocin, stromelysin inhibitors, sulfinosine, sulofenur, superactive vasoactive intestinal peptide antagonist, suradista, suramin, swainsonine, synthetic glycosaminoglycans, talisomycin, tallimustine, tamoxifen methiodide, tauromustine, tazarotene, tecogalan sodium, tegafur, tellurapyrylium, telomerase inhibitors, teloxantrone hydrochloride, temoporfin, temozolomide, teniposide, teroxirone, testolactone, tetrachlorodecaoxide, tetrazomine, thaliblastine, thalidomide, thiamiprine, thiocoraline, thioguanine, thiotepa, thrombopoietin, thrombopoietin mimetic, thymalfasin, thymopoietin receptor agonist, thymotrinan, thyroid stimulating hormone, tiazofurin, tin ethyl etiopurpurin, tirapazamine, titanocene dichloride, topotecan hydrochloride, topsentin, toremifene citrate, totipotent stem cell factor, translation inhibitors, trestolone acetate, tretinoin, triacetyluridine, triciribine, triciribine phosphate, trimetrexate, trimetrexate glucuronate, triptorelin, tropisetron, tubulozole hydrochloride, turosteride, tyrosine kinase inhibitors, tyrphostins, UBC inhibitors, ubenimex, uracil mustard, uredepa, urogenital sinus-derived growth inhibitory factor, urokinase receptor antagonists, vapreotide, variolin B, velaresol, veramine, verdins, verteporfin, vinblastine sulfate, vincristine sulfate, vindesine, vindesine sulfate, vinepidine sulfate, vinglycinate sulfate, vinleurosine sulfate, vinorelbine, vinorelbine tartrate, vinrosidine sulfate, vinxaltine, vinzolidine sulfate, vitaxin, vorozole, zanoterone, zeniplatin, zilascorb, zinostatin, zinostatin stimalamer, and zorubicin hydrochloride, as well as salts, homologs, analogs, derivatives, enantiomers and/or functionally equivalent compositions thereof.
[0042] Although the present invention has been described in connection with the preferred embodiments, it is to be understood that modifications and variations may be utilized without departing from the principles and scope of the invention, as those skilled in the art will readily understand.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates generally to beverage container holders and, more particularly, to a compact cup holder adapted to be used in an automobile wherein curved cup rings mounted to a slidable drawer are pivoted to an open position in which they cooperate with semicircular openings in the drawer to form complete circular retainers for a beverage container, and wherein a cup supporting member is pivoted to a position centered below the complete circular retainers to support the bottoms of beverage containers received in the circular openings.
2. Description of the Related Art
Individuals traveling by automobile or other motor vehicle frequently find it useful or enjoyable to consume a beverage while en route. Such travelers may carry with them individual bottles or cans of their favorite refreshment. More frequently, travelers will utilize the convenient services of restaurant "drive-thrus" at which they typically receive their beverages in cups of expanded polystyrene foam or paper. However, the individual cans, bottles or cups which one receives when a carry-out beverage is ordered are typically small, light in weight, and easily upset or spilled when set down on a seat or the floor of a vehicle. Obviously, this is to be avoided as the spilled liquid may soil the interior of the vehicle as well as the clothes and personal possessions of the vehicle's occupants.
Consequently, a number of devices have been developed for retaining and supporting beverage containers used in automobiles. U.S. Pat. No. 4,511,072, entitled Drinking Cup Holder for Automobiles and issued Apr. 16, 1985 to Owens, discloses a folding cup holder which may be stored in the glove compartment when not in use and which further includes magnets for securing the cup holder to an appropriate metal surface. This device is obviously limited in use, because a suitable mounting surface may not be within easy reach of the user.
Several prior patents disclose trays which may be slidably mounted below an automobile dashboard for movement between a retracted storage position below the dashboard and an extended position of use above or close to the leading edge of the front passenger seat. Such trays may be provided with fixed circular apertures for receiving beverage containers. Examples of these devices are disclosed in U.S. Pat. No. 2,825,611, entitled Tray for Automobiles and Other Similar Vehicles and issued Mar. 4, 1958 to Aynesworth, U.S. Pat. No. 3,606,112, entitled Retractable Beverage Holder for Motor Vehicles and issued Sept. 20, 1971 to Cheshire, and U.S. Pat. No. 3,899,982, entitled Pull Out Table for Attachment Beneath an Automobile Dashboard and issued Aug. 19, 1975 to Fetzek.
Other references disclose trays which may be swingably mounted below an automobile dashboard for movement between a storage position below the dashboard and a position of use extending from the dashboard toward the seat. These trays also may be provided with fixed circular apertures for receiving beverage containers. Examples of the latter devices are disclosed in U.S. Pat. No. 2,772,934, entitled Food Service Tray and issued Dec. 4, 1956 to Eraut, and U.S. Pat. No. 3,190,241, entitled Serving Tray for Vehicles and issued June 22, 1965 to Rodgers et. al.
U.S. Pat. No. 2,845,315, entitled Utility Shelf for an Automobile Instrument Panel and issued Jul. 29, 1958 to McCoy, discloses a shelf which is slidably mounted for movement into a recess in a dashboard for storage and for movement outwardly of the recess for use, but the shelf does not provide means for retaining a beverage container.
The prior art devices which provide specific means for supporting and retaining beverage containers disclose trays having complete and fixed circular apertures arranged in a side-by-side or front-to-back relation. This necessarily requires that the width or depth, respectively, of the tray be greater than the diameter of two beverage containers to allow enough area to enclose a pair of fixed, complete circular apertures. Such devices obviously occupy considerable space below the vehicle dashboard.
However, with the increased use of mobile telephones, citizen band radios, and other electronic equipment in automobiles, the available space below the automobile dashboard is becoming more and more limited. In addition to the foregoing electronic devices, automobiles are increasingly being outfitted with bulky standard features such as stereophonic radios, tape players, compact disc players, and air conditioning, which further limit the available space behind the dashboard for the installation of an in-dash beverage container holder. Thus, it is desirable to provide a compact beverage container holder which occupies a minimum amount of space below the dashboard or which, alternatively, can be mounted in a small recess in the automobile dashboard, in a recess in an automobile door armrest, or on the underside of a fold-down armrest of a type used to separate the two portions of a split bench style seat.
To provide maximum flexibility, a beverage container holder should include a means for supporting a bottom surface of the container. If the sole means for supporting the container is provided by circular apertures of fixed size, then many beverage containers may be either too small or too large to be adequately supported by the holder. However, the provision of a fixed means for supporting the bottom surface of a beverage container substantially increases the space occupied by the holder, which space as mentioned above is at a premium in current production automobiles. Therefore, it is also desirable to provide a compact means for supporting the bottom surface of a beverage container.
SUMMARY OF THE INVENTION
The present invention provides a cup holder for supporting at least one beverage container in a vehicle and comprising movable drawer means, fixed support means therefor, and container retaining means carried by the drawer means for movement therewith and movable relative thereto between a retaining position and a collapsed position. More particularly, the fixed support means includes means for mounting the holder in a vehicle and means for supporting the drawer means on the mounting means for reciprocating movement relative thereto between an operative position extending outwardly of the mounting means and a storage position extending inwardly relative to the mounting means. The container retaining means, being mounted on the drawer means for movement relative thereto, in its retaining position forms with the drawer means a container retaining configuration, and in its collapsed position forms with the drawer means a compact configuration occupying a space smaller than the space occupied by the container retaining configuration.
The cup holder further comprises means carried by the drawer means for biasing the container retaining means toward the retaining position. The fixed means includes cam means engageable with the container retaining means to urge the latter to the collapsed position upon movement of the drawer means from the operative position to the storage position.
In accordance with the invention, the drawer means may comprise a substantially flat horizontal drawer member formed with a pair of curved indentations at opposed lateral edge portions thereof; and the container retaining means may comprise a pair of cup rings and means for mounting the cup rings on the drawer member for pivotal movement relative thereto in opposite directions and in horizontal planes between the retaining position and the collapsed position. Each of the cup rings is formed with a curved edge complementary to one of the indentations whereby a container-receiving aperture is defined when the cup rings are in the retaining position. The biasing means may comprise a spring means interposed between the drawer member and each of the cup rings.
Each of the cup rings is preferably formed with a pivot aperture, the cup rings being partially overlapped so that the pivot apertures thereof are aligned to receive the means mounting the cup rings on the drawer member, whereby the pivotal movement of the cup rings is executed about a common vertical axis.
In preferred embodiments, the container receiving means further comprises a bail, and means for mounting the bail to a lower surface of the drawer member for pivotal movement relative to the drawer member about a horizontal axis between the retaining position and the collapsed position. In the retaining position, the bail is disposed to support the bottom of a beverage container received in either of the container-receiving apertures. The biasing means for the bail may include a torsion spring interposed between the drawer member and the bail.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the invention, reference should now be had to the embodiment illustrated in the accompanying drawings and described below by way of example.
In the drawings:
FIG. 1 is a perspective view of an automobile dashboard showing the invention in the form of a cup holder mounted in a recess in the dashboard;
FIG. 2 is a plan view of the cup holder of FIG. 1 in an extended position for use;
FIG. 3 is a plan view similar to FIG. 2 but showing the cup holder in a retracted position for storage;
FIG. 4 is an elevational view of the cup holder of FIGS. 1 to 3 in an extended position for use;
FIG. 5 is an elevational view similar to FIG. 4 but showing the cup holder of FIGS. 1 to 4 in a retracted position for storage; and
FIG. 6 is a sectional view of the pivoting cup holder taken along lines 6--6 of FIG. 2;
FIG. 7 is a perspective view of the pivoting cup holder similar to FIG. 2 but showing the pivoting cup holder removed from the retainer and the shell;
FIG. 8 is a sectional view of the first pivot means taken along lines 8--8 of FIG. 7; and
FIG. 9 is a sectional view of the second pivot means taken along lines 9--9 of FIG. 7.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to the drawings, and in particular to FIG. 1, the invention in the form of a cup holder, designated generally as 10, is shown in conjunction with an automobile dashboard 12, it being understood that the dashboard forms no part of the invention in its broader aspects. It will be easily recognized by those skilled in the art that the cup holder 10 may alternatively be secured to an underside of the dashboard 12, mounted in a recess in an automobile door armrest, or secured to an underside of a fold-down armrest/divider as might be used in an automobile having a split bench-style front seat.
Also in FIG. 1 the cup holder 10 is shown to be supporting a beverage container 14 which forms no part of the invention, but which is illustrated in the form of a cup. It will be recognized that beverage containers other than the cup depicted in FIG. 1 may be satisfactorily accommodated by the cup holder 10.
Referring now to FIGS. 2 to 9, the cup holder 10 comprises principally a fixed support means 15, a drawer means 17, and a container retaining means 20. The fixed support means 15 includes a means 16 for mounting the cup holder 10 in a vehicle and a means 18 for supporting the drawer means 17 on the mounting means 16. The mounting means 16 comprises a retainer 22 having a flat base 24 intermediate a pair of vertical side walls 26 formed at lateral edges 28 of the base 24 and maintained in a parallel relation to each other. The retainer 22 may be set into a recess in an automobile dashboard 12 (see FIG. 1) or an automobile door armrest (not shown in the drawings) or it may be secured to an underside of the automobile dashboard 12. Alternatively, it may be secured to the underside of a fold-down armrest/divider of a type commonly used in conjunction with split bench style seating (also not shown in the drawings). The mounting means 16 further includes a shell 23 to cover the retainer 22. The shell 23 is formed with a bottom surface 23a, a pair of parallel side surfaces 23b formed at lateral edges of the bottom surface 23a, and a partial top surface 23c formed at a forward end 23d of the shell 23.
The fixed support means 15 includes means 18 for supporting the drawer means 17 on the mounting means 16 As best shown in FIG. 6, the means 18 for supporting the drawer means 17 comprises a pair of side rails 30. Each side rail 30 is secured to the side walls 26 of the retainer 22 and is formed with a top wall 34, a bottom wall 36 parallel to the top wall 34, and a side wall 38 intermediate the top and bottom walls 34, 36. Each bottom wall 36 is further provided with a lip 40 at a free end 41 of the bottom wall 36, the lip 40 being parallel to the side wall 38. The bottom wall 36 extends the length of the side wall 30 but is of a reduced width at a rear end 43 of the respective side rail 30 thereby creating a ridge 42. The arrangement of each top wall 34, bottom wall 36, side wall 38, and lip 40 provides a channel 44 which extends the length of each side rail 30.
The drawer means 17 comprises a drawer 32 having a substantially flat horizontal drawer member 46 having parallel downwardly projecting side members 48 formed at opposite sides or opposed lateral edge portions 50 thereof. Also formed in opposite sides 50 of the drawer 32 at an approximately central portion 78 thereof are a pair of adjacent semicircular indentations 76 or first curved edge portions 76. The drawer 32 is further provided with rigidifying and strengthening side ribs 52 formed integral with an underside 33 of the drawer 32 and a stop 54 mounted to the rib 52 at a rear end 56 of the drawer 32. Mounted to a forward end 58 of the drawer 32 is a flange 60 which has formed at an upper portion 62 thereof a handle 64 in the form of a contoured lobe 66. (FIGS. 4 and 5).
Referring again to FIG. 6, each side member 48 of the drawer 32 is received in that channel 44 situated in the respective side rail 30 for sliding movement into and out of the retainer 22. An outside edge 48a, a lower surface 48b, and an upper surface 48c of each side member 48 are in sliding engagement respectively with channel surfaces 44a, 44b, 44c. The stop 54 limits the outward movement of the drawer 32 when a laterally projecting finger 55 formed integrally with the stop 54 engages the ridge 42.
The container retaining means 20 comprises a cup side support means 68, a cup bottom support means 70, and a first and second pivot means 72, 74, respectively for the cup side support means 68 and the cup bottom support means 70.
The cup side support means 68 comprises a pair of first and second cup rings 80, 81. The first pivot means 72 mounts the cup rings 80, 81 to the drawer 32.
Each cup ring 80, 81 is formed with an approximately delta-shaped portion 82, having first, second and third legs 84, 86, 88, and a curved arm section 90. Each cup ring 80, 81, between the first and second legs 84, 86 of the delta shaped portion 82, is provided with a contoured edge 92 having a radius of curvature substantially the same as that of each semicircular indentation 76. Each contoured edge 92 is continuous with an inside edge 94 of the curved arm section 90, which inside edges 94 also have radii of curvature substantially similar to that of each semicircular indentation 76. An aperture 96 is provided in the third leg 86 of each delta shaped portion 82, which apertures 96 cooperate with the first pivot means 72 to rotatably mount the cup rings 80, 81 to the drawer 32, as explained more fully below.
The first pivot means 72 comprises a pivot housing 98, a pivot pin 100 which is in the form of an anvil rivet having a shaft 100a and a head 100b, and a biasing means 102 shown in the form of a torsion spring having a central helical portion 102a and a pair of legs 102b, 102c. The pivot housing 98 is mounted to the underside 33 of the drawer 32 between a transverse rib 103 and a central rib 105 and is provided with an axial bore 98a to receive the pivot pin 100 in a vertical orientation. Alternatively, the pivot housing 98 may be formed integrally with the underside 33 of the drawer 32 at the same location.
In assembly, the cup rings 80, 81 are arranged in an overlapping relationship such that the respective apertures 96 are vertically aligned. The pivot pin 100 registers with the vertically aligned apertures 96 and the axial bore 98a in the pivot housing 98 to mount the cup rings 80, 81 to the drawer 32. The central helical portion 102a of the biasing means 102 is received by the shaft 100a of the pivot pin 100 between the overlapping cup rings 80, 81. The legs 102b, 102c of the biasing means 102 respectively nest within pockets 80a, 81a respectively formed in a lower surface 80b of the third leg 86 of the delta shaped portion 82 of the first cup ring 80 and an upper surface 81b of the third leg 86 of the delta shaped portion 82 of the second cup ring 81.
The cup bottom support means 70 of the container retaining means 20 comprises a bail 104, secured to an end 104a of which, in a plane normal to the bail 104, is an approximately square C-shaped cup supporting member 106. The second pivot means 74 mounts the cup bottom support means 70 to the drawer 32. The second pivot means 74 comprises a pivot 108 in the form of a tubular rivet and a biasing means 110 in the form of a torsion spring having a central circular portion 110a and legs 110b, 110c.
In assembly, a distal end 112 of the bail 104 is received between cup ring ribs 114, 116 formed integral with the underside 33 of the drawer 32. The distal end 112 of the bail 104 is further provided with a transverse bore 118 which is aligned with holes 120 formed in the cup ring ribs 114, 116. The pivot 108 registers with the transverse bore 118 and the holes 120 to mount the cup bottom support means 70 to the drawer 32. The central circular portion 110a of the biasing means 110 is received by the pivot 108 and the legs 110b, 110c of the biasing means 110 respectively engage the bail 104 and the underside 33 of the drawer 32.
In operation, the drawer 32 is slidable between an extended or operative position for use and a retracted position for storage. In the extended position (as best shown in FIGS. 1, 2, 4 and 7), the forward end 58 and the central portion 78 of the drawer 32 project beyond the retainer 22. The biasing means 102 for the first pivot means 72 and the biasing means 110 for the second pivot means 74 respectively allow the cup rings 80, 81 and the cup bottom support means 70 to pivot to their respective container retaining configurations or use positions when the drawer 32 is in the extended position. Each cup ring 80, 81 is adapted to be horizontally rotated, the degree of rotation being limited by stops 122.
In the extended position for use, each contoured edge 92 of the respective delta shaped portion 82 is substantially superimposed over a respective inside edge 124 of the respective semicircular indentation 76. Further, each inside edge 94 of the respective curved arm section 90 is colinear with a respective inside edge 124 of the respective semicircular indentation 76, and a distal end 126 of each curved arm section 90 slightly overlies the drawer 32 where the respective inside edge 124 interrupts a portion 50a of the opposite sides 50 of the drawer 32. In this manner, the cup rings 80, 81 cooperate with the semicircular indentations 76 to provide the cup side support means 68, and complete circular retainers or container-receiving apertures 128, which are dimensioned to receive and accommodate the beverage container 14, which may be of any size typically available to consumers.
Also in the extended position (still referring to FIGS. 1, 2, 4 and 7) the cup bottom support means 70 is vertically rotated such that the bail 104 projects downward and forward and the cup supporting member 106 is centered below the circular retainers 128. In this arrangement, a side wall 14b of the beverage container 14 is laterally supported by the respective complete circular retainer 128 and a bottom surface 14a of the beverage container 14 is braced by the cup supporting member 106.
The drawer 32 is moved to the retracted or stored position (shown in FIGS. 3 and 5) by applying an inwardly directed force to the handle 64 to slidably move the drawer 32 within the channels 4 of the side rails 30 and into the retainer 22 until the flange 60 of the drawer 32 is adjacent to a forward end 129 of the retainer 22. Adjusting the drawer 32 to the retracted position results in an outside edge or camming surface 130 of each of the second legs 86 of the respective delta shaped portion 82 being engaged by a cam means 131 comprising a forward end 132 of the respective side rail 30. Continued retraction of the drawer 32 thereby causes each cup ring 80, 81 to be rotated in horizontal planes to a collapsed position wherein the cup rings 80, 81 are located between the side rails 30 and to a compact configuration wherein the cup rings 80, 81 are overlapped with respect to each other and with respect to the semicircular indentations 76.
Moving the drawer 32 to the retracted position also results in the bail 104 of the cup bottom support means 70 being engaged by the bottom surface 23a of the shell 23 at the forward end 23d of the shell 23. Continued retraction of the drawer 32 causes the cup bottom support means 70 to be vertically rotated to a location such that the bail 104 is positioned between the cup ring ribs 114, 116 and the cup supporting member 106 projects upward and into the semicircular indentations 76.
Thus, it can be seen that the cup holder 10 provides a compact beverage container holder. Because both the cup side support means 68 and the cup bottom support means 70 are rotatably mounted to the drawer 32, the width of the drawer 32 is considerably less than twice the diameter of two beverage containers and the height of the cup holder 10 is also substantially reduced.
The drawer 32 may be easily moved from the retracted storage position to the extended position by applying an outwardly directed force to the handle 64. As the central portion 78 of the drawer 32 is drawn beyond the side rails 30, the cup rings 80, 81 and the cup bottom support means 70 will be rotated under the urging of the biasing means 102, 110 to assume the positions described above and shown in FIGS. 1, 2, 4 and 7.
While the invention has been described in connection with a preferred embodiment, it will be understood that the invention is not intended to be limited to that embodiment. On the contrary, all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims is intended. | A pivoting cup holder for supporting a beverage container in a vehicle. The cup holder comprises a flat movable drawer which can slide into and out of a retainer set into or below the dashboard or an armrest of an automobile. A semicircular indentation is formed in each side of the drawer. Pivotally mounted to the drawer are a pair of cup rings, each of which is formed with a curved edge complementary to the semicircular indentation. The cup rings are spring-loaded to rotate horizontally to a use position when the drawer is pulled outwardly of the retainer. In the use position the cup rings cooperate with the semicircular indentation to form complete circular retainers for supporting the side wall of a beverage container. The cup holder further comprises a spring loaded bail and cup support which, when the drawer is opened, vertically pivot to a position centered below the circular retainers to brace the bottom surface of the beverage container. When the drawer is moved to a closed position the cup rings pivot to a location in which they overlap with each other and with the semicircular indentations. The bail and cup support similarly pivot to a position in which the cup support projects through the semicircular indentations in the drawer. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application takes priority from U.S. patent application Ser. No. 60/070,753, filed Jan. 8, 1998, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to drilling wellbores and more particularly to a drilling system utilizing a downhole pressure intensifier for jet-assisted drilling.
2. Background of the Art
To obtain hydrocarbons such as oil and gas, boreholes are drilled by rotating a drill bit attached to a drill string. A large proportion of the current drilling activity involves directional drilling, i.e., drilling deviated and horizontal boreholes, to increase the hydrocarbon production and/or to withdraw additional hydrocarbons from the earth's formations.
Modern directional drilling systems generally employ a drill string having a drill bit at the bottom that is rotated by a drill motor (commonly referred to as the “mud motor”). A plurality of downhole devices are placed in close proximity to the drill bit to measure certain downhole operating parameters associated with the drill string and to navigate the drill bit along a desired drill path.
Positive displacement motors are commonly used as mud motors. U.S. Pat. No. 5,135,059, assigned to the assignee hereof and which is incorporated herein by reference, discloses a downhole drill motor that includes a power section having a housing, a stator having a helically-lobed inner elastomeric surface secured within the housing and a rotor having a helically-lobed exterior metallic surface disposed within the stator. Pressurized drilling fluid (commonly known as the “mud” or “drilling mud”) is pumped into a progressive cavity formed between the rotor and stator. The force of the pressurized fluid pumped into the cavity causes the rotor to turn in a planetary-type motion. A suitable shaft connected to the rotor via a flexible coupling compensates for eccentric movement of the rotor. The shaft is coupled to a bearing assembly having a drive shaft (commonly referred as the “drive sub”) which in turn rotates the drill bit attached thereto. Radial and axial bearings in the bearing assembly provide support to the radial and axial movements of the drill bit. For convenience, the power section and bearing assembly are collectively referred to herein as the “motor assembly.” Other examples of the drill motors are disclosed in U.S. Pat. Nos. 4,729,675, 4,982,801 and 5,074,681, the disclosures of which are incorporated herein by reference.
For drilling in rock, the assistance of a jet of high pressure fluid facilitates the drilling operation. Some of the current operations supply the high pressure directly from the surface by either generating the high pressure for the entire fluid flow or operating a smaller amount of high pressure fluid via additional conduits inside the drill pipe. These prior art high pressure systems utilize high pressure pumps or pressure intensifiers at the surface. These systems are relatively expensive and unreliable and thus have not gained commercial acceptance.
The present invention addresses the above-described problems with the prior art methods for jet-assisted drilling and provides novel apparatus and methods for generating high pressure fluid flow downhole.
SUMMARY OF THE INVENTION
The present invention provides apparatus and methods for generating high pressure fluid jet downhole during drilling of the boreholes. The high pressure jet is discharged at the drill bit bottom to aid drilling of the boreholes. A preferred embodiment of the system includes a pressure intensifier disposed between a drilling motor and the drill bit. The drilling motor produces a rotary force as the drilling fluid passes through the drilling motor. The pressure intensifier includes a rotatable sleeve having at least one port for admitting drilling fluid. The rotary force of the drilling motor rotates the rotating sleeve causing the drilling fluid to enter a chamber. A reciprocating differential piston in the rotating sleeve discharges the fluid from the chamber at a high pressure to the drill bit bottom. The preferred embodiment utilizes a dual acting piston that reciprocates between two chambers. During each rotation of the rotating sleeve, the piston discharges at high pressure the fluid from each such chamber.
The pressure intensifier generates pulses of a defined frequency, which act as a carrier of signals and data transmitted uphole (to the surface). A pulse frequency control device or valve coupled to the drilling motor acts as the frequency modulator. A controller or processor in the downhole assembly operates the pulse control frequency device at at least two (at two or more) frequencies, each such frequency representing a binary bit of a digital signal.
Examples of the more important features of the invention have been summarized rather broadly in order that the detailed description thereof that follows may be better understood, and in order that the contributions to the art may be appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject of the claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
For detailed understanding of the present invention, references should be made to the following detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, in which like elements have been given like numerals, and wherein:
FIG. 1 shows a schematic diagram of a drilling system having a drill string containing a drill bit, mud motor and pressure intensifier according to a preferred embodiment of the present invention.
FIGS. 2A-2E show a cross-sectional view of a portion of a downhole assembly which includes a pressure intensifier that is driven or controlled by a mud motor and a data transmission apparatus that utilizes the pulses generated by the pressure intensifier to transmit data to the surface.
FIG. 2F is a section view taken from FIG. 2B along line 2 F— 2 F showing the flow of low-pressure mud from the inlet channel to the pressure intensifier via the upper port of the pressure intensifier.
FIG. 2G is a section view taken from FIG. 2B along line 2 G— 2 G showing the flow of low-pressure mud from the lower port to the outlet channel of the pressure intensifier.
FIG. 3 ( 3 A- 3 B) is a partial, cross-sectional view of a second preferred embodiment of a double-acting pressure intensifier with a control valve sub used as the driving mechanism for the pressure intensifier.
FIG. 4 ( 4 A- 4 B) is a partial, cross-sectional view of a preferred embodiment of a driving mechanism operating with a single-acting pressure intensifier.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In general, the present invention provides a drilling system that utilizes a downhole pressure intensifier that provides high-pressure fluid jet or pulses which discharges at the telemetry to the drill bit bottom to more efficiently drill the boreholes. The drilling system further incorporates a system that utilizes the pressure pulses to transmit measurement-while-drilling (“MWD”) signals and data uphole (to the surface). FIG. 1 is a schematic diagram showing a drilling system 10 which utilizes a drill string 20 for drilling a borehole 24 . The drill string 20 includes a drill bit 26 at its bottom end carried by a bottom hole assembly or drilling assembly 74 . FIGS. 2A-2G show an embodiment of a rotating pressure intensifier 100 for use in the drilling assembly 74 of the system 10 . FIGS. 3-4 show alternative embodiments 100 A- 100 B of the pressure intensifier 100 for use in a drill string 20 .
The drilling system 10 of FIG. 1 is a schematic diagram of a typical drilling system 10 utilizing a mud motor 12 for driving the drill bit 26 . The drilling system 10 includes a conventional derrick 14 erected on a platform 16 that supports a rotary table 18 that is rotated by a prime mover (not shown) such as a motor at a desired rotational speed. It is contemplated that the mud motor 12 of this invention may also be used with the so-called snubbing and coiled-tubing units (not shown).
A drill string 20 , that includes a tubing 22 , extends downward from the rotary table 18 into the borehole 24 . The drill bit 26 disintegrates the earth formation 28 at the borehole bottom 50 when the drill bit 26 is rotated to drill the borehole 24 . The drill string 20 is coupled to a drawworks 30 via a kelly joint 32 , a swivel 34 and a line 36 through a pulley 38 . During the drilling operation, the drawworks 30 is operated to control the weight-on-bit (“WOB”) and the rate-of-penetration (“ROP”) of the drill string 20 into the borehole 24 . The operation of the drawworks 30 is well known in the art and is thus not described in detail herein.
During drilling operations a suitable drilling fluid (commonly referred to in the art as the “mud”) 40 from a mud pit 42 is circulated under pressure through the drill string 20 by a mud pump 44 . The mud 40 passes from the mud pit 42 into the drill string 20 via a desurger 46 , a fluid line 48 and the kelly joint 32 . The mud 40 flows downward through the tubing 22 and then the bottom hole assembly 74 and is discharged at the bottom of the borehole 24 through one or more openings 52 in the drill bit 26 , such as passages 338 a- 338 b and 339 shown in FIG. 3 B. The drilling mud 40 carrying the cuttings circulates uphole through the annular 54 between the drill string 20 and the borehole 24 and is discharged into the mud pit 42 via a return line 56 .
A surface control unit 60 coupled to a sensor 62 placed in the fluid line 48 is used to control the drilling operation and to display desired drilling parameters and other information on a display/monitor 64 . The surface control unit 60 preferably contains a computer, memory for storing data, recorder for recording data and other peripherals (not shown). The control unit 60 processes data with a central processing unit (not shown) and executes program instructions and responds to user commands entered through a suitable means, such as a keyboard, a graphical pointing device or any other suitable device (not shown). The surface control unit 60 preferably activates alarms 66 when certain unsafe or undesirable operating conditions occur. The surface control unit 60 also operates as the receiver for the mud pulse data transmission.
The drilling motor or mud motor 12 , coupled to the drill bit 26 via the drive shaft (not shown) disposed in the bearing assembly 70 , rotates the drill bit 26 when the drilling mud 40 is passed through the mud motor 12 under pressure. The bearing assembly 70 supports the radial and axial forces of the drill bit 26 , the downthrust of the drill motor 12 and the reactive upward loading from the applied weight-on-bit. A stabilizer 72 coupled to the bearing assembly 70 acts as a centralizer for the lowermost portion of the mud motor assembly 74 .
The first preferred embodiment of the pressure intensifier system 100 is illustrated in FIGS. 2A-2G. This embodiment also includes a data transmission apparatus or device 110 for transmitting data pulses to the surface in the form of modulated pressure pulses generated by the pressure intensifier.
The various devices of the pressure intensifier system 100 are disposed in an outer housing 105 which connects at its upper end to a tubing (not shown). Various electronic circuits and components relating to the system 100 are preferably disposed in a pressure tight housing 106 disposed uphole of the data transmission apparatus 110 . The operation of the mud motor 130 and the pressure intensifier 200 will be described before describing the operation of the data transmission apparatus 110 .
The mud motor 130 includes a power section that contains an elastomeric stator 132 having an inner lobed surface 134 . The stator 132 is securely affixed in an outer housing 136 . A rotor 140 having an outer lobed surface 142 is rotatably disposed in the stator 130 . The lobes of the stator 130 and the rotor 140 are such that they create a series of cavities 144 between the rotor and stator lobed surfaces. The rotor 140 has a passage 146 which can be utilized to bypass a certain amount of the drilling fluid to alter the mud motor 130 rotational speed. As the mud 40 a flows from the pulse frequency controller 110 to the mud motor 130 , it passes through the cavities 144 , thereby turning (rotating) the rotor 140 . The mud 40 a leaves the mud motor 130 at the lower end of the power section of the drilling motor and enters the pressure intensifier 200 at ports 232 a. The bypass fluid leaves the rotor at ports 149 . The rotor 130 rotates a flexible shaft 150 , which is coupled to the pressure intensifier 200 via a coupling 152 .
The pressure intensifier 100 is preferably integrated into the mud motor assembly which is usually composed of the mud motor 130 , flexible shaft 150 and the bearing assembly 160 . The pressure intensifier 100 is shown disposed between the flexible shaft 150 and the bearing assembly 160 in the configuration of FIGS. 2A-2G. The pressure intensifier 200 includes a rotatable housing 225 , which is coupled at its upper end 225 a to the flexible shaft 150 at the coupling 154 . The lower end 225 b of the housing 225 is coupled to the drive shaft 162 in the bearing assembly 160 via a coupling 226 . As the rotor 140 rotates, it rotates the flexible shaft 150 , which rotates the coupling 154 and thus the pressure intensifier housing 225 . The housing 225 in turn rotates the coupling 226 , which rotates the drive shaft 162 and thus the drill bit 170 . In the system 100 , the mud motor 130 drives the pressure intensifier 100 rather than a separate driving mechanism, such as shown in FIGS. 3-4.
The rotating housing 225 is disposed in a non-rotating valve sleeve 227 , which is fixed within the outer housing 105 . The non-rotating sleeve 227 creates two channels: an inlet fluid channel 232 (FIG. 2F) between the outer housing 105 and the non-rotating sleeve 227 that receives the low pressure drilling fluid 40 a from the motor 130 and an outlet channel 231 for discharging the low pressure fluid 40 a to the bearing assembly 160 . An upper seal 260 a and a lower seal 260 b provide seals between the non-rotating sleeve 227 and the outer housing 105 . The non-rotating sleeve 227 has openings 227 a and 227 b, which allow fluid 40 a to flow from the channel 232 to the rotating sleeve 225 . The rotating sleeve 225 has an upper port 225 a and a lower port 225 b, each of which comes in fluid communication with fluid 40 a via the openings 227 a and 227 b during each rotation of the rotating sleeve 225 .
A double acting piston 235 reciprocates between an upper chamber 236 a and a lower chamber 236 b which are formed by the piston and the rotating sleeve 225 . The upper end of the piston 235 has an upper pressure plunger 240 a that reciprocates in an upper plunger chamber 242 a. The lower end of the piston 235 has a lower pressure plunger 240 b that reciprocates in a lower plunger chamber 242 b. An upper suction check valve 245 a is disposed in a hydraulic line 244 a connecting the upper chamber 236 a and the upper plunger chamber 242 a to allow the fluid 40 a to flow from the upper chamber 236 a to the upper plunger chamber 242 a. Similarly, a lower suction check valve 245 b is disposed in a hydraulic line 244 b that connects the lower chamber 236 b and the lower plunger chamber 242 b to allow the fluid 40 a to flow from the lower chamber 236 b to the lower plunger chamber 242 b. An upper outlet check valve 250 a allows the high pressure fluid 40 b to discharge from the upper plunger chamber 242 a into a high pressure channel 248 . Similarly, a lower outlet check valve 250 b allows the high pressure fluid 406 to discharge from the lower plunger chamber 242 b into the high pressure channel 249 .
The operation of the pressure intensifier 100 will now be described while referring to FIGS. 2A-2G. The low pressure drilling fluid 40 a causes the mud motor 130 to rotate, which rotates the rotating sleeve 225 causing the upper port 225 a and the lower port 225 b to come in fluid communication with the inlet channel 232 depending on the rotational position of the rotating sleeve 225 relative to the non-rotating sleeve 227 . FIG. 2F is the cross-section of the pressure intensifier 200 taken along 2 F— 2 F. It shows the upper port 225 a in fluid communication with the inlet channel 232 . FIG. 2G is the cross-section of the pressure intensifier taken at 2 G— 2 G when the rotating sleeve is in the same position as shown in FIG. 2 F. It shows the lower port 225 b in fluid communication with the outlet channel 231 after a rotation of ninety degrees (90°). Here the rotating sleeve 225 is in transition phase i.e., from connecting the upper port 225 a with the inlet channel 232 and the lower port 235 b with the outlet channel 231 to connecting the upper port 225 a with the outlet channel 231 and the lower port 235 b with the inlet channel 232 . For a certain amount of time during this transition phase, each of the ports 235 a and 235 b connects to both the inlet channel 232 and the outlet channel 231 . During this time, the fluid 40 a bypasses the pressure intensifier 200 , which ensures continuous supply of the fluid 40 a to the drill bit 170 and a constant rotation of the mud motor 130 . During each revolution of the rotating sleeve 225 , (i) the upper port 225 a comes in fluid communication with the outer channel 231 for a portion of the rotation, (ii) the lower port with the inlet channel 232 for a portion of the rotation, and (iii) for a portion of the rotation such fluid communications occur simultaneously. This is accomplished by configuring the radial dimensions of the inlet channel 232 , outlet channel 231 , and the upper and lower ports 225 a- 225 b such that there always is a certain amount of low pressure fluid 40 a flowing from the inlet channel 232 to the outlet channel 231 , which ensures continuous rotation of the mud motor 130 .
When the upper port 225 a is in fluid communication with the inlet channel 232 , the low pressure fluid 40 a enters the upper chamber 236 a as shown by arrow 260 pushing the piston 235 and the lower plunger 240 b downward. The downward movement of the piston 235 (a) discharges the low pressure fluid 40 a from the lower chamber 236 b into the outlet channel 231 and (b) causes the lower plunger 240 b to discharge the fluid from the lower plunger chamber 242 b into the high pressure channel 248 via check valve 250 b. The high pressure fluid 40 b from the line 248 passes to the drill bit 270 via a connecting high pressure line 249 . Simultaneous with the discharge of the fluid from the lower chamber 236 b, the low pressure fluid 40 a enters into the upper chamber 236 a and into the upper plunger chamber 242 a via suction check valve 245 a and line 244 a. It should be noted that the inlet channel 232 , the outlet channel 231 and the upper and lower ports 225 a- 225 b are configured such that there always is a certain amount of the low pressure fluid 40 a flowing from the inlet channel 232 to the outlet channel 231 to ensure continuous rotation of the mud motor 130 .
When the lower port 225 b comes in fluid communication with the inlet channel 232 , the low pressure fluid 40 a enters the lower chamber 236 b, filling the lower chamber 236 b and the lower plunger chamber 242 b. The piston 235 moves upward, causing the upper plunger 240 a to discharge the fluid from the upper plunger chamber 242 a into the high pressure channel 248 at the high pressure. Thus, each rotation of the rotating sleeve 225 causes the piston 235 to stroke once upward and once downward, thereby supplying two pulses of the high pressure fluid 41 a to the drill bit 170 . The low pressure fluid 40 a is supplied continuously to the drill bit.
The high pressure line 249 supplies the high pressure fluid to the drill bit 170 via a suitable channel 162 . The low pressure fluid 40 a from the outlet channel 231 discharges into the passage 164 in the drive shaft 166 , which rotates the drill bit 170 . The bearing assembly 160 includes radial bearings 168 and axial bearings 167 , which respectively provide radial and axial support to the drive shaft 166 . The high pressure fluid 40 b is discharged at the drill bit bottom via a passage 162 while the low pressure fluid 40 a is discharged via multiple passages 164 .
The pressure intensifier 100 described above and shown in FIGS. 2A-2G produces pressure pulses during each rotation of the housing 225 (FIG. 2 D). These pressure pulses normally interfere with mud pulse telemetry signals commonly utilized for transmitting data and signals from the downhole assembly 100 to the surface. This invention provides a novel method for transmitting signals uphole that are unaffected by the pressure pulses generated by the pressure intensifier 100 . In the preferred mode, this is accomplished by utilizing a pulse frequency control device or valve 110 to transmit signals from the downhole assembly 74 to the surface. The preferred pulse frequency control valve 110 includes a solenoid valve 101 , which contains a solenoid coil 102 with a conical end 111 . The solenoid coil is energized according to programmed instructions from a control circuit (not shown) in the downhole assembly 74 via conductors 103 . A valve poppet 108 having a compliant conical side 113 is disposed in the conical end 111 . The other end 114 of the valve poppet 108 seals an opening 115 in a seat 107 . The valve poppet seals the opening in the normal closed position, as shown in FIG. 2 A. When the solenoid coil 102 is energized, the valve poppet moves uphole, which unseats the valve poppet 108 from the valve seat 107 thereby allowing the low pressure drilling fluid 40 a to pass from the passage 118 to the mud motor via the passage 115 .
As described above with reference to FIG. 1, data from the measurement-while-drilling devices and other sensors carried by the downhole assembly is transmitted to the surface. In the present invention, the signals are transmitted as pulse-modulated signals produced by the pulse frequency control valve 110 utilizing the pressure pulses produced by the pressure intensifier 100 as a carrier. To transmit a signal, for example a series of ones and zeroes, the solenoid is selectively activated and deactivated to increase or reduce the frequency to produce the required signal. For example a “one” may be defined as a first operating frequency of the pulse frequency control valve 110 and a zero as a second operating frequency. Thus, the signals are transmitted as a series of pulses. More than two frequencies may be utilized for special signals, such as the beginning and/or end of a signal series or for other special purposes. The above method provides for frequency modulated signals. Amplitude modulated pulses and other types of pulses may also be utilized to transmit signals. A processor or controller, preferably in the electronic section 106 (FIG. 2 A), controls the operation of the pulse frequency control valve 110 . This processor includes a microprocessor, memory and other related circuitry. One or more programs are stored in the memory downhole, which provide instructions to the microprocessor respecting the control of the valve 110 . The process also may include circuitry to receive command signals from the surface control unit 60 (FIG. 1 ), which may be programmed to send command signals to the downhole processor. The downhole processor controls the operation of the valve 110 according to the programmed instructions stored downhole and/or commands received from the surface control unit 60 .
The second preferred embodiment of the pressure intensifier 100 A that uses an alternative double-acting pressure intensifier/piston 300 is shown in FIG. 3 . This pressure intensifier 100 A includes a control valve sleeve 302 and a pressure intensifier sub 304 . The control valve sleeve 302 is the driving mechanism for the double-acting pressure intensifier/piston 300 and includes a valve piston 306 and an oscillating piston 308 . The valve piston 306 is slidably mounted in the control valve sleeve 302 . A valve spring 310 urges the valve piston 306 upwards into its open, biased position. The oscillating piston 308 also is slidably mounted within the control valve sleeve 302 . A main spring 312 urges the oscillating piston 308 upwards into its open, biased position.
An optional bypass nozzle 314 is used in the preferred embodiment to optimize the action of the drilling system 10 . The operation of the bypass nozzle 314 is well known in the industry and, therefore, is not discussed in detail. For ease of understanding, the following description assumes that the bypass nozzle 314 is in the closed position.
One cycle of the double-acting pressure intensifier/piston 300 includes four phases. In the first phase, the oscillating piston 308 is forced upward by the biasing action of the main spring 312 . At the end of Phase 1, a valve 316 is closed when a valve seat 318 contacts a valve body 320 of the valve piston 306 and the oscillating piston 308 comes to rest against the valve piston 306 .
In Phase 2, the valve 316 is closed and the drilling mud 40 cannot flow between the valve seat 318 and the valve body 320 . This creates flow pressure against both the valve piston 306 and the oscillating piston 308 , forcing the valve spring 310 and the main spring 312 to compress. This compression allows the valve piston 306 and the oscillating piston 308 to move downwards at the same rate, thus keeping the valve 316 in the closed position. When the valve piston 306 reaches the stop shoulder 322 , Phase 2 ends.
In Phase 3, the valve piston 306 stops its downward motion when the valve piston 306 reaches the stop shoulder 322 and the valve spring 310 forces the valve piston 306 to oscillate back upwards, pulling the valve body 320 away from the valve seat 318 . At the same time, due to high inertia, the oscillating piston 308 maintains its downward direction of movement, further widening the gap between the valve body 320 and the valve seat 318 , thereby opening the valve 316 which allows the mud 40 to flow downhole. This ends Phase 3.
The fourth and final phase starts (a few tenths of a second after the valve piston 306 reverses its direction) when the oscillating piston 308 stops due to the full compression of the main spring 312 . Because the mud 40 is flowing through the open valve 316 relieving the fluid pressure on the top of the oscillating piston 308 , the main spring 312 decompresses thereby forcing the oscillating piston 308 upward. The upward movement of the oscillating piston 308 is the beginning of Phase 1 and the cycle starts again.
The oscillating piston 308 of the preferred embodiment is designed as a sliding valve which connects the flow of drilling mud 40 to either a first actuator channel 324 a or a second actuator channel 324 b. The connection is made between the mud 40 and the first actuator channel 324 a when the oscillating piston 308 is located towards the top of its upward path such that an aperture 326 in the oscillating piston 308 is adjacent a first inlet chamber 330 a which is in fluid communication with the first actuator channel 324 a. Similarly, when the oscillating piston 308 is towards the bottom of its downward path, the aperture 326 is adjacent to a second flow chamber 330 b which is in fluid communication with the second actuator channel 324 b thereby allowing the mud 40 to flow into the second actuator channel 324 b.
Pressure is created by the delta in the flow rate across the low-pressure nozzles 338 a-b. If fluid is pumped into one of the low-pressure actuator channels 324 a, then that flow rate is removed from the other low-pressure actuator channel 324 b and a pressure differential is created. The double-acting piston 300 is driven by whichever channel (the first or second actuator channel 324 a-b ) is connected to the flow path of the drilling mud 40 a. Driving pressure is established by the difference (drop) in pressure across the low-pressure nozzles 338 a-b.
An upper plunger 336 a and a lower plunger 336 b act as pumps in conjunction with four check valves 332 a-d (two per plunger). The high pressure is created across the high-pressure nozzle 339 inside the drill bit 26 . The high-pressure fluid jet (not shown) is directed at the bottom of the wellbore 24 to support the drilling process.
Both low-pressure actuator channels 324 a-b are connected to the double-acting pressure intensifier 300 and to the outlets (low-pressure nozzles) 338 a-b, respectively. Part of the flow of low-pressure mud 40 a from the first actuator channel 324 a goes through a first low-pressure line 346 a and exits the drill string 20 through the first low-pressure nozzle 338 a. Due to high pressure forming in the double-acting pressure intensifier 300 by the action of high-pressure plungers 336 a-b, another part of the low-pressure mud 40 a flows into an upper chamber 342 a of the double-acting pressure intensifier 300 through a first chamber line 340 a.
The final part of the low-pressure mud 40 a flows into a first low-pressure inlet 328 a in the pressure intensifier 304 . The first check valve 332 a opens when the double-acting pressure intensifier/piston 300 is traveling downwards creating lower pressure in an upper plunger cavity 334 a. This causes the upper plunger cavity 334 a to equalize the pressure by sucking the low-pressure mud 40 a from the first low-pressure inlet channel 328 a through the first check valve 332 a into the upper plunger cavity 334 a. Continuing downward, the double-acting piston 300 forces the mud 40 in a lower plunger cavity 334 b through a fourth check valve 332 d at a higher pressure into a first high-pressure nozzle line 344 a.
As the double-acting piston 300 reaches its bottom stroke, it reverses direction whereby the mud 40 from the second low-pressure input channel 328 b is sucked from a second low-pressure nozzle line 346 b through a third check valve 332 c into a lower chamber 342 b in the pressure intensifier 300 . As the upper plunger 336 a moves upwards, the pressure on the mud 40 in the upper plunger cavity 334 a increases and keeps a second check valve 332 b closed.
The low-pressure mud 40 a that flows through the second actuator channel 324 b passes through an aperture 326 into a second inlet chamber 330 b and through a second low-pressure line 346 b and exits the drill bit 26 through a second low-pressure nozzle 338 b.
A third preferred embodiment 100 B is illustrated in FIG. 4 . This embodiment uses a single-acting pressure intensifier 400 . A lower end 402 of the drill string 20 is connected to a pressure intensifier 404 . A valve piston 406 and a pressure intensifier piston 408 are slidably mounted inside the pressure intensifier sub 404 . The valve piston 406 and the pressure intensifier piston 408 are pushed back into their normal biased positions (up) by a valve spring 410 and a main spring 412 , respectively.
As in the double acting pressure intensifier 300 (as shown in FIG. 3 ), one cycle of the single acting pressure intensifier 400 includes four phases. In Phase 1, the pressure intensifier piston 408 is driven upward by the biasing action of the main spring 412 . When a valve seat 414 reaches a valve body 416 of the valve piston 406 , a valve 418 closes and Phase 1 ends.
At the start of Phase 2, the valve 418 is closed and the drilling mud 40 a cannot flow between the valve seat 414 and the valve body 416 . This creates flow pressure against both springs (the valve spring 410 and the main spring 412 ) forcing them downward which allows the valve piston 406 and the pressure intensifier piston 408 to move downward until the valve piston 406 reaches a stop shoulder 420 . This is the end of Phase 2.
In Phase 3, the valve piston 406 stops its downward motion when the valve piston 406 reaches the stop shoulder 422 and the valve spring 410 forces the valve piston 406 to oscillate back upwards pulling the valve body 416 away from the valve seat 414 . At the same time, due to high inertia, the pressure intensifier piston 408 maintains its downward direction of movement, further widening the gap between the valve body 416 and the valve seat 414 thereby opening the valve 418 which allows the mud 40 to flow through. This ends Phase 2.
The fourth and final phase starts (a few tenth of a second after the valve piston 406 reverses its direction) when the pressure intensifier piston 408 stops due to the full compression of the main spring 412 . Because the mud 40 is flowing through the open valve 418 relieving the fluid pressure on the top of the pressure intensifier piston 408 , the main spring 412 decompresses thereby forcing the pressure intensifier piston 408 upwards. This upward movement of the pressure intensifier piston 408 is the beginning of Phase 1 and the cycle starts again.
The pressure intensifier piston 408 includes a plunger 422 which is guided inside a cylindrically-shaped passageway 424 and is protected by a bellows 426 which also acts as a means for pressure compensation. A high-pressure seal 428 separates a high-pressure channel 430 from a low-pressure channel 432 of the plunger 422 . To have clean drilling mud 40 in both channels (the high pressure channel 430 and the low-pressure channel 432 ), a high-pressure membrane 434 is positioned to separate the high-pressure drilling mud 40 b from a pressure-transmitting fluid 436 . A ball-check valve 438 serves as a suction valve for the plunger 422 .
The up and down action of the plunger 422 in the passageway 424 , creates a pressure differential and low-pressure mud 40 a in the low-pressure channel 432 is sucked through an inlet 444 into the ball-check valve 438 . The high-pressure mud 40 b discharging through the ball-check valve 438 flows through the high-pressure channel 432 and exits the drill bit 26 as a high-pressure jet through the high-pressure nozzle 440 which is located inside the drill bit 26 and directed downwards towards the bottom of the wellbore 24 .
The remainder of the low-pressure mud 40 a (that is not diverted through the inlet port 444 to the ball-check valve 438 ) continues flowing through the low-pressure channel 432 and exits the drill string 20 through a low-pressure nozzle 442 in the drill bit 26 where it circulates uphole through the annular space 54 (see FIG. 1) between the drill string 20 and the borehole 24 for discharge back into the mud pit 42 to complete the cycle.
While the foregoing disclosure is directed to the preferred embodiments of the invention, various modifications will be apparent to those skilled in the art. It is intended that all variations within the scope and spirit of the appended claims be embraced by the foregoing disclosure. | A drilling system utilizing the drilling fluid in a borehole to drive an apparatus to generate a high-pressure jet of fluid to facilitate the drilling operation. A pressure intensifier disposed between a drilling motor and the drill bit generates high pressure fluid jet. The drilling motor rotates the pressure intensifier. Fluid enters a high pressure chamber in the pressure intensifier at selected location during each rotation. A piston in the pressure intensifier discharges the fluid from the high pressure chamber to the drill bit bottom at a high pressure. An electrically-operated pulse frequency control device generates fluid pulses of at least two frequencies, each such frequency defining a bit of a binary system. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to agitator-less washing machines and specifically to washing machines in which multiple high-pressure fluid streams agitate a wash load.
BACKGROUND OF THE INVENTION
[0002] A typical vertical washing machine features a centrally oriented finned agitator that swings back and forth around a central axis so that the fins beat the washing articles in a first direction, then in a second opposite direction. The continued beating results in noticeable physical wear of the articles being cleaned.
[0003] To reduce the contact between the wash load and the agitator and hence wear of the articles, one class of washing machines feature agitators that include water jets and are seen in U.S. Pat. Nos. 4,420,952: 4,419,870: 4,402,198 and 4,077,239. While water jet agitators increase article movement through the wash load, they do not significantly reduce the resultant wear on the articles.
[0004] Washing machines without agitators that use a water jet to circulate the wash load are known: U.S. Pat. No. 3,444,710 teaches a single water jet affixed to, and dispensing water from, the periphery of the washing basket; and U.S. Pat. No. 3,867,821 teaches a single centrally located rotating water jet.
[0005] The drawback of water jet agitating machines is that the singular water jet interacts with only a small portion of the wash load at any given time, thereby failing efficiently agitate the articles. Inefficient agitation results in inadequately cleaned articles.
[0006] In spite of the tremendous need and advantage for an efficient agitator-less vertical washing machine that efficiently cleans articles, there is no washing machine devoid of the above limitations.
SUMMARY OF THE INVENTION
[0007] The present invention comprises a washing machine having multiple high velocity water streams positioned around a washing basket to agitate the wash load during a wash cycle.
[0008] 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. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
[0009] There is thus provided, an aspect of an embodiment of the present invention comprising a fluid stream wash load agitating system, comprising a vertical axis washing tub and a vertical axis washing basket coaxially placed within the tub. The invention further comprises at least one fluid output positioned to remove water from the basket during the operation and at least one first and at least one second high velocity fluid stream inputs around the basket and positioned to substantially agitate at least a portion of the wash load during the operation.
[0010] In an exemplary embodiment, the system above includes at least one first and at least one second high velocity fluid inputs each comprise at least two high pressure fluid nozzles.
[0011] In a further exemplary embodiment, an axis passing through the at least one first and at least one second high velocity fluid input nozzles is substantially at least one of: vertical, between 0 and 45 degrees to a vertical axis, horizontal and between 0 and 45 degrees to a horizontal axis.
[0012] Additionally, in further embodiments, the at least one first high velocity fluid input nozzle is positioned to provide a stream to an upper portion of a wash load during the operation and the at least one second high velocity fluid input nozzle is positioned to provide a stream to a lower portion of a wash load during the operation.
[0013] In additional embodiments, the at least one first high velocity fluid input nozzle is independently controlled to operate only when an upper portion of the basket is filled with a wash load during the operation.
[0014] Optionally, at least one first and at least one second high velocity fluid inputs provide pulsed streams of high pressure fluid. Alternatively, the at least one first fluid input and the at least one second input provide simultaneous pulsed streams to the wash load.
[0015] In an exemplary embodiment, the at least one fluid output comprises at least two fluid outputs, including at least one first fluid output and at least one second fluid output. Optionally, the at least two fluid outputs output the fluid in pulses.
[0016] In a further embodiment of the present invention, the at least one first fluid output is synchronized to output fluid pulses from the basket simultaneous to the input of the pulsed streams by the at least one first fluid input pulse and the at least one second fluid output is synchronized to output fluid pulses from the basket simultaneous to the input of the pulsed streams by the at least one second fluid input pulse.
[0017] In further exemplary embodiments, the at least one first fluid input and the at least one second input provide sequential pulsed streams to the wash load.
[0018] Optionally, the at least one first fluid output is synchronized to output fluid pulses from the basket simultaneous to the input of the pulsed streams by the at least one first fluid input pulse; and the at least one second fluid output is synchronized to output fluid pulses from the basket simultaneous to the input of the pulsed streams by the at least one second fluid input pulse.
[0019] In an additional exemplary embodiment, at least one first fluid pump connected to the at least one fluid output and at least one second fluid pump connected to the at least two high velocity fluid inputs.
[0020] Furthermore, the at least one first fluid pump and the at least one second fluid pump are operatively associated so as to provide recycling of fluid from the wash load during the operation.
[0021] In an exemplary embodiment, the at least two fluid inputs are positioned to cause rotation of fluid in at least a portion of the wash load. Alternatively, the at least two fluid inputs are positioned to cause rotation of at least a portion of the wash load.
[0022] Optionally, the at least two fluid inputs are positioned to cause centrifugally balanced rotation of at least a portion of the wash load. Additionally, the basket additionally rotates at during at least a portion of the operation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The present invention, a washing machine having multiple water streams around the wash basket, is by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the preferred method of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the methods of the invention may be embodied in practice.
[0024] FIG. 1 is a schematic view of a Wash basket having a fluid stream agitator system, in accordance with an embodiment of the present invention;
[0025] FIGS. 2 and 3 are schematic representations of an embodiment of the fluid stream agitator shown in FIG. 1 ; and
[0026] FIG. 4 is a three dimensional schematic representation of the fluid stream agitator system shown in FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] In broad terms, the present invention relates to a fluid stream agitator system. The principles and operation of the system according to the present invention may be better understood with reference to the drawings and accompanying descriptions.
[0028] 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 the arrangement of the components set forth in the following description or illustrated in the drawings. The invention 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.
[0029] The principles, uses and implementations of the teachings of the present invention may be better understood with reference to the accompanying description, figures and examples, perusal of which allows one skilled in the art to implement the teachings of the present invention without undue effort or experimentation. In the figures, like reference numerals refer to like parts throughout.
[0030] Generally, the nomenclature used herein and the laboratory procedures utilized in the present invention include techniques from the fields of biology, engineering, material science, medicine and physics. Such techniques are thoroughly explained in the literature.
[0031] 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 the invention belongs. In addition, the descriptions, materials, methods and examples are illustrative only and not intended to be limiting. Methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
[0032] As used herein, the terms “comprising” and “including” or grammatical variants thereof are to be taken as specifying the stated features, integers, steps or components but do not preclude the addition of one or more additional features, integers, steps, components or groups thereof. This term encompasses the terms “consisting of” and “consisting essentially of”.
[0033] The phrase “consisting essentially of” or grammatical variants thereof when used herein are to be taken as specifying the stated features, integers, steps or components but do not preclude the addition of one or more additional features, integers, steps, components or groups thereof but only if the additional features, integers, steps, components or groups thereof do not materially alter the basic and novel characteristics of the claimed composition, device or method.
[0034] The term “method” refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of the relevant arts. Implementation of the methods of the present invention involves performing or completing selected tasks or steps manually, automatically, or a combination thereof.
[0035] FIG. 1 is a schematic view of a vertical wash tube 196 coaxially disposed around a wash basket 190 including a fluid stream agitator system 100 , in accordance with an embodiment of the present invention.
[0036] In System 100 , fluid 121 is delivered through input source 123 into a fluid input pump 110 , comprising a standard centrifugal or positive displacement pump. Pump 110 has input pipes 120 and 130 that send fluid 121 into a wash load 192 . Fluid 121 is removed from wash load 192 via two output pipes 220 and 230 via a standard centrifugal or positive displacement output pump 210 through output source 223 . A controller 102 controls input pump 110 and output pump 210 , for example by operating output pump only after fluid pumped into wash load 192 has reached a specified height. In a further exemplary embodiment, input pump 110 and output pump 120 are connected so that fluid 121 from basket 190 is continually recirculated during a wash cycle.
[0037] In an exemplary embodiment, input pump 110 is connected to a fluid input pipe 120 having high pressure input nozzles, 122 , 124 , 126 , and 128 that shoot high pressure streams of fluid 121 . Pump 110 is further connected to a fluid input pipe 130 having high pressure input nozzles, 132 , 134 , 136 , and 138 that similarly shoot high pressure streams of fluid 121 .
[0038] In an exemplary embodiment, input nozzles, 122 , 124 , 126 , and 128 work simultaneously with input nozzles, 132 , 134 , 136 , and 138 to send streams passing into wash basket 190 and serve to agitate a wash 192 in basket 190 and cause rotation of wash 192 in a direction 194 .
[0039] In a further exemplary embodiment, output pump 210 , via a fluid suction pipe 220 connected to suction outputs, 222 , 224 , 226 , and 228 ; and via a fluid suction pipe 230 connected to suction outputs, 232 , 234 , 236 , and 238 removes fluid 121 from basket 190 .
[0040] In an exemplary embodiment, wash basket 190 is connected to belts and pulleys (not shown) that provide rotation to basket 190 during a wash cycle and/or during high-speed rotation and rotation of load 192 during evacuation of fluid 121 .
[0041] During washing, optional rotation of basket 190 produces fluid 121 motion that results, in addition to agitation provided by fluid 121 from inputs 120 and 130 and outputs 220 and 230 , vertical motion, radial motion and/or circumferential motion of wash load 192 .
[0042] In an exemplary embodiment, fluid 121 is optionally sprayed on the rotating wash load 192 during high speed centrifugal of basket 190 thereby helping rid the articles of soap during evacuation of fluid 121 .
[0043] FIG. 2 , is a schematic representation of basket 190 shown in FIG. 1 , during input of fluid 121 .
[0044] In an exemplary embodiment, fluid 121 is introduced into wash load 192 with simultaneous and continuous streams from all input nozzles, 122 and 132 ; 124 and 134 ; 126 and 136 ; and 128 and 138 . Alternatively, fluid may be introduced into wash load 192 with simultaneous pulses of fluid 121 from all input nozzles, 122 and 132 ; 124 and 134 ; 126 and 136 ; and 128 and 138 .
[0045] Alternatively, in sequential pulsing, a first pulse of fluid 121 is pulsed via input nozzles, 122 , 124 , 126 , and 128 , followed by a second, pulse of fluid 121 via input nozzles, 132 , 134 , 136 and 138 ; after which the pulse cycle is repeated.
[0046] In alternative embodiments, for example where there three, rather than two input pipes 120 and 130 , and/or one or more pumps in addition to pump 110 , ( FIG. 1 ) sequential pulsing may provide a first pulse of fluid 121 , followed by a second pulse and then a third pulse, continually repeating three pulses of fluid 121 input during the washing cycle of wash load 192 .
[0047] FIG. 3 , is a schematic representation of basket 190 shown in FIG. 1 , during an exemplary embodiment of output of fluid 121 .
[0048] In an exemplary embodiment, fluid 121 is removed from wash load 192 with simultaneous and continuous sucking from all suction outputs, 222 and 232 ; 224 and 234 ; 226 and 236 ; and 228 and 238 . Alternatively, in conjunction with simultaneous pulsing as explained above in relation to FIG. 1 , fluid is removed from wash load 192 with simultaneous pulsed sucking of fluid 121 from all suction outputs, 222 and 232 ; 224 and 234 ; 226 and 236 ; and 228 and 238 .
[0049] Alternatively, for example in conjunction with sequential pulsing as explained above in relation to FIG. 1 , a first pulse of fluid 121 is sucked via output nozzles, 222 , 224 , 226 , and 228 , followed by a second, pulse of fluid 121 via output nozzles, 232 , 234 , 236 and 238 ; after which the pulse cycle is repeated.
[0050] In alternative embodiments, for example where there three, rather than two output pipes 220 and 230 , and/or one or more pumps in addition to pump 210 , ( FIG. 1 ) sequential water removal may provide a first suction of fluid 121 through a first set of output suctions, followed by a suction pulse and then a third suction, continually repeating three suctions of fluid 121 removal during the washing cycle of wash load 192 .
[0051] There are many physical arrangements of input nozzles and suction outputs and patterns of input pulsing and output suction, all of which are readily appreciated by those familiar with the art.
[0052] FIG. 4 is a three dimensional schematic representation of an alternative embodiment fluid system 400 comprising multiple input pipes 420 , 421 , 422 , 423 , 424 , 425 , 426 , and 427 , each controlled by a corresponding controller; 420 ′, 421 ′, 422 ′, 423 ′, 424 ′, 425 ′, 426 ′, and 427 ′ that are connected to, for example, solenoids in conjunction with output pump 110 . Each input pipe includes six high-pressure nozzles 425 A, 425 B, 425 C, 425 D, 425 E, and 425 F, seen on input pipe 425 .
[0053] In an exemplary embodiment, fluid 121 is dispensed simultaneously or sequentially via input pipes 420 , 421 , 422 , 423 , 424 , 425 , 426 , and 427 . Alternatively, the pattern of input can be varied so that pairs of pipes on opposite sides of basket 190 input fluid 121 simultaneously, for example paired pipes 420 and 424 , followed by paired pipes 421 and 425 ; followed by 422 and 426 ; and finally pipes 423 and 427 after which the cycle is repeated.
[0054] Similarly, system 400 includes multiple output pipes 460 , 461 , 462 , 463 , 464 , 465 , 466 , and 467 , each controlled by a corresponding controller; 460 ′, 461 ′, 462 ′, 463 ′, 464 ′, 465 ′, 466 ′, and 467 ′ that are connected to, for example, solenoids in conjunction with output pump 210 . Each output pipe includes six output suctions 462 A, 462 B, 462 C, 462 D, 462 E, 462 F, seen on output pipe 462 .
[0055] In an exemplary embodiment, fluid 121 is suctioned from basket 190 simultaneously or sequentially via output pipes 460 , 461 , 462 , 463 , 464 , 465 , 466 , and 467 or in alternate patterns.
[0056] For example in conjunction with input of pipes 420 and 424 , output pipes 460 and 464 suction fluid 121 . As input pipes 421 and 425 input fluid 121 , pipes 461 and 465 suction fluid 121 , with the cycle continuing sequentially around basket 190 .
[0057] The many arrangements by for dispensing fluid 121 and removing fluid, through input pipes 420 , 421 , 422 , 423 , 424 , 425 , 426 , and 427 ; and output pipes 460 , 461 , 462 , 463 , 464 , 465 , 466 , and 467 respectively, are well known to those familiar with the art.
[0058] Washing systems 100 and 400 are optionally installed in additional where agitation by fluid 121 , without a mechanical agitator, is desired and with fluids other than water, i.e. dry cleaning with special dry cleaning fluids, or cleaning of mechanical parts with solvents, etc. The many applications of systems 100 and 400 will be readily apparent to those familiar with the art.
[0059] While the invention has been shown and described with respect to a particular embodiment thereof, this is for the purpose of illustration rather than limitation. Variations and modifications of the specific embodiment herein shown and described will be apparent to those skilled in the art. All of these modifications are within the intended spirit and scope of the invention. Accordingly, the patent is not to be limited in scope and effect to the specific embodiment herein shown and described or in any other way that is inconsistent with the extent to which the progress in the art has been advanced by the invention.
[0060] Additional objects, advantages, and novel features of the present invention will become apparent to one ordinarily skilled in the art upon examination of the following examples, which are not intended to be limiting. Additionally, each of the various embodiments and aspects of the present invention as delineated hereinabove and as claimed in the claims section below finds experimental support in the following examples.
[0061] It is expected that during the life of this patent many relevant delivery systems will be developed and the scope of the terms of the patent are intended to include all such new technologies a priori.
[0062] As used herein the term “about” refers to ±10%.
[0063] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
[0064] Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. All publications, patents and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention. | A fluid stream wash load agitating system, comprising a vertical axis washing tub, a vertical axis washing basket coaxially placed within said tub, at least one fluid output positioned to remove water from said basket during said operation, and at least one first and at least one second high velocity fluid stream inputs around said basket and positioned to substantially agitate at least a portion of said wash load during said operation. | 3 |
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The invention relates to the field of sensors and methods for measuring one or more select components of a material. In particular, the invention relates to measuring the components by emitting electromagnetic radiation at the material and detecting the amount of emerging radiation at separate locations. The invention can accurately measure the components (e.g., moisture) of different grades of paper by eliminating the effects of the scattering power and determining absorption power at each band of the spectrum necessary for the particular measurement.
(2) Description of the Related Art
Because paper is produced in a sheet from an aqueous suspension, which includes wood pulp fibers, cotton fibers and various chemicals, it initially contains a considerable amount of moisture. Most of this moisture is removed during paper production. However, for a variety of reasons, it is often desirable to include at least some moisture in the paper. For example, if the paper is too dry, it will tend to curl at the edges or may increase the cost of production.
A paper sheet is typically dried by passing it around heated drying drums. However, this tends to dry the sheet unevenly across its cross-direction width, producing paper of uneven quality. Devices have been developed to selectively moisten or dry the cross-directional sections of the sheet. Boissevain et al. U.S. Pat. No. 5,020,469, assigned to Measurex Corporation, describes such a device. Typically, the moistening or drying occurs after the sheet has passed around the drying drums. Of course, the paper mill operator, or the paper mill's process control computer, must determine the cross-directional moisture profile of the sheet before these devices can be used effectively. Thus, moisture sensors have been developed to measure the cross-directional moisture profile.
Water absorbs electromagnetic radiation across the infrared spectrum as a function of wavelength. Some moisture sensors take advantage of this phenomenon by emitting infrared radiation at the sheet and detecting the amount of the radiation passing through or reflected from the sheet at or near the water absorption peak. The more moisture in the sheet, the less radiation at or near the water absorption peak that will pass through or be reflected from the sheet.
An infrared moisture sensor can be set up with an infrared radiation source located on one side of the sheet and two detectors on the opposite side. Each detector has an associated band pass filter positioned between the source and the detector so that the detector only receives radiation in a select band of the spectrum. A first band pass filter passes that portion of radiation which is near a water absorption peak to a first detector. Thus, the first detector is primarily sensitive to the amount of water in the sheet and receives more infrared radiation when the sheet is dry and less infrared radiation when the sheet is moist.
A second band pass filter passes radiation in a band of the spectrum where there is less moisture absorption. In this band, most of the absorption is from sheet fibers rather than moisture in the sheet. Thus, when the basis weight (i.e., weight per unit area) of the sheet fiber increases, the second detector receives less infrared radiation. The output of the second detector corrects for changes in the basis weight of the sheet fiber. When the outputs from these two detectors are properly combined, the sensor provides an accurate measurement of the moisture in the sheet so that the changes in the basis weight of the sheet fiber do not affect the moisture measurement.
Howarth et al. U.S. Pat. No. 4,928,013, assigned to Measurex Corporation, describes an infrared moisture sensor of this type with two band pass filters that are selected to compensate for sheet temperature changes which shift the absorption spectrum to either shorter or longer wavelengths. In this sensor, a first band pass filter, associated with a measure detector, is selected so that it is surrounds the water absorption peak at about 1.93 microns. When the sheet temperature increases, the intensity of radiation increases at the long wavelength side of the pass band filter while an approximately equal decrease occurs at the short wavelength side. Accordingly, the amount of infrared radiation reaching the measure detector remains substantially constant when the sheet temperature changes. A second band pass filter, associated with a reference detector, is selected so that it is in a band of the infrared spectrum that is predominantly absorbed by the sheet fibers. The intensity of the radiation detected by the reference detector primarily indicates the basis weight of the sheet.
However, the intensity of the detected radiation is not only dependent upon the moisture, basis weight and temperature of the sheet. Each grade of sheet has its scattering and absorption powers that affect the intensity of the detected radiation. A scattering power of a material defines its ability to change the direction of light incident upon the material from either the line of incidence when transmitted through or from a specular direction when reflected from the material. An absorption power defines the material's ability to absorb the incident light rather than allow it to be transmitted through or reflected from the sheet.
The source of the wood fiber used to make paper products may affect the value of the scattering coefficient and/or the broadband absorption coefficients. This in turn may affect the accuracy of an infrared moisture sensor. Changes in the scattering power of paper are often caused when the source of the paper pulp changes from one species of wood to another or from virgin to recycled fiber. Broadband absorption change may be caused by the carbon black in printer inks used in recycled paper or added to colored paper.
Howarth U.S. Pat. No. 3,793,524, assigned to Measurex Corporation, describes an infrared moisture sensor for measuring the moisture of a sheet of material such as paper. The moisture sensor includes an infrared source that directs infrared radiation out of an aperture through paper and into another aperture to a detector. The source and detector apertures are located in opposing reflective paper guides disposed on either side of the paper and are offset from one another so that the radiation is reflected repeatedly back and forth between the paper guides in traveling from the source aperture and to the detector aperture (FIG. 2). The offset geometry results in relatively low sensitivity to the scattering power of the paper but may require calibration to measure different grades of paper.
Tamura et al. U.S. Pat. No. 4,345,150 ("Tamura") describes a moisture meter. As shown in FIG. 8A, the moisture meter is shown with an irradiation aperture 4 having an optical axis aligned with that of the incident aperture 5 but not (or offset from) with that of incident aperture 5'. As a result, signals R t and M t are generated from the light which has been incident upon the aperture 5 and signals R n and M n are generated from light which has been incident upon aperture 5'.
Because paper includes both elements which scatter and absorb light, the signals R 5 , M t , R n and M n will be sensitive to both the scattering and absorption powers of the paper being measured. Tamura fails to recognize the problem of the scattering power affecting these signals and thereby the measurements or describe any technique for determining the absorption power of the paper by itself.
Tamura's moisture meter would therefore require a number of calibrations to measure all grades of paper, otherwise, the scattering power affects the accuracy of the moisture measurements. It would be highly desirable to have a moisture sensor which has one calibration for a broad range of grades of paper. To achieve this goal any sensitivity to the scattering power must be eliminated.
SUMMARY OF THE INVENTION
The present invention relates to a sensor and method for measuring one or more select components (e.g., moisture) of a material by emitting radiation at the material and detecting the amount of radiation emerging from the material at separate locations from the radiation source after the radiation has multiple interactions with the material.
In one embodiment, the invention provides a sensor for measuring select components of a material such as a sheet, including: (1) a radiation source for emitting radiation at a sheet; (2) a plurality of detecting means, wherein at least one detecting means is offset from the source, for detecting radiation after interaction with the sheet; (3) means for directing the radiation so that the radiation makes multiple interactions with the sheet when moving from the source to the detecting means; and (4) means for computing the absorption power of the sheet from the detected radiation.
In another embodiment, the invention provides a sensor for measuring select components such as the moisture of a sheet, including: (1) a source for emitting radiation through a source aperture; (2) means for detecting radiation after multiple interactions with the sheet, including at least two apertures, wherein at least one detector aperture is offset from the source aperture, for receiving the radiation; (3) first and second reflector means for directing the radiation so that the radiation has multiple interactions with the sheet when moving from the source to the detecting means; and (4) means for computing the absorption power of the sheet from the detected radiation.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects, features and advantages of the invention will become more apparent from the following detailed description of the preferred embodiments taken in conjunction with accompanying drawings, in which:
FIG. 1 is a partial perspective view of a sensor mounted on a scanner which moves back and forth in the cross-direction across the sheet.
FIG. 2 is a schematic elevation view illustrating an embodiment of a sensor according to the present invention.
FIG. 3a illustrates a reflective paper guide of the lower head of the sensor with a source aperture.
FIG. 3b illustrates a reflective paper guide of the upper head of the sensor with two detector apertures.
FIG. 4 illustrates the infrared transmission spectra of a light weight paper sheet, containing moisture, at two different temperatures with indication of appropriate detected measure, reference, temperature correction, cellulose and synthetic wavelength bands.
FIG. 5 illustrates the infrared transmission spectra of a medium weight paper sheet, containing moisture, at two different temperatures with indication of appropriate detected measure, reference, temperature correction and cellulose wavelength bands.
FIG. 6 illustrates the infrared transmission spectra of a heavy weight paper sheet, containing moisture, at two different temperatures with indication of appropriate detected measure, reference, temperature correction, cellulose and second reference wavelength bands.
FIG. 7 illustrates the geometry and nomenclature used for the analysis of the light distribution on two parallel planes.
FIG. 8 illustrates a graph of the absorption and scattering powers of a paper sheet plotted as a function of the reciprocal of the intensity of radiation individually detected at a straight-through and offset transmission detector.
FIG. 9 illustrates an alternative embodiment for the source and detector apertures of the reflective paper guides and a possible variation for the surface of the paper guides.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following description covers the best mode of carrying out the invention. For the sake of simplicity the invention will be described primarily as measuring the amount of moisture in a paper sheet by use of infrared radiation. However, this is only to illustrate the principles of the invention and should not be taken in a limiting sense. The principles of the invention may be also used to measure other select components or physical properties (e.g., basis weight) of a sheet of other types of materials (e.g., plastic film) with other forms of electromagnetic radiation (e.g., ultraviolet and visible light). Therefore, the scope of the invention is best determined by reference to the appended claims. In the accompanying drawings like numerals designate like parts.
FIG. 1 illustrates a scanner 10 which includes a framework 12 of a pair of spaced upper and lower parallel beams 14 and 16 extending in the cross-direction across the sheet of material or paper 18. Paper 18 travels through the scanner 10 in the direction shown by arrow 20. Lower and upper gauging heads 22 and 24 are provided on the framework 12 and travel longitudinally of framework 12 and in the cross-direction of paper 18.
FIG. 2 illustrates an infrared moisture sensor 32. It includes a lower head 22 with a radiation source for directing infrared radiation 42 through a source aperture 34 to paper 18. Favorable results were achieved by using a radiation source including an incandescent lamp 38 and an elliptical reflector 40 with a source aperture 34 of about 1/2 inch in diameter. It is preferred, but not necessary to the invention, that the amount of radiation emitted from lamp 38 and falling on paper 18 be modulated at a known frequency.
This modulation may be accomplished by any one of several devices. For example, the tines 44 of a tuning fork 46 may be disposed in the path of the radiation 42. The vibrating tines 44 modulate the radiation 42 as the tines 44 move alternatively in and out of the path of radiation 42. Alternatively, an opaque disk (not shown) having a plurality of evenly spaced radial slots may be rotated in the path of the radiation so that the radiation is alternately transmitted through the slots and blocked by the opaque portions of the disk. With either device, radiation 42 is modulated at a known frequency. The reason for modulating the radiation is explained below.
The lower and upper heads 22 and 24 include opposing surfaces which function as paper guides 28 and 30. Each of the guides 28 and 30 includes a reflective coating 48 (FIGS. 3a and 3b) for directing radiation from a source aperture 34 to detector aperture 36. FIG. 3a illustrates that guide 28 includes a reflective coating 48 and source aperture 34. FIG. 3b illustrates that guide 30 has a similar reflective coating 48 and detector apertures 36 and 37.
Reflective coating 48 is preferably a non-specular or diffuse reflective surface. For example, coating 48 may consist of a layer of translucent quartz or glass ceramic backed by a reflective material. To provide an easily cleaned surface the surfaces of guides 28 and 30 may be anodized aluminum. In one preferred embodiment, the guides 28 and 30 may consist of two diffuse reflective parallel plates about 0.4 inches apart.
In the embodiment of FIG. 2, radiation 42 is reflected back and forth between lower and upper guides 28, 30, before entering detector aperture 36. This ensures that radiation 42 makes multiple interactions with paper 18, that is, passes through the paper 18 a number of times. This provides certain advantages when measuring the moisture content of very light grades of paper, such as tissue, and very heavy paper grades. This technique and the advantages of such multiple interactions with the paper sheet are more fully discussed in Howarth U.S. Pat. No. 3,793,524, assigned to Measurex Corporation, which is incorporated herein by reference.
The radiation 42 of source aperture 34 reaches detector aperture 36 by a somewhat complex set of paths, partially illustrated by the dashed lines. The radiation 42 initially impinges on paper 18 with part of the radiation 42 passing through and part being reflected by the paper 18. Guides 28 and 30 reflect this radiation 42 back to the paper 18 where it undergoes the same process of partial transmission and reflection. In addition, the paper 18 itself, being translucent, acts to diffuse the radiation 42 to increase the number of paths.
The mean number of times the radiation 42 passes through the paper 18 on its path from the source aperture 34 to the detector aperture 36 can be easily controlled by adjusting the geometry of sensor 32. In this manner, paper 1 can be made to appear thicker than its actual thickness.
As shown in the embodiment of FIG. 2, radiation 42 from source aperture 34 reaches detector aperture 37 by a single path illustrated by the dashed line. Thus, the radiation 42 entering detector aperture 36 has greater interaction with paper 18 than that entering detector aperture 37.
The radiation 42 enters upper head 24 through detector aperture 36. The upper head 24 includes a light pipe 50 which guides the radiation 42 to a lens 52 which collimates the radiation. The first beam splitter 54 splits the radiation 42 into three separate beams 56, 58 and 60. Band pass filters 62 and 64 are positioned in the respective paths of beams 56 and 60. Lenses 66 and 68 focus the radiation on a temperature detector 70 and a synthetic detector 72. Detectors 70 and 72 may be of the lead sulfide type. Each filter 62 and 64 is designed to pass radiation in a select spectral band. Radiation not within the pass band of filters 62 and 64 is reflected by these filters to beam splitter 54 and does not reach temperature detector 70 or synthetic detector 72.
The portion of radiation 42 transmitted through the first beam splitter 54, that is, beam 58, impinges on a second beam splitter 74. The second beam splitter 74 splits beam 58 into three beams 76, 84 and 92. Band pass filters 78, 86 and 94 are positioned in the respective paths of beam 76, 84 and 92. Lenses 80, 88 and 96 focus the radiation on a cellulose detector 82, a measure detector 90 and a reference detector 98. Detectors 82, 90 and 98 also may be of the lead sulfide type. Each filter 78, 86 and 94 is selected so that it passes radiation in a separate band of the spectrum. Thus, a radiation 42 enters the upper head 24 through detector aperture 36, but the optics in the upper head 24 split the radiation 42 into five beams 56, 60, 76, 84 and 92 each of which is detected by an associated infrared detector 70, 72, 82, 90 and 98.
In a similar manner, the upper head 24 includes a detector aperture 37, a light pipe 51 which guides radiation 42 to a collimating lens 53 between the light pipe 51 and a first beam splitter 55. The first beam splitter 55 splits radiation 42 into three separate beams 57, 59 and 61. Band pass filters 63 and 65 are positioned in the respective paths of beams 57 and 61. Lenses 67 and 69 focus the radiation on a temperature detector 71 and synthetic detector 73. Detectors 71 and 73 may be of the lead sulfide type. Each filter 63 and 65 is selected so that it passes radiation in a separate band of the spectrum. Radiation not within the pass band of filters 63 and 65 is reflected by these filters to the first beam splitter 55 and does not reach temperature detector 71 or synthetic detector 73.
The portion of radiation 42 transmitting through first beam splitter 55, that is, beam 59, impinges on a second beam splitter 75. The second beam splitter 75 splits the beam 59 into three separate beams 77, 85 and 93. Band pass filters 79, 87 and 95 are positioned in the respective paths of beam 77, 85 and 93. Lenses 81, 89 and 97 focus the radiation on a cellulose detector 83, a measure detector 91 and a reference detector 99. Detectors 83, 91 and 99 may be of the lead sulfide type. Each filter 79, 87 and 95 is selected so that it passes radiation in a separate band of the spectrum. Thus, radiation 42 enters the upper head 24 through detector aperture 37, but the optics in the upper head 22 split up the radiation 42 into five beams 57, 61, 77, 85 and 93, each of which is detected by an associated detector 71, 73, 83, 91 and 99.
The bandpass filters associated with each detector aperture 36 and 37 are preferably substantially similar. Thus, in one preferred embodiment, filter 62 is substantially similar to filter 63; filter 64 is similar to filter 65; filter 78 is similar to filter 79; filter 86 is similar to filter 87; and filter 94 is similar to filter 95.
FIG. 9 illustrates an alternative arrangement for source aperture 34 and detector apertures 36 and 37. Source aperture 34 and detector aperture 37 are formed in guide 28 and offset "A" from one another, while detector aperture 36 is formed in guide 30 and offset "B" from source aperture 34. The embodiment of FIG. 9 merely illustrates that detector apertures 36 and 37 can be in either guide 28 and/or 30 as long as their offset from the source aperture 34 is a different amount. As shown in FIG. 9, the guides 28 and 30 would include a quartz layer 120, 122 and 124 with a reflective backing (not shown) and a radiation absorbing medium 118.
The advantage of this arrangement is it reduces the dependence on the transmitted portion of the radiation reaching detector aperture 37 and thereby enhances its dependence on scattering. The ultimate advantage would be in the reduction of number of grade groups required to calibrate the sensor 32.
FIG. 4 illustrates the infrared transmission spectrum 101 of a light weight paper sheet, e.g., 70 grams/meter 2 (gsm), containing moisture, at a temperature of approximately 22° C. and of 60° C. The cross-hatched areas denoted MES, REF, CORR, CEL and SYN indicate the wavelength bands detected by measure detector 90, reference detector 98, temperature correction detector 70, cellulose detector 82 and synthetic detector 72 in upper head 24 (FIG. 2). Similarly, the cross-hatched areas MES, REF, CORR, CEL and SYN indicate the wavelength bands detected by measure detector 91, reference detector 99, temperature correction detector 71, cellulose detector 83 and synthetic detector 73 in the upper head 24.
To obtain the data for the infrared transmission spectrum 101, two plates of glass are placed on the opposing sides of a paper sheet and act to prevent loss of moisture during heating between the desired temperatures. The plates of glass serve not only to maintain constant moisture values during the measurements, but also to provide a thermal mass which maintains the paper sheet temperature to make possible measurements at temperatures above the ambient or at a lower temperature. To accomplish this, the glass-enclosed paper sheet is first heated, then measurements of the infrared transmission through the glass enclosing the paper sheet are made at the higher and lower temperatures.
The infrared absorption spectrum of water and paper is peculiar in that the absorption characteristics of the entire spectrum shift to shorter wavelengths as the paper sheet temperature is increased and to longer wavelengths as the paper sheet temperature decreases. As illustrated in FIG. 4, the infrared spectra of the light weight paper sheet at the higher temperature is shown by the dashed line 102. The infrared spectra at the lower temperature is shown by the solid line 104. Of course, the infrared spectrum 102 of the paper sheet at the higher temperature has approximately the same absorption characteristic as the lower temperature paper sheet, but at shorter wavelengths.
The infrared spectrum is affected by both the absorption by water and by paper fibers. In the band around 1.93 microns wavelength, water is much more efficient at absorbing infrared radiation than paper fibers. Thus, in this band of the spectrum the absorption is most strongly affected by the water content of the paper 18.
As shown in FIG. 4, for a light weight paper sheet (e.g., 70 gsm), an infrared band pass filter 86 (FIG. 2) associated with a measure detector 90 may have its pass band 112 approximately centered around the water absorption peak 106, for example, at approximately 1.93 microns. For this purpose, we may use a band pass filter 86 (FIG. 2) with a range from 1.92 to 1.95 microns, the lower and upper wavelengths at which the transmission reaches half that which is achieved at the transmission peak.
In this way, as the sheet temperature increases, the intensity of detected infrared radiation in the MES band increases at the long wavelength side of the band, while an approximately equal decrease in detected infrared radiation occurs at the opposite short wavelength side of the band. With this technique, the total amount of infrared radiation reaching the measure detector 90 is strongly sensitive to the moisture content and substantially insensitive to sheet temperature. Thus, the signal from measure detector 90 (the "MES" signal) provides a rough measurement of the sheet moisture content which is substantially insensitive to temperature change.
As mentioned earlier, the basis weight of the paper 18 also affects the infrared transmission spectrum. To provide a signal which is sensitive to the basis weight, as shown in FIG. 2, a band pass filter 94 is positioned before a reference detector 98. The filter 94 has its pass band 110 (FIG. 4) defining a REF band which is less sensitive to water and substantially insensitive to the sheet temperature. For example, a filter with a band pass range from 1.82 to 1.86 microns (normal incidence) has both of these characteristics. Because the pass band 110 of the filter is less than 1.9 microns, it is sensitive to the basis weight of paper 18. Accordingly, as the basis weight increases, the amount of infrared radiation passing through the sheet decreases. Thus, the signal from detector 98 (the "REF" signal) provides a rough measurement of the basis weight of the paper.
Because the MES and REF signals may be sensitive to the sheet temperature, the invention provides a temperature correction detector 70 (FIG. 2) for temperature correction with an associated band pass filter 62. The signal from this temperature correction detector 70 (the "CORR" signal) may be used to correct the measurement of the sensor 32 for the effects of varying sheet temperature as described below. The pass band 108 chosen for this filter 62 passes radiation in a band of the transmission spectrum 101 so that the amplitude of the signal from the temperature correction detector 70 is sensitive to changes in the sheet temperature. The changes in the CORR signal from the temperature correction detector 70 are used to compensate for temperature induced changes in the MES and/or REF signals.
A preferred position for the detected CORR band or pass band 108 of this filter is shown in FIG. 4. For example, a band pass filter of 1.68 to 1.72 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for light weight paper.
The invention may also provide a cellulose detector 82 (FIG. 2) with an associated band pass filter 78. The signal from this cellulose detector 82 (the "CEL" signal) may be used to correct the moisture measurement for varying cellulose content or to provide a measurement of the moisture content as a percentage of the total sheet weight. The pass band 114 chosen for this filter 78 passes radiation in a band of the transmission spectrum 101 that is sensitive to the cellulose content of the paper 18.
A preferred position for the detected CEL band or pass band 114 of this filter is shown in FIG. 4. For example, a band pass filter of 2.06 to 2.10 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for light weight paper.
The invention may also provide a synthetic detector 72 (FIG. 2) with an associated band pass filter 64. The signal from this synthetic detector 72 (the "SYN" signal) may be used to correct the moisture measurement for varying synthetic content. Although relatively less common in paper products, synthetic fibers (e.g., polyester fibers and polyethylene fiber) may be included in light weight paper products (e.g., tea bags) to strengthen the paper to avoid bursting when wet. The pass band 116 chosen for this filter 72 passes radiation in a band of the transmission spectrum 101 that is sensitive to the synthetic fiber content of the paper 18.
A preferred position for the detected SYN band or pass band 108 of this filter is shown in FIG. 4. For example, a band pass filter of 2.33 to 2.37 microns passes a band of the infrared spectrum where favorable synthetic detection has been achieved for light weight paper.
It is preferred that an identical set of band pass filters be arranged in like manner for detector aperture 37.
FIG. 5 illustrates the infrared transmission spectrum 101 for a medium weight paper sheet (e.g., a 205 gsm liner board), containing moisture at a temperature of approximately 22° C. and of 60° C. The infrared spectrum of the sheet at the higher temperature is shown by the dashed line 102. The infrared spectrum of the sheet at the lower temperature is shown by the solid line 104. To obtain the infrared spectrum, the paper sheet was sealed between two plates of glass to prevent loss of moisture during heating. Then measurements of the infrared penetration through the glass enclosed sheets were made at the higher and lower temperature. The cross-hatched areas denoted MES, REF, CORR and CEL again illustrate the separate wavelength bands to be passed through the respective filters and detected.
As mentioned earlier, a heavier weight paper product typically contains more moisture than a light weight paper. As the amount of moisture increases, the water absorption peak increases in magnitude as well as broadens in the wavelength direction. As illustrated by FIG. 5, both of these effects tend to reduce the amount of radiation transmitted through the sheet. In fact, at and around the water absorption peak, the strong water and cellulose absorptions of a heavier grades of paper may effectively absorb much of the infrared radiation directed at the sheet from the infrared source. Thus, the narrow band pass filter as used for the light weight paper discussed earlier may be entirely inadequate in terms of passing the required amount of radiation to the detector.
Rather than selecting such a narrow band pass filter to pass infrared radiation in a band adjacent to the water absorption peak, the invention overcomes the problem of relatively low transmission by providing a relatively broad band pass filter around the water absorption peak. This also minimizes temperature sensitivity by ensuring that the integrated areas beneath the infrared transmission spectrum for a wide range of temperatures remain roughly equal and that the water absorption peak remains within the filter envelope.
For this medium weight paper sheet, an infrared band pass filter 86 (FIG. 2) associated with the measure detector 90 may have its pass band 112 around the water absorption peak 106. For this purpose, we may use a band pass filter 86 (FIG. 2) with a range from 1.88 to 2.04 microns (at normal incidence).
In this way, as the sheet temperature increases, the absorption peak remains within the pass band 112, and the intensity of detected infrared radiation in the MES band increases at the long wavelength side of the band, while an approximately equal decrease in detected infrared radiation occurs at the opposite short wavelength side of the band. With this technique, the total amount of infrared radiation reaching the measure detector 90 is strongly sensitive to the moisture content and substantially insensitive to sheet temperature. This is because total amount of infrared radiation reaching the measure detector 90 is proportional to the integrated area underneath the transmission curve. Thus, the signal from measure detector 90 (the "MES" signal) provides a rough measurement of the sheet moisture content which is substantially temperature insensitive.
As previously mentioned, the infrared absorption spectrum is also affected by the basis weight of paper 18. To provide a signal dependent upon the basis weight of paper 18, a band pass filter 94 is positioned before a reference detector 98. As shown by FIG. 5, this filter 94 has its pass band 110 at a wavelength band which is less sensitive to water and substantially insensitive to the sheet temperature. For example, a band pass filter with a range from 1.82 to 1.86 microns (normal incidence) has both of these characteristics. Because the pass band 110 of this filter 94 is less than 1.9 microns, it is also sensitive to the basis weight of the paper 18. Accordingly, as the basis weight increases, the amount of infrared radiation which passes through paper 18 decreases Thus, the signal from this reference detector 98 (the "REF" signal) provides a rough measurement of the basis weight of the paper.
As in the measurement of the light weight paper, because the MES and REF signals may still be sensitive to the sheet temperature, the invention provides a temperature correction detector 70 (FIG. 2) for temperature correction with an associated infrared band pass filter 62. The signal from this temperature correction detector 70 (the "CORR" signal) may be used to correct the moisture measurement of the sensor 32 for the effects of varying sheet temperature. The pass band 108 chosen for this filter 62 passes radiation in a band of the transmission spectrum i so that the amplitude of the signal from the temperature correction detector 70 is sensitive to changes in the sheet temperature. The changes in the CORR signal from the temperature correction detector are used to compensate for the temperature induced changes in the MES signal.
A preferred position for the detected CORR band or pass band 108 of this filter is shown in FIG. 5. For example, a band pass filter of 1.68 to 1.72 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for medium weight paper.
The invention may also provide a cellulose detector 82 (FIG. 2) with an associated band pass filter 78. The signal from this cellulose detector 82 (the "CEL" signal) may be used to correct the moisture measurement for varying cellulose content. The pass band 114 chosen for this filter 78 passes radiation in a band of the transmission spectrum 101 that is sensitive to the cellulose content of the paper 18.
A preferred position for the detected CEL band or pass band 114 of this filter is shown in FIG. 5. For example, a band pass filter of 2.06 to 2.10 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for medium weight paper.
Again it is preferred that an identical set of band pass filters be arranged in like manner for detector aperture 37.
FIG. 6 illustrates the infrared transmission spectrum 101 for a heavy weight paper sheet (e.g., a 345 gsm liner board), containing moisture, at a temperature of approximately 22° C. and of 60° C. As in FIGS. 4-5, the infrared spectrum of the sheet at the higher temperature is shown by the dashed line 102. The infrared spectrum of the sheet at the lower temperature is again shown by the solid line 104. To obtain the infrared spectrum, the paper sheet was again sealed between two plates of glass to prevent loss of moisture during heating then measurements of the infrared penetration through the glass-enclosed sheets are made at the higher temperature and at the ambient or room temperature. The cross-hatched areas designated MES, REF, CORR, CEL and REF2 illustrate the separate wavelength bands to be passed through the respective filters and detected.
As mentioned earlier, a heavier grade of paper typically contains more moisture than a lighter weight paper. As the amount of moisture increases even more than that contained in a medium weight paper sheet, the water absorption peak increases in magnitude as well as broadens in the wavelength direction even more. As illustrated by FIG. 6, both of these effects tend to further reduce the amount of radiation transmitted through the sheet. In fact, around the water absorption peak, the strong water and cellulose absorptions of the heavier grades of paper absorb much of the infrared radiation directed at the sheet from the infrared source. Thus, a narrow band pass filter as specified for the light weight paper, or even the broader band pass filter specified for the medium weight paper may be inadequate to pass the required amount of radiation to the detector.
The invention overcomes the problem of relatively low transmission by providing an even broader band pass filter around the water absorption peak than in the situations illustrated in FIGS. 4 and 5. This also reduces temperature sensitivity by ensuring the water absorption peak remains within the filter envelope.
For this heavy weight paper sheet, an infrared band pass filter 86 (FIG. 2) associated with the measure detector 90 may have its pass band 112 around the water absorption peak 106. For this purpose, we may use a band pass filter 86 (FIG. 2) with a range from 1.88 to 2.04 microns (at normal incidence).
In this way, as the sheet temperature increases the peak remains within the pass band, and the intensity of the infrared radiation increases on the long wavelength half of the filter 86, while a decrease in the intensity of the infrared radiation occurs at the opposite short wavelength half of the filter 86. However, this technique does not result in temperature insensitivity, because the total amount of infrared radiation reaching the measure detector 90 may not be substantially equal for the high and low temperatures. Thus, the measurement detector 90 is not only strongly dependent upon the moisture content of the paper 18, but may also be sensitive to the sheet temperature. Thus, the signal from measure detector 90 (the "MES" signal) provides a moisture measurement which may be temperature sensitive.
The infrared absorption spectrum is affected by the basis weight of the paper 18. To provide a signal sensitive to the basis weight of the paper 18, a band pass filter 94 is positioned before a reference detector 98. To compensate for any temperature sensitivity of the MES signal, the filter 94 has its pass band 110 defining a REF band which is less sensitive to the water in the sheet than the MES band surrounding the water absorption peak, but is sensitive to the sheet temperature For example, a filter with a band pass range from 1.82 to 1.86 microns (normal incidence) has these characteristics. Because the pass band 110 of this filter 94 is less than 1.9 microns, it is also sensitive to the basis weight of the paper 18. Accordingly, as the basis weight increases, the amount of infrared radiation which passes through the paper 18 decreases. Thus, the signal from this detector 98 (the "REF" signal) provides a rough measurement of the basis weight of the paper.
Because the MES and REF signals may be sensitive to the sheet temperature, the invention provides a temperature correction detector 70 (FIG. 2) for temperature correction with an associated band pass filter 62. The signal from this temperature correction detector 70 (the "CORR" signal) may be used to correct the moisture measurement of the sensor 32 for the effects of varying sheet temperature. The pass band 108 chosen for this filter 62 passes radiation in a band of the transmission spectrum 101 so that the amplitude of the signal from the temperature correction detector 70 is sensitive to changes in the sheet temperature. The changes in the CORR signal from the temperature correction detector are used to compensate for the temperature induced changes in the MES signal.
A preferred position for the detected CORR band or pass band 108 of this filter is shown in FIG. 6. For example, a band pass filter of 1.68 to 1.72 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for medium weight paper.
The invention may also provide a cellulose detector 82 (FIG. 2) with an associated band pass filter 78. The signal from this cellulose detector 82 (the "CEL" signal) may be used to correct the moisture measurement for varying cellulose content. The pass band 114 chosen for this filter 78 passes radiation in a band of the transmission spectrum 101 that is sensitive to the cellulose content of the paper 18.
A preferred position for the detected CEL band or pass band 114 of this filter is shown in FIG. 6. For example, a band pass filter of 1.47 to 1.53 microns passes a band of the infrared spectrum where favorable temperature correction has been achieved for heavy weight paper.
Finally, the invention may also provide a second reference detector with an associated band pass filter. Although the second reference detector is not shown in FIG. 2, the second reference detector and associated filter could be disposed at the same physical location as the synthetic detector 72 and filter 78. The REF2 band or pass band 126 chosen for this filter passes radiation in a band of the transmission spectrum 101 that is less sensitive to the cellulose than the cellulose detector 82. Thus, the cellulose reference detector serves as a reference.
A preferred position for the REF2 band or pass band 126 of this filter is shown in FIG. 6. For example, a band pass filter of 1.30 to 1.34 microns passes a band of the infrared spectrum where favorable results have been achieved for heavy weight paper.
It is preferred that an identical set of band pass filters be arranged in like manner for detector aperture 37.
Table 1 gives the appropriate band pass filters for basis weights of up to 550 gsm. Band pass ranges are expressed as the lower and upper wavelengths at which the transmission reaches half that which is achieved at the transmission peak.
TABLE 1__________________________________________________________________________Maximum SYN/REF2Basis MES Filter REF Filter CORR Filter CEL Filter FilterWeight microns microns microns microns micronsgsm lower upper lower upper lower upper lower upper lower upper__________________________________________________________________________ 70 1.92 1.95 1.82 1.86 1.68 1.72 2.06 2.10 2.33 2.37150 1.90 2.01 1.78 1.82 1.68 1.72 2.06 2.10 -- --250 1.88 2.04 1.82 1.86 1.68 1.72 2.06 2.10 -- --325 1.87 2.05 1.82 1.86 1.68 1.72 1.47 1.53 1.30 1.34550 1.84 2.03 1.82 1.86 1.68 1.72 1.47 1.53 1.30 1.34__________________________________________________________________________
The "Maximum Basis Weight" column specifies the maximum basis weight in gsm of the paper product for which the filter set should be used. The maximum water weight is approximately no more than 10% for each grade of paper product. Thus, for a particular context, the customer specifies the maximum basis weight and the maximum percent moisture for the paper being manufactured and the appropriate filter sets are then selected from Table 1 which satisfy both of these conditions.
As shown in FIG. 2, the infrared radiation from lamp 38 is modulated by the tines 44 of the vibrating tuning fork 46. For the sake of simplicity the modulating of the radiation 42 is explained for detector aperture 36 alone. However, the same arrangement is also preferred for the detector aperture 37. The output of each detector 70, 72, 82, 90 and 98 is sinusoidally modulated at the same frequency and phase as the detected infrared beams 56, 60, 76, 84 and 92. However, infrared radiation from paper 18 itself and from other external sources (not shown) will also reach the detectors. Thus, each detector signal also includes a DC component.
The output of each of the five detectors 70, 72, 82, 90 and 98 is transmitted to the signal processing circuitry 45. The circuitry 45 is designed to filter out the DC component of the detector signals. The filtered detector signals are then passed on to a phase synchronous demodulation circuit included within the signal processing circuitry 45. The purpose of the phase synchronous demodulator is to filter out changes in the signals from the detectors 70, 72, 82, 90 and 98 which are not caused by the varying infrared absorption of the paper 18. For example, 60 Hz line noise in the detector signals is filtered out by the demodulator circuit, as explained below.
A sine wave oscillator 43 drives the tines 44 of tuning fork 46 at its resonant frequency. The output of this oscillator 43 is converted to a square wave with the same frequency and phase as the sine waves driving the tuning fork 46. This square wave output 41 is fed to a phase synchronous demodulator portion of the signal processing circuitry 45, along with the filtered signals from each of the five detectors 70, 72, 82, 90 and 98. Of course, the filtered signals are modulated at the same frequency and phase as the output of oscillator 43. By demodulating the outputs from each of the detectors 70, 72, 82, 90 and 98 with a square wave having the same frequency and phase as the output of the oscillator 43 and averaging the demodulated outputs over a number of cycles, the sensor 32 filters out detector signals changes from changes in the intensity of external infrared sources or extraneous signals such as the 60 Hz line voltage. This filtering technique using a phase synchronized demodulation circuit is known. This reduces erroneous moisture measurements. The output signal of each detector indicates the intensity of radiation 42 passing through the associated band pass filter.
The invention provides a graph as shown in FIG. 8 from a mathematical analysis for determining the scattering and absorption power of diffuse media such as paper. The scattering and absorption powers are determined to be a function of the intensity of the detected radiation at both detector apertures of the moisture sensor. The following analysis depends in part on the Kubelka-Munk theory. This theory describes the behavior of light interacting with diffuse media such as paper and provides a mathematical analysis for determining the amount of light transmitted through and reflected from the paper. W. Wendlandt and H. Hecht, Reflectance Spectroscopy, Chapter 111 (1966) provides a description of the Kubelka-Munk theory and is incorporated herein by reference.
As shown in FIG. 7, the technique is best illustrated by an example which involves two parallel planes, S and P. It will be assumed that the planes act as Lambertian surfaces, that is, they are perfect diffusers of radiation and follow Lambert's law:
I(Φ)=I.sub.o cos(Φ)
where:
Φ=the angle from the normal to the surface and the direction of light leaving the surface
I(Φ)=the intensity of light per unit solid angle leaving the surface in the direction
I o =the intensity of light per unit solid angle leaving the surface in the normal direction.
It also will be assumed that a radiation source is in plane S and is distributed symmetrically about an axis normal to the surfaces of planes and centered in the middle of the illuminated area of plane. Finally, it will be assumed that the sheet being measured acts as a diffusing material such as paper and has the reflection and transmission properties described by the theory of Kubelka and Munk.
The first step in the analysis is to determine the distribution of light incident on the surface of the parallel sheet facing the source from light coming from the source plane. The process used is that for every point on the parallel sheet, the total intensity of light reaching it from every point on the source plane is calculated.
FIG. 7 shows the two parallel planes, S and P. Consider an element of area da, at a point on the S plane located at radial distance r s and at angle θ s from the Y axis. The intensity of light per unit area per unit solid angle leaving normal to that surface at that point is given to be i s (r s ) (watts/cm 2 *sr). The total light intensity reaching an element of area da p on plane P at r p and θ p from da, is given by:
d.sup.2 F(r.sub.p,r.sub.s,θ.sub.s,θ.sub.p,Φ)=i.sub.s (r.sub.s) cos(Φ) da.sub.s (da.sub.p cos(Φ)/r.sup.2) (watts)
where r is the distance between da s and da p . The first cos(Φ) term on the right is from applying Lambert's law. The term in parentheses on the right is the solid angle subtended by da p . The angle Φ is between the normal to the planes and a line drawn between da s and da p . The intensity per unit area incident on da p from da s is:
df(r.sub.p,r.sub.s,θ.sub.s,θ.sub.p,Φ)=i.sub.s (r.sub.s) da.sub.s (cos.sup.2 (Φ)/r.sup.2) (watts/cm.sup.2)
The value of cos(Φ) be written in terms of the separation between planes (1) and r:
cos(Φ)=l/r
The intensity per unit area becomes:
df(r.sub.p,r.sub.s,θ.sub.s,θ.sub.p,Φ)=i.sub.s (r.sub.s) da.sub.s (l.sup.2 /r.sup.4) (watts/cm.sup.2)
The value of r can be written in terms of the position variables r p , r s , θ s and θ p :
r=sqrt(l.sup.2 +r.sub.s.sup.2 +r.sub.p.sup.2 -2r.sub.s r.sub.p cos(θ.sub.x -θ.sub.p))
The incremental area da s can also be written in terms of the position variables r s and θ s .
da.sub.s =r.sub.s dr.sub.s dθ.sub.s
Combining we have the intensity per unit area in terms of position variables only:
df(r.sub.p,r.sub.s,θ.sub.s,θ.sub.p,Φ)=i.sub.s (r.sub.s) r.sub.s l.sup.2 dr.sub.s dθ.sub.s /(l.sup.2 +r.sub.s.sup.2 +r.sub.p.sup.2 -2r.sub.s r.sub.p cos(θ.sub.s -θ.sub.p)).sup.4 (watts/cm.sup.2)
To obtain the total intensity per unit area on elemental area da p on plane P from the entire surface of plane S, the equation above must be integrated over the entire surface from r s =0 to r s =r smax , the maximum radius of plane S and θ s =0 to 2π: ##EQU1##
This integral is best solved by a numerical method. One suitable method is the trapezoidal method. To obtain the distribution of incident intensity on plane P, the integral must be solved at all positions of r p and θ p .
If plane P represents a sheet of diffusing material between two planes, S and T (not shown), the distribution of incident light on plane P can be used to calculate the intensity of the reflected and transmitted light. If the sheet is paper, the theory of Kubelka-Munk provides an accurate way to calculate the reflected and transmitted light when the absorption and scattering coefficients are known. The transmission calculated from Kubelka-Munk theory multiplied by the incident light distribution on plane P is now a source distribution to plane T. Similarly, the reflection calculated from Kubelka-Munk theory multiplied by the incident light distribution on plane P is now a source distribution back to the plane S.
The same method is used again to determine the distribution of incident light on plane T. The incident light distribution on plane T is reflected back, becoming a source distribution of light which impinges on the back side of plane P. This light is reflected and transmitted by plane P as described above. The light thus transmitted adds to the light that was incident from plane S and is reflected back from plane P. This forms a new distribution of light that is now incident on the plane S.
The new distribution of light on plane S is the incident light from plane P reflected back plus the original illuminated area. With this new source distribution the calculations are repeated to find new distributions on all planes. After several iterations there will be no change, that is the results will have converged to a final value and additional iterations of the calculations will not produce different results.
Once the light distribution is known for planes S and T, the calculated light intensity can be determined for a detector placed anywhere on plane S or on plane T. Two positions have been analyzed in detail, but the same approach would work for any position. The positions analyzed are where: (1) the detector is
on plane T and offset from the illuminated area; and (2) the detector is on plane T and aligned with the source of light or the illuminated area. The former is referred to as an offset transmission detector and the latter as a straight-through transmission detector.
Up to this point we have shown that if the absorption and scattering coefficients of the sheet are known the intensity distribution of light on all planes can be calculated. In actual operation, a sensor would be set up to measure the intensity at two or more detector locations and then absorption and scattering coefficient would be determined. To implement this technique, the intensity distributions are calculated for all values of absorption and scattering coefficients likely to be encountered.
FIG. 8 illustrates a graph of the absorption and scattering powers of a paper sheet plotted as a function of the intensity of radiation individually detected at an offset transmission detector and a straight-through transmission detector. The ordinate of the graph is determined by calculating an intensity ratio from the offset transmission detector located on plane T. The abscissa is determined by calculating an intensity ratio from the straight-through transmission detector located on plane T. The intensity ratio for both detectors is defined as the intensity with no sheet of material between plane S and T to the intensity when the sheet of material is interposed therebetween. Contour lines connect equal absorption powers and equal scattering powers associated with those ratios.
To use a graph as illustrated in FIG. 8 the sheet to be measured is placed between the planes S and T. The intensity of a select signal, such as the MES signal, is measured by the detectors at the two locations. Next, the intensity is determined when there is no sheet interposed between planes S and T. The intensity ratio, that is, the intensity with no sheet in interposed divided by intensity with the sheet interposed is then calculated. The intensity ratios are then used to find the absorption and scattering powers of the sheet. Of course, by interpolating between the contour lines of equal absorption powers and equal scattering powers the actual value of absorption and scattering coefficients can be determined.
Two approaches can be used to correct temperature error in the absorption measurements. Under the first approach, we can assume that the temperature dependent part of the absorption coefficient can be separated:
k.sub.i (T)=k.sub.io f.sub.i (T) (1)
where T=temperature; f i (T) is a function that depends on temperature alone; and and k io =absorption coefficient of signal i at the calibration temperature.
We can also assume that the temperature function for any signal is a linear function of the temperature function of the correction signal:
f.sub.i (T)=αf.sub.corr (T)+β (2)
By combining (1) and (2) we have ##EQU2## Then for each signal the corrected absorption coefficient is: ##EQU3## and α i and β i would be determined experimentally.
A second approach to removing temperature error is to correct the ratios before determining the absorption coefficients. For each wavelength we have signal taken with no sheet at Standardize, REFS, and a signal on-sheet, REF. We then calculate a ratio for that wavelength:
RREF=REFS/REF,
RMES=MESS/MES,
RCEL=CELS/CEL, and
RCORR=CORRS/CORR.
Calculate a Temperature Correction Ratio: ##EQU4## Coefficients C1, C2 and C3 are chosen so that RT is approximately zero at calibration temperature. Use this value to correct the signal for each wavelenght:
RREFcor=RREF*(1+C4*RT),
RMEScor=RMES*(1+C5*RT), and
RCELcor=RCEL*(1+C6*RT).
Once the absorption coefficients are known for the moisture and reference wavelengths the moisture calculation is straight forward. For the simple case of plain paper with no fillers or broad band absorbers:
k=k.sub.water *%MOI/100+k.sub.fiber *(1-%MOI/100)
where
k=absorption coefficient of paper at 1.94 microns determined by the process described above
k water =absorption coefficient of water a known constant
k=absorption coefficient of fiber a known constant
%MOI=percent moisture in paper
solving for %MOI
%MOI=(k-k.sub.fiber)*100/(k.sub.water -k.sub.fiber)=ak+b
where a is a constant equal to 100/(k water -k fiber ) and is in a constant equal to k fiber *a
Thus, in principle a single wavelength is sufficient to determine moisture in the simplest case.
In the more realistic case where broad band absorbers are present then two wavelengths are required:
kmes=kmes.sub.water *%MOI/100+kmes.sub.fiber *(1-%MOI/100)+kmes.sub.bb *bbwt
and
kref=kref.sub.water *%MOI/100+kref.sub.fiber *(1-%MOI/100)+kref.sub.bb *bbwt
where
kmes=absorption coefficient of paper at 1.94 micron
kmes water =absorption coefficient of water at 1.94 micron
kmes fiber =absorption coefficient of fiber at 1.94 micron
kmes=absorption coefficient of broad band absorber at 1.94 micron
kref=absorption coefficient of paper at 1.8 micron
kref water =absorption coefficient of water at 1.8 micron
kref fiber =absorption coefficient of fiber at 1.8 micron
kref bb =absorption coefficient of broad band absorber at 1.8 micron
bbwt=broad band absorber basis weight
Since the absorption coefficients of the broad band absorber at the mes and ref wavelengths are the same, the difference between kmes and kref give the moisture without the effect of broadband absorption: ##EQU5## where dk=kmes-kref;
a=100/(dk water -di fiber ); and
b=-dk fiber -a
Sometimes a better approximation is obtained by using a polynomial of dk where
%MOI=adk+b(dk).sup.2 +C
Based on these measurements, a sheet moisture correction can be accomplished manually. However, many modern paper mills are highly automated. In these paper mills, the signals produced by the sensor 32 are preferably fed to a computer 47 which computes the sheet moisture profile using the signals from the detectors and then, based on this computation, selectively activates one or more known devices 49 for altering the moisture content of certain portions of the paper 18. Many such devices 49 for altering the sheet moisture profile exist, including such devices as selectively controllable water showers for increasing the moisture content of select cross-directional sections of paper 18 and/or infrared heaters for selectively drying such sections of paper 18. | A sensor and method is provided for measuring one or more select components of a material. In one embodiment, a method measures the components by emitting electromagnetic radiation at the material and detecting the intensity of the emerging radiation at separate locations from the source. In another embodiment, a sensor provides a radiation source for emitting radiation at a sheet, a plurality of detecting means, wherein at least one detecting means is offset from the source, for detecting radiation after interaction with the sheet and first and second reflectors for directing the radiation so that the radiation makes multiple interactions with the sheet when moving from the source to the detecting means. The invention can accurately measure the select components (e.g., moisture) of different grades of paper by eliminating the effects of the scattering power and determining absorption power at each band of the spectrum considered necessary for a particular measurement. | 3 |
CLAIM OF PRIORITY
[0001] The present application is a continuation of U.S. patent application Ser. No. 11/675,049 entitled “LIGHT WEIGHT, STRONG, FIRE RETARDANT DUNNAGE PLATFORM BAG AND SYSTEM OF LOADING, DISPENSING AND USING BAG,” inventors Seagle et al., filed Feb. 14, 2007, which claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 60/773,454 entitled “LIGHT WEIGHT, STRONG, FIRE RETARDANT DUNNAGE PLATFORM BAG AND SYSTEM OF LOADING, DISPENSING AND USING BAG,” inventors Seagle, et al., filed Feb. 15, 2006; Application No. 60/817,868 entitled “FREIGHT FORWARDING SYSTEM,” inventors Seagle, et al., filed Jun. 30, 2006; and Application No. 60/817,989 entitled “SYSTEM FOR RETAINING LEGS ON A LIGHT WEIGHT THERMOPLASTIC DUNNAGE PLATFORM AND INSTALLING MOLDED LEGS ON A DUNNAGE PLATFORM DECK,” inventor Vance L. Seagle, filed Jun. 30, 2006. These applications are herein expressly incorporated by reference in their entireties.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0002] This application is related to the following applications:
[0003] U.S. Utility patent application Ser. No. 11/672,863, entitled “MODULAR, KNOCK-DOWN, LIGHT WEIGHT, THERMALLY INSULATING, TAMPER PROOF SHIPPING CONTAINER AND FIRE RETARDANT SHIPPING BAG,” inventors Seagle, et al., filed Feb. 8, 2007; and
[0004] U.S. Utility patent application Ser. No. 12/569,655, entitled “LIGHT WEIGHT, STRONG, FIRE RETARDANT DUNNAGE PLATFORM BAG AND SYSTEM OF LOADING, DISPENSING AND USING BAG,” inventor Vance L. Seagle, filed Sep. 29, 2009, which applications are herein expressly incorporated by reference in their entireties.
FIELD OF THE INVENTION
[0005] This invention is in the general field of a dunnage platform bag that is light weight, strong and made of a fire retardant material. The dunnage platform bag can accommodate a modified dunnage platform assembled from a dunnage platform base and legs attached to the base. The dunnage platform bag can form an ultra violet light, weather and dust barrier to protect the integrity of the dunnage platforms when not in use. A system and method for supplying, dispensing, positioning, tracking, transporting, forwarding and storing dunnage platforms based on the dunnage platforms bag is disclosed.
BACKGROUND OF THE INVENTION
[0006] The adoption of International Standardized Phytosanitary Monitoring (ISPM)-15 for wood packaging material (WPM) requires kiln dry treatment of all wood used in shipping crates and dunnage platforms (pallets). The United States in cooperation with Mexico and Canada began enforcement of the ISPM 15 standard on Sep. 16, 2005. The North American Plant Protection Organization (NAPPO) strategy for enhanced enforcement will be conducted in three phases. Phase 1, Sep. 16, 2005 through Jan. 31, 2006, call for the implementation of an informed compliance via account managers and notices posted in connection with cargo that contains noncompliant WPM. Phase 2, Feb. 1, 2006 through Jul. 4, 2006, calls for rejection of violative crates and pallets through re-exportation from North America. Informed compliance via account managers and notices posted in cargo with other types of non-compliant WPM continues to remain enforce. Phase 3, Jul. 5, 2006, involves full enforcement on all articles of regulated WPM entering North America. Non-compliant regulated WPM will not be allowed to enter the United States. The adoption of ISPM-15 reflects the growing concern among nations about wood shipping products enabling the importation of wood-boring insects, including the Asian Long horned Beetle, the Asian Cerambycid Beetle, the Pine Wood Nematode, the Pine Wilt Nematode and the Anoplophora Glapripwnnis.
[0007] Thus the wooden dunnage platform has become unattractive for the international shipment of products. Further, the wooden surface is not sanitary since it potentially can harbor in addition to insects, mould and bacteria. Thus, the wooden crate is generally ill-suited for the shipment of foodstuffs and other produce requiring sanitary conditions.
[0008] Plastic dunnage platforms or pallets are known, see U.S. Pat. No. 3,915,089 to Nania, and U.S. Pat. No. 6,216,608 to Woods et al., which are herein incorporated by reference in their entirety. Plastic pallet manufacturing techniques typically involve injection molding, which significantly increases the cost of the plastic pallets. In order to justify this initial investment cost of the plastic pallet, the pallet must be extensively re-used. Thus, while the plastic surface of the plastic pallet obviates some of the sanitary problems with wood pallets, because of the required repetitive use the surface can become unsanitary. As a consequence when used for the shipment of foodstuffs and other produce requiring sanitary conditions, the high cost of the plastic pallet requires that the plastic surface be cleaned and kept clean prior to use.
[0009] Some wood pallet manufacturers have attempted to produce a more sanitary surface by combining foam with wooden surfaces. These dunnage platforms still suffer a number of disadvantages including their weight, the presence of wood requiring kiln treatment and the possibility of the foam being stripped away to expose the wood surface.
[0010] Thermoplastic molded dunnage platforms are known. U.S. Pat. No. 5,833,796 to Dummett, which is herein incorporated by reference in its entirety, which discloses applying thermoplastic sheets to a preformed rigid structure for manufacturing dunnage platforms.
[0011] Irrespective of the material used to make the dunnage platform sanitary, there remains a problem in the field of keeping sanitary dunnage platforms clean while they are being stored or otherwise not in use.
[0012] Further, irrespective of whether the dunnage platforms are made of wood, plastic, foam or thermoplastic, they are a source of fuel for a fire and thus represent a fire hazard. Storage of dunnage platforms after unloading, either inside or outside the delivery location increases the risk of a significant fire. Flame retardant materials are known, however, they have not been successfully incorporated into dunnage platform construction materials. Thus there is a need for a sanitary dunnage platform suitable for transporting foodstuffs, which is light, cheap and does not present a fire hazard. Since materials being shipped can also represent a fire hazard, while somewhat beneficial, it is not essential that the dunnage platform per se be fire resistant. However, there is a need for a method of storing, loading, dispensing and shipping empty sanitary dunnage platforms, which are light, inexpensive and not a fire hazard.
[0013] Optiledge™ feet are lightweight, strong, phytosanitary, molded feet in an L-shape designed to attach to the bottom of a crate or shipping unit and which can act as a transport device. Optiledge™ can in some circumstances be used as an alternative to a wood pallet for loading and shipping units. When the product to be shipped contains a deck, Optiledge™ can be made integral to the packaged product and can act as a pallet during the storage and distribution of the packaged product. Optiledge™ or any similar device is not appropriate when the unit load does not include a deck surface onto which the Optiledge™ type device can be mounted
SUMMARY OF THE INVENTION
[0014] In one embodiment of the invention, a dunnage platform bag is disclosed that is light weight, strong, made of a fire retardant material and which forms an ultra violet light, weather and dust particle barrier to protect the integrity of the dunnage platforms when not in use. In addition, a system and method for loading, storing, dispensing, positioning, tracking, and transporting empty dunnage platforms based on the dunnage platform bag is disclosed.
[0015] In an alternative embodiment of the present invention, a dunnage platform with damaged feet is modified such that the feet can be removed and replacement feet can be attached. In an embodiment of the present invention, the damaged feet of a dunnage platform can be removed and Optiledge™ feet can be attached to the dunnage platform deck. In another embodiment of the invention, a dunnage platform deck with stubs is manufactured and molded feet are press fitted into the stubs or otherwise attached to the dunnage platform deck. In various embodiments of the invention, the modified dunnage platforms can be loaded into the dunnage platform bag.
[0016] This summary is not intended to be a complete description of, or limit the scope of, the invention. Other embodiments of methods for manufacturing a dunnage platform and repairing the legs of damaged dunnage platforms, within the spirit and scope of the invention, can be understood by a person having ordinary skill in the art. Alternative and additional features, aspects, and objects of the invention can be obtained from a review of the specification, the figures, and the claims.
BRIEF DESCRIPTION OF THE FIGURES
[0017] FIG. 1 shows the dunnage platform bag (length, 1027 mm (50 inches)×width, 1067 mm (42 inches)×height, 30.5 m (120 inches)) holding 22 dunnage platforms (each of dimension 1219 mm (48 inches)×1016 mm (40 inches)×139 mm (5.5 inches)) prior to stretching and hanging, where the zippered bag is opened for manual insertion, removal or inspection of the dunnage platforms;
[0018] FIG. 2 shows the dunnage platform bag lying on a level surface holding a dunnage platform, at one end, and two zippers open for manual insertion, removal and inspection;
[0019] FIG. 3 shows a Computer Assisted Drawing (CAD) perspective of the dunnage platform bag attached to a base frame;
[0020] FIG. 4 shows CAD of (A) a front and (B) a side perspective of the dunnage platform bag attached to a base frame;
[0021] FIG. 5 shows (A) a CAD perspective of the dunnage platform bag attached to the transport base frame shows and (B) a close-up of the dunnage platform bag method of attachment to the transport base frame;
[0022] FIG. 6 shows a CAD drawing of the dunnage platform stop lever (A) external and (B) internal to the transport base frame;
[0023] FIG. 7 shows a CAD drawing of the dispensing base frame where (A) the transport base frame wheels are positioned and (B) the gear mechanism, trigger strikers and dunnage platform release handle for dispensing;
[0024] FIG. 8(A-D) shows a CAD drawing showing the guide wheels used for dispensing the dunnage platforms in different orientations;
[0025] FIG. 9(A-C) show CAD drawings of the gear and chain used to drive the guide wheels shown in FIG. 11 ;
[0026] FIG. 10(A-C) show CAD drawings of the dispensing base frame with the transport base frame wheels showing the position of the trigger strikers in different orientations;
[0027] FIG. 11 show CAD aerial projections of the reloading base frame and the lifting bar used to force the dunnage platform up into the dunnage platform bag;
[0028] FIGS. 12(A and B) show a CAD drawing of a side view of the reloading base frame with the tension link in different orientations;
[0029] FIG. 13 shows a CAD drawing of the sprocket and ratchet used to hold the dunnage platform in place once it is lifted;
[0030] FIG. 14(A-D) show CAD drawings of a dunnage platform bag being loaded onto a dispensing base frame in different orientations;
[0031] FIG. 15(A-E) show CAD drawings of an empty dunnage platform bag being folded onto its dispensing base frame in different orientations;
[0032] FIG. 16 shows a pair of inverted Optiledge™ high density polyethylene legs suitable for attachment onto a thermoplastic dunnage platform deck;
[0033] FIG. 17 shows the bottom side of a thermoplastic dunnage platform deck with stub-leg inserts attached;
[0034] FIG. 18 shows a side view of the Optiledge™ high density polyethylene legs attached to a thermoplastic dunnage platform deck;
[0035] FIG. 19 shows the edge of the Optiledge™ high density polyethylene legs abutting the edge of the thermoplastic dunnage platform deck; and
[0036] FIG. 20 shows a frontal view of the Optiledge™ high-density polyethylene legs attached to a thermoplastic dunnage platform deck.
DETAILED DESCRIPTION OF THE INVENTION
[0037] In one embodiment of the invention, a manufacturer makes a commitment to an airfreight cargo forwarder of a cargo lift volume contract in return for supply of thermoplastic dunnage platforms to resolve ISPM-15 issues and other advantages such as cargo safety, human safety, convenience and resolving fire risk issues involved with storage of flammable dunnage platforms. Client agrees to pay shipping freight cost as would be incurred with wood pallets. In return the manufacturer makes a commitment of sufficient thermoplastic dunnage platforms for shipping the cargo. The airfreight cargo forwarder who assigns manufacturing capacity to clients requires a balancing commitment from the client of a cargo lift volume contract. The airfreight cargo forwarder saves between 17 and 33% of the total freight cost of shipping the cargo (after subtracting the cost of the thermoplastic dunnage platforms), while solving clients ISPM-15 concerns.
[0038] In an embodiment of the invention, a dunnage platform manufacturer (hereinafter ‘manufacture’), shipping forwarder (hereinafter ‘forwarder’) and manufacturer with cargo to ship (hereinafter ‘client’) co-operate to ship a client's cargo without ISPM-15 concerns at a reduced cargo freight cost, thereby producing a useful concrete and tangible result. In another embodiment of the present invention, the manufacturer ships the thermoplastic dunnage platforms in a fire retardant bag which the client can use to hang and store the dunnage platforms thereby saving space while eliminating a fire hazard and thereby producing a useful concrete and tangible result. In an alternative embodiment of the present invention, the manufacture supplies dunnage platforms with RFID tags thereby allowing the forwarder to track the shipment while en route thereby producing a useful concrete and tangible result.
[0039] Forwarders to provide dunnage platforms to their clients free of charge in exchange for retaining the financial benefit of weight savings, while giving their clients: (1) improved convenience, (2) cost of not having to buy pallets, (3) eliminating ISPM-15 issues, (4) improving cargo safety (5) improving human safety and (6) gaining greater contracted cargo volume from clients.
[0040] Manufacturer production facilities are: (1) remarkably portable and inexpensive, (2) easily deployed anywhere, and (3) able to produce up to 15,000 pallets per month. Factories can be readily placed in forwarders' market regions to service their local clients. No other competitive pallet production can match this scalability and the manufacturer manufacturing process is fully patented.
[0041] Each forwarder can secure exclusive “Agency” rights for a port or market region and pre-sell the full monthly production allocation of 15,000 pallets (per manufacturer machine) by consigning them free of charge to strategic clients in exchange for cargo lift volume contracts. When the first allocation is gone, pre-sale of a second unit can begin until the major market clients can be fully sold on a first-option basis. This strategy removes all risks from the program rollout. Clients can be selected based on optimum profiles for cargo destinations, freight costs, type of cargo, size and importance of client and overall value of service the program provides to forwarder and client.
[0042] Revenues to forwarder can be calculated on a cargo weight savings basis of 40 pounds per pallet and pallet costs can be paid to manufacturer from those savings, leaving the cash balance to the forwarder. At $1 per pound, each pallet can yield $15 cash profit ($225,000 month) to the forwarder. At $0.75 pound, it can produce $75,000 per month, especially considering surcharges alone are reaching as much as $0.80 per pound in some markets. The forwarder can have no cash risk, as manufacturer is paid $25 per pallet from the saving stream (following collection of client's invoices) and the remainder is held by the forwarder. The only investment of the forwarder is the cost of sales efforts to pre-sell the cargo region.
[0043] In one embodiment of the invention, the dunnage platform bag is a modular, lightweight, strong, ultra violet light insulating, fire resistant, tamper proof receptacle for storing, reloading, dispensing, tracking and transporting dunnage platforms. FIGS. 1 and 2 depict an embodiment of the dunnage platform bag invention in which the dunnage platform bag is 30.5 m (120 inches)×1.27 m (50 inches)×1.07 m (42 inches) and weighs 3.2 kg (7 lb). In another embodiment, the dunnage platform bag includes a spreader and base. In other embodiments the dimension of the dunnage platform bag will vary depending on the dimension of the dunnage platform to be stored in the bag. In one embodiment of the invention, the dunnage platform bag consists of four sides a top and a bottom sewn together. In one embodiment of the invention, two parallel zippers separated by between approximately 52-78 mm (20-30 inches) can each sewn into one side of the bag and located on that side approximately 13 mm (5 inches) down from top of the bag and approximately 10 m (40 inches) from the bottom of the bag. In this invention, it will be understood by persons having skill in the art that the use of the term ‘approximately’ when used together with dimensions that indicate a preferred range can vary by up to 50% of the preferred range. In another embodiment of the invention, the zippers extend the full length of the bag. In another embodiment, a cord string is attached to the two zippers to enable both zippers to be opened or close simultaneously. In an alternative embodiment, Velcro™ is used to reseal one or more openings in the dunnage platform bag. In another embodiment, one or more re-sealable openings can be used for inserting, removing or inspecting the plurality of dunnage platforms.
[0044] FIG. 1 , shows the dunnage platform bag holding 22 dunnage platforms (of dimension 1219 mm (48 inches)×1016 mm (40 inches)×139 mm (5.5 inches)) prior to stretching and hanging. FIGS. 1 and 2 show that the dunnage platform bag material is sufficiently strong to allow handling of the fully loaded dunnage platform bag.
[0045] In one embodiment of the invention, the material of the bag is strong enough to allow the bag to be hoisted and the dunnage platform bag and transport base left hanging for dispensing. In an embodiment, of the invention thermoplastic molded dunnage platforms can be loaded in the dunnage platform bag. In an embodiment of the invention, the thermoplastic dunnage platforms have RFID tags inserted into the core prior to coating the core with the thermoplastic layer. A RFID reader mounted in the base or the spreader can then read the RFID tags in the individual dunnage platforms. In an alternative embodiment of the invention, plastic dunnage platforms can be loaded in the dunnage platform bag. In another embodiment, cargo loaded on one or more dunnage platforms can be inserted into the dunnage platform bag. In various embodiments, sufficiently strong material can be used and the seams can be strengthened to compensate for the additional weight of the plastic dunnage platforms or the cargo.
[0046] FIG. 1 shows that the dunnage platform bag holding twenty-two dunnage platforms remains stable when the zippered bag is opened for manual insertion, removal or inspection of the dunnage platforms. FIG. 2 shows the dunnage platform bag lying length wise on a surface holding a dunnage platform and two zippers open for manual insertion, removal and inspection of the dunnage platforms.
[0047] FIG. 3 shows a perspective of the dunnage platform bag 300 attached to a transport base frame total height 3.267 m (128 11/16 inches). In an embodiment of the invention, the dunnage platform bag 320 has a top and four sides, where the four sides can be attached to a transport base, which forms the bottom side. In an embodiment of the invention, the transport base frame 350 has a flange attached to the inside of the frame which abuts the lowest dunnage platform (i.e., the dunnage platform in contact with the dunnage platform stop trigger 910 ) so as to seal the bottom of the dunnage platform bag. The flange is flexible enough to allow the dunnage platforms to be dispensed or reloaded while retaining sufficient rigidity to form a seal between the transport base frame 650 and the undercarriage or sides of the lowest dunnage platform in the stack of dunnage platforms loaded in the bag. In various embodiments of the invention, the flange can be made of flexible rubber or plastic.
[0048] In FIG. 3 , a spreader plate 310 has dimensions slightly larger than the length and width of the bag 320 to which it is attached through load binders 330 . In an embodiment of the invention, a hook 340 with plate submerged into the spreader plate 310 is used to hold the bag 320 upright. In an embodiment of the invention, the bag is sealed at the top. A spreader plate and/or a hook is also referred to herein as a bracket attached to the dunnage platform bag, wherein the bracket can be used for lifting the dunnage platform bag.
[0049] In an embodiment of the invention, the bag 320 fits into a transport base frame or base 350 , with dimensions 1435 mm (56 9/16 inches)×1101 mm (43⅜ inches) with four wheels attached at the four corners of the transport base frame. In one embodiment of the invention, the wheels can be fixed in an orientation where their axis of rotation is perpendicular to the length of the base frame, which allows the base to be rolled in the direction of its longitudinal axis. In another embodiment of the invention, the wheels can be fixed in an orientation where their axis of rotation is perpendicular to the width of the base frame, which allows the base to be rolled perpendicular to the direction of its longitudinal axis. In an alternative embodiment of the invention, two or more wheels are not fixed in an orientation or are able to swivel, allowing greater flexibility in the direction in which the base can be rolled. In one embodiment of the invention, the base has two wheels attached at two corners and two supports at the other two corners, which enable the bag to be tilted and the base and bag to be wheeled about on the two wheels.
[0050] In one embodiment of the invention, the transport base frame can be used to dispense dunnage platforms. FIG. 4 shows (A) a side and (B) a front view of the dunnage platform bag 420 attached to a base frame 450 . In the embodiment shown in FIG. 4 , wheels 460 can be positioned at each of the four corners. The front view shows the base plate 480 submerged beneath the spreader plate 410 , held in place by the load binders 330 and the hook 440 . In this embodiment of the invention, the distance between the dunnage platform and the floor is 11 mm ( 7/16 inch). In an alternative embodiment of the invention, the base frame can be raised above the floor allowing the dunnage platform to be dispensed from beneath the transport base frame.
[0051] FIG. 5 shows (A) a perspective of the dunnage platform bag attached to a transport base frame and (B) a close-up cross section of the dunnage platform bag fastening to a transport base frame. FIG. 5A shows two of the four dunnage platform stop triggers 590 which can be positioned on either side of, and 250 mm from the front and 250 mm from the rear of the (1101 mm width side) of the transport base frame. Dunnage platform stop triggers are also referred to herein as dunnage platform stops. Dunnage platform stop triggers are also referred to herein individually or collectively as an indexing mechanism. The bag 510 is secured to the frame with the rope 530 sewn into the lower edge of the bag 510 , which is drawn under the pipe frame 505 and secured with rope pegs 520 . Dunnage platform stop trigger 590 holds the pallet in place. In FIG. 5B , the base frame is made of ‘C’ cross-section steel frame 580 to which each wheel 560 is attached through a socket shoulder screw 565 . The bottom of the bag 510 is sewn or otherwise attached to rope pegs 520 , which can be passed through rope 530 , attached to the pipe frame 505 and the frame 580 . A dunnage platform stop 590 mounted inside a 12 mm ‘C’ section frame holds the dunnage platform 570 in place and impedes it from being dispensed. A trigger 506 holds the dunnage platform stop 590 in place. When the trigger is released the dunnage platform stop 590 completely retracts into the ‘C-section. In another embodiment of the invention, the bag 510 is secured to the pipe frame 505 by a clamping mechanism secured to the pipe frame where the clamping mechanism is able to clamp onto the bag material.
[0052] FIG. 6 shows a perspective of the transport base frame. FIG. 6A shows one embodiment of the invention where the dunnage platform stop 690 pivots on Teflon glacier bushes 691 and is restrained by a return spring 692 . The dunnage platform stop lever swings on the axel bolt 693 to release a dunnage platform. FIG. 6B shows the dunnage platform stop 690 , which holds the dunnage platforms in place (see also FIG. 9 for triggering through the dispensing base). FIG. 7 shows a perspective of the dispensing base frame 700 . FIG. 7A shows the dispensing base mouth 785 where the transport base frame inserts into the dispensing base. The ‘L’ cross section steel (angle iron) 786 hold the wheels of the transport base above the exit cavity 787 where the dispensed dunnage platform can be retrieved. In this embodiment of the invention, the wheels can be mounted perpendicular to the width of the transport base and the wheels enter the mouth 785 and can be held in place by the ‘L’ section brackets. FIG. 7B shows the dispensing base 700 with the isolator drive 775 , isolator wheels 776 , trigger strikers 777 , lever axel 778 , exit cavity 787 and dunnage platform release handle 779 . In alternative embodiments of the invention, rather than a motor, a ratchet of other mechanical system is used to drive the isolator wheels.
[0053] FIG. 8 shows a side view of the dunnage platform bag attached to a transport base frame and inserted in a dispenser base frame. FIG. 8A shows guide wheels 865 and 866 used for dispensing the dunnage platforms 870 . Rectangular hollow tube is welded into a star configuration to form the guide wheels. The left hand side (LHS) 865 guide wheel turns clockwise while the right hand side (RHS) guide wheel 866 , turns anticlockwise. Both the LHS 865 and the RHS guide wheels 866 can be chain guided in order to synchronize the motion. The guide wheels will tolerate 19 mm or ¾ inch variation in position of the dunnage platforms 870 . FIG. 8B shows the guide wheels 865 and 866 after approximately a 50° rotation. The same dunnage platform 870 is still held by the guide wheels but the dunnage platform is lower and the next arm of the star is starting to turn into position to retain the next dunnage platform. FIG. 8C shows the guide wheels 865 and 866 after an additional approximately 30° rotation, where the dunnage platform 870 is about to be released by the guide wheels and the next arm of the star is in position to retain the next dunnage platform. FIG. 8D shows the guide wheels 865 and 866 after an additional approximately 10° rotation, where the dunnage platform 870 is released and the next arm of the star is holding the next dunnage platform.
[0054] FIG. 9 shows a perspective of one embodiment of the invention where the dunnage platform bag attached to a transport base frame and inserted in a dispenser base frame. FIG. 9A shows the gear 946 and chain 945 used to drive the guide wheels. In one embodiment of the invention a motor is used to turn the spigot 947 and drive the gears and thereby the chain to deliver a dunnage platform. In another embodiment, a ratchet can be used to turn the spigot. The guide wheels can be mounted on only one side of the dispensing base frame 900 . FIG. 9B shows the trigger activation mechanism (see also FIG. 7B ). In the base release position, the striker pivots 944 , attached to the slide rail 941 can be moved via a linkage 943 , connected to a pivot arm 942 and the striker pivots can be retracted away from the dunnage platform stop strikers to allow withdrawal of the dunnage platform bag and transport base from the dispenser. The striker pivots 944 when not in the base release position (see FIG. 9C ) can engage the dunnage platform stop triggers (see 590 FIG. 5A ). As the linkage 943 moves, the slide rail 941 and the striker pivots 944 move toward the direction of the lever 942 axel (see also 778 FIG. 7B ). When the release handle is upright, the dunnage platform stop trigger 590 holds the dunnage platforms from dropping down. Pulling downward on the dunnage platform release handle 779 turns the lever 942 which swings the linkage 943 bringing the striker pivots in contact with the triggers 590 thereby releasing the next dunnage platform. FIG. 10 shows an overhead view of the dunnage platform bag attached to a transport base frame and inserted in a dispenser base frame. FIG. 10A shows the strikers 1048 in the retracted position to allow clearance for the dunnage platform bag and transport base to be loaded or removed. The strikers 1048 , attach to the slide rail 1041 can be moved via a linkage 1043 , connected to a pivot arm 1042 . FIG. 10B shows the strikers 1048 in the perpendicular position when the dunnage platform release handle is in the upright position and the strikers 1048 are rotated into a position ready to contact the striker release triggers 1090 . FIG. 10C shows the strikers 1048 contacting the striker release triggers 1090 when the dunnage platform release handle is lowered.
[0055] In one embodiment of the invention, the dunnage platforms can be re-loaded using a reloading base 1100 . In one embodiment of the invention, the reloading base frame 1100 is identical in dimension to the dispensing base frame (see 700 FIG. 7 ). FIG. 11 shows an aerial projection of the reloading base frame 1100 and the lifting bar 1135 , which is used to force the dunnage platform up into the bag. FIG. 12 shows a side view of the reloading base frame 1200 , where the lifting bar 1235 is connected by a compression link 1225 , a lever 1226 with a pivot point 1227 , and a tension link 1228 to a crank wheel 1229 driven by a motor 1224 . The motor 1224 turns the crank wheel 1229 , which is coupled via a universal joint to the tension link 1228 which traces out a circular trajectory, driving the lever 1226 up and thereby the lifting bar down for loading a dunnage platform onto the lifting bar ( FIG. 12A ). The dunnage platform 1270 is accepted into the space shown in the reloading base frame 1205 without the need for the lifting bar 1235 to drop lower than shown in FIG. 12A as the middle section of the lifting bar 1235 accepts the middle leg of the dunnage platform. Continuing the elliptical trajectory of the tension link 1228 mounted at the crank 1229 , the lever 1226 is driven down and thereby the compression link 1225 forces the lifting bar 1235 up. FIG. 12B shows the lifting bar connected to a linear slide 1223 with linear bearings and two linear bushes 1222 to give stability and keep the motion vertical, thereby evenly raising the inserted dunnage platform 1270 back into the bag. FIG. 13 shows that the dunnage platform once it is lifted into place is held by a one-way sprocket and ratchet 1315 . In an alternative embodiment a foot pedal can raise the lifting bar. In an alternative embodiment, pneumatic air pressure can be used to drive a lever to raise the lifting bar. In an alternative embodiment a jack can supply mechanical energy to raise the lifting bar.
[0056] In an embodiment of the invention, the bag attached to the transport base can be loaded onto the dispensing base 700 . In another embodiment of the invention, the bag attached to the transport base can be loaded onto the reloading base 1100 . In another embodiment of the invention, the bag attached to the transport base can be loaded onto the combined dispensing base and reloading base. FIG. 14 shows a diagram of the bag 1420 attached to the transport base being raised with a hoist 1416 and spring 1418 attached to a boom pipe 1417 onto the dispensing base 1400 . FIG. 14A shows the bag 1420 and transport base tilted and leaning on the dispensing base 1400 so that the spring tensioning connection 1418 can be attached to the hook. FIG. 14B shows the bag and transport base after it has been hoisted off the ground and still leaning on the dispensing base 1400 . FIG. 14C shows the bag and transport base after hoisting where the wheel 1460 of the transport base is aligned with the mouth of the dispensing base 1400 . FIG. 14D shows the bag and transport base after the wheels 1460 roll the bag and transport base into the dispensing base 1400 .
[0057] In an embodiment of the invention, the bag 1520 can be angle folded onto itself to pack the bag for storage when not in use. FIG. 15 shows the angle bag folding method. FIG. 15A shows the erect empty bag 1520 and hook 1540 attached to the transport base 1550 with wheels 1560 . FIG. 15B shows the first fold of the erect empty bag and transport base 1500 . FIG. 15C shows the next step in the folding of the erect empty bag and transport base 1500 . FIG. 15D shows the second fold of the erect empty bag and transport base 1500 , where the hook 1540 is passed through a hole in the bag. FIG. 15E shows the next step in the folding of the erect empty bag and transport base 1500 , where the empty bag 1520 is pulled tight, the spreader plate can be attached to the transport base frame using clips or straps and the hook 1540 is available for lifting the packed bag and transport base 1500 . In an alternative embodiment of the invention, the bag is folded concertina style. In another embodiment of the invention, drawstrings can be used to assist the folding of the bag.
[0058] In an alternative embodiment of the invention, the base frame allows dunnage platform dispensing and dunnage platform loading.
[0059] In one embodiment of the invention, the bag is made of one or more materials selected from the group consisting of Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE) and polypropylene (PP). In another embodiment of the invention, the bag is made of flame retardant material. In an embodiment of the invention, the bag is made from polyethylene, aromatic bromine and antimony trioxide. In one embodiment of the invention, the bag is made of one or more of the following materials: LDPE, HDPE and PP and treated with ARX 501 FR 05 LD. In an embodiment of the invention, the bag meets standards DIN 4102 B2, DIN 4102 B1 and CEE. In a further embodiment of the invention, the bromine additive is heat stable up to 350° C.
[0060] In an embodiment of the present invention, the damaged feet of a dunnage platform can be removed and molded feet can be attached to the legless dunnage platform deck. Optiledge™ feet have been designed to be integral with the deck of cargo and then the deck, cargo and Optiledge™ feet can be strapped together. FIG. 16 shows a pair of Optiledge™ feet. When a dunnage platform is damaged, all the feet can be removed using a band saw or other suitable cutting device to remove the damaged feet thereby generating a thermoplastic dunnage platform deck. In an embodiment of the present invention, leg stubs can be attached to the thermoplastic dunnage platform deck. The leg stubs in the dunnage platform base can be generated by cutting up damaged thermoplastic dunnage platforms. In an alternative embodiment, the leg stubs can be affixed to the thermoplastic dunnage platform deck using molding. The leg stubs can also be attached using other means of adhering or affixing. Once affixed to the thermoplastic dunnage platform deck the leg stubs appear as shown in FIG. 17 . The leg stubs can be used to locate a lightweight, strong, phytosanitary, molded feet in an L-shape designed to attach to the bottom of a deck. In an embodiment of the present invention the leg stubs can be used to attach to Optiledge™ feet. By applying suitable force the molded (Optiledge™) feet can be press fitted into the leg stubs. Once affixed the thermoplastic dunnage platform deck appears as shown in FIGS. 18-20 . Shown in FIG. 19 , the L shaped section of the Optiledge™ feet is abutting the edge of the thermoplastic dunnage platform deck. In FIGS. 16 and 19 the ‘L’ shaped molded feet can be made up of a first and a second member, which can be joined to form the ‘L’ shape. The hollow feet extend from one of the first or second members. The hollow feet can be press fitted into the leg stubs shown in FIG. 17 .
[0061] Alternatively, a third leg can be added in between the two molded feet to provide additional support for the thermoplastic dunnage platform deck and cargo. By using molded feet without the L shaped retainer (or by removing the L-shaped section of the Optiledge™ feet), the molded feet can be applied to a flat surface. By affixing leg stubs in the center of the thermoplastic dunnage platform deck, and placing leg stubs in the center position an additional set of legs can be placed at any position under the deck.
[0062] In an alternative embodiment of the present invention, a thermoplastic dunnage platform with one or more damaged feet can be modified such that one or more of the damaged feet can be removed and one or more replacement feet can be attached in the location of the removed feet.
[0063] In an embodiment of the present invention, thermoplastic dunnage platforms in which the feet have been damaged can be collected at a point of destination shipping location. The feet of the thermoplastic dunnage platforms can be removed and the thermoplastic dunnage platforms decks can be stored in a flame retardant bag. Once the bag is filled the bag with the thermoplastic dunnage platforms decks can be shipped to a desired point of origin shipping location. Separately, or together molded feet can be shipped to the same location. Alternatively, the damaged thermoplastic dunnage platforms can be shipped to a desired point of origin shipping location and the legs can be removed at this location. Also at this location, one or more stub feet can be affixed to the thermoplastic dunnage platform deck and the molded feet can be affixed by press fitting into the stub legs. Alternative means of assembling molded feet onto the thermoplastic dunnage platform deck can be envisaged by one of ordinary skill in the art. Cargo can then be loaded on the assembled thermoplastic dunnage platforms with molded feet, strapped and shipped to the desired location.
[0064] In another embodiment of the invention, a Radio Frequency IDentification (RFID) tag is imbedded in one or more of: the spreader 310 , the transporter base frame 350 , the dispenser base 700 , the reloading base 1100 and the material of the four walls 320 . In one embodiment of the invention, the RFID tag operates using an Ultra High Frequency (UHF) signal. In another embodiment of the invention, the RFID tag operates using a microwave frequency signal.
[0065] In an embodiment of the present invention, a RFID tags can be inserted into the exposed polystyrene core after the damaged legs have been removed and prior to affixing the stub legs. In an embodiment of the present invention, a RFID reader mounted in the bag used to collect the thermoplastic dunnage platform decks can then read the RFID tags in the individual dunnage platforms. In an embodiment of the invention, the RFID reader in the bag and the RFID tag in the thermoplastic dunnage platform decks can be positioned so that the RFID tag antenna is least affected by any conducting material in the dunnage platform legs or dunnage platform bag.
[0066] In one embodiment, the RFID tag is centered in the middle of the spreader, the transporter base, the dispenser base, the reloading base and the material of the four walls. In another embodiment, the RFID tag is placed on the edge of the spreader, the transporter base, the dispenser base, the reloading base and the material of the four walls. In an embodiment of the invention, the RFID tag can be positioned so that the RFID tag antenna is least affected by the metal in the dunnage platform bag and base.
[0067] In one embodiment the RFID tag is read only. In another embodiment, the RFID tag contains an Electrically Erasable Programmable Read-Only Memory (EPROM), which enables both read and write functions. In an embodiment of the invention, the RFID tag is passive. In another embodiment of the invention, the RFID tag is semi passive containing a source of energy such as a battery to allow the tag to be constantly powered. In a further embodiment of the invention, the RFID tag is active, containing an internal power source, such as a battery, which is used to power any Integrated Circuits (ICs) in the tag and generate the outgoing signal. In another embodiment, the tag has the ability to enable location sensing through a photo sensor.
[0068] In an embodiment of the invention, the cargo and each dunnage platform contain a passive RFID tag and each dunnage platform bag contains an active RFID tag and RFID tag reader. Each dunnage platform bag is able to monitor the cargo and the dunnage platforms loaded in the dunnage platform bag. In a shipment, one or more master dunnage platform bag contains an RFID tag reader which is able to monitor all the other dunnage platform bags in the vicinity of the master dunnage platform bag. The master dunnage platform is then able to relay the position and condition of the entire shipment to a base station.
[0069] In one embodiment of the invention, means of communication with a base station is imbedded in the dunnage platform bag in one or more of the spreader, the transporter base, the dispenser base, the reloading base and the material of the four walls. In an alternative embodiment of the invention, one or more dunnage platforms loaded in the dunnage platform bag contain the apparatus to communicate with the base station in order to relay the condition and global position of the cargo.
[0070] In one embodiment of the invention, the communication means utilizes one or more of a wireless local area network; a wireless wide area network; a cellular network; a satellite network; a Wi-Fi network; and a pager network. In one embodiment of the invention, the device embedded is a modem capable of communicating with one or more of the aforementioned networks. In the following discussion the term ‘cellular modem’ will be used to describe the device embedded. The term ‘cellular modem’ will be herein used to identify any device of comparable size capable of communicating over one or more of the aforementioned networks. In one embodiment of the invention, the cellular modem can be a Code Division Multiple Access (CDMA) modem. In an embodiment of the invention, a RFID reader and associate integrated circuit processor can be embedded together with the cellular modem in the spreader, the transporter base, the dispenser base, the reloading base and the material of the four walls. In such an embodiment, the RFID tags and RFID reader can be positioned to optimize the RFID read of the RFID tags from the other surfaces, which make up the dunnage platform bag.
[0071] In an embodiment of the invention, where a RFID reader and a cellular modem can be embedded in one or more of the spreader, the transporter base, the dispenser base, the reloading base and the material of the four walls; the RFID reader is in communication with one or more RFID readers, associated cellular modems and the RFID tags of one or more dunnage platform bags in the vicinity of the RFID reader. Through communications with the RFID reader and associated integrated circuit processor of the plurality of dunnage platform bags in the vicinity, a RFID reader and associated integrated circuit processor is able to distinguish the RFID tag from dunnage platforms loaded in the bag and dunnage platforms loaded in dunnage platform bags in the vicinity based on one or more of location, strength of signal, variation of RFID tag signal with position in the dunnage platform bag relative to the reader, variation of RFID tag signal with time and prior input data. In an embodiment of the invention, one or more antenna inserted into the material of the bag can be used to help discriminate the location of the dunnage platforms loaded in a dunnage platform bag. In an embodiment of the invention, the RFID reader and associate processor can be in communication with the embedded cellular modem. In an embodiment of the invention, the cellular modem is in communication with a base station and can transmit one or more parameters selected from the group consisting of one or more RFID tag location, one or more RFID tag identification code, number of dunnage platforms loaded in the bag, dunnage platform bag information, previous shipment information, dunnage platform condition, dunnage platform bag condition and time stamp.
[0072] In one embodiment of the invention the RFID code uses the IEEE format and is Electronic Product Code (EPC) readable. In another embodiment of the invention the RFID code uses the UCC format and is Universal Product Code (UPC) readable. In another embodiment, the format is compatible for EPC, European Article Number (EAN) and UPC read and write functions.
[0073] Various embodiments can be implemented using a conventional general purpose or specialized digital computer(s) and/or processor(s) programmed according to the teachings of the present disclosure, as will be apparent to those skilled in the computer art. Appropriate software coding can readily be prepared by skilled programmers based on the teachings of the present disclosure, as will be apparent to those skilled in the software art. The invention can also be implemented by the preparation of integrated circuits and/or by interconnecting an appropriate network of component circuits, as will be readily apparent to those skilled in the art.
[0074] Various embodiments include a computer program product which is a storage medium (media) having instructions and/or information stored thereon/in which can be used to program a general purpose or specialized computing processor(s)/device(s) to perform any of the features presented herein. The storage medium can include, but is not limited to, one or more of the following: any type of physical media including floppy disks, optical discs, DVDs, CD-ROMs, micro drives, magneto-optical disks, holographic storage devices, ROMs, RAMs, EPROMs, EEPROMs, DRAMs, PRAMS, VRAMs, flash memory devices, magnetic or optical cards, nano-systems (including molecular memory ICs); paper or paper-based media; and any type of media or device suitable for storing instructions and/or information. Various embodiments include a computer program product that can be transmitted in whole or in parts and over one or more public and/or private networks wherein the transmission includes instructions and/or information, which can be used by one or more processors to perform any of the features, presented herein. In various embodiments, the transmission can include a plurality of separate transmissions.
[0075] Stored on one or more of the computer readable medium (media), the present disclosure includes software for controlling both the hardware of general purpose/specialized computer(s) and/or processor(s), and for enabling the computer(s) and/or processor(s) to interact with a human user or other mechanism utilizing the results of the present invention. Such software can include, but is not limited to, device drivers, operating systems, execution environments/containers, user interfaces and applications.
[0076] The execution of code can be direct or indirect. The code can include compiled, interpreted and other types of languages. Unless otherwise limited by claim language, the execution and/or transmission of code and/or code segments for a function can include invocations or calls to other software or devices, local or remote, to do the function. The invocations or calls can include invocations or calls to library modules, device drivers and remote software to do the function. The invocations or calls can include invocations or calls in distributed and client/server systems. | The present invention provides a dunnage platform bag that is light weight, strong, made of a fire retardant material and which forms an ultra violet light, weather and dust particle barrier to protect the integrity of the dunnage platforms when not in use. A system and method for supplying, dispensing, positioning, tracking, transporting, forwarding and storing dunnage platforms based on the dunnage platforms bag is disclosed. In an embodiment of the invention, a modified dunnage platform made up of a dunnage platform base and attached legs can be stored in the dunnage platform bag. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a cleaner such as a carpet cleaning device having a powered brush assembly. More particularly, the present application pertains to such a brush assembly that can be easily removed from the nozzle of a carpet extractor.
[0003] 2. Background Information
[0004] It is known in the prior art to provide a carpet extractor having powered brushes to assist in scrubbing of the surface being cleaned. The brush assembly is generally affixed to the main body of the carpet extractor. However, after many times of use, a user may want to remove the brush assembly to clean the brushes or replace them due to the wear and tear of their bristles.
[0005] One example of a brush removal device is illustrated by commonly owned U.S. Pat. No. 6,009,593 issued to Crouser. This patent generally comprises an elongate brush support beam having integrally molded, spaced apart, vertically aligned cylindrical bearings each receiving therein a vertically directed axle shaft of an associated rotary scrubbing brush. The brush assembly has outwardly projecting resilient tangs 51 depending from the lower end of gear guard 32 A. Each tab snaps into vertically elongated grooves or slots 53 and 57 respectively of lower housing in the base module 10 of the carpet extractor. Each tab has hook portions at its free end that will engage the bottom end of the vertical slot to support the guard and brush support beam. The resilient tabs are pressed inwardly by a user to disengage the hooks from the bottom end of the vertical slot and thus, allow removal of the brush block. However, due to the structure and arrangement of the tangs with respect to the brush block, a user has some difficulty in accessing, grasping, and pressing the tabs inwardly. Often, a tool such as a screwdriver has to used by the user to press the tabs inwardly.
[0006] Hence, it is an object of the present invention to provide a brush block having a device that allows it to be easily removed by a user from the cleaner, carpet extractor, or the like.
[0007] It is another object of the present invention to provide a simple inexpensive removal device for a brush block of a cleaner, carpet extractor, or the like.
SUMMARY OF THE INVENTION
[0008] The foregoing and other objects of the present invention will be readily apparent from the following description and the attached drawings. In one embodiment of the present invention a cleaner for cleaning a surface is provided comprising a main body and a brush assembly for engaging the surface being cleaned. An engaging member on either the main body or brush assembly and a retaining portion on the other main body or brush assembly. The engaging member and retaining portion are releasably connected to each other such that either the engaging member or retaining portion is accessible for engagement by a user to disengage the engaging member from the retaining portion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The invention will now be described, by way of example, with reference to the attached drawings, of which:
[0010] [0010]FIG. 1 is a left side elevational view of the base module of an upright cleaner having the forward portion thereof cut away to illustrate the general positioning of the brush assembly therein according to the present invention;
[0011] [0011]FIG. 2 is a top perspective view of the brush assembly according to the present invention;
[0012] [0012]FIG. 3 is a perspective view of the forward portion of the base module illustrated in FIG. 1, having the top cover portion being removed; and
[0013] [0013]FIG. 4 is a sectional view as taken along line 4 - 4 in FIG. 3 with the brushes removed and the base module being lifted off the surface.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] In one embodiment of the present invention, a base module 10 for an upright carpet extractor is shown in FIG. 1. The base module is similar to the one found in previously mentioned co-owned U.S. Pat. No. 6,009,593. In general, a base module 10 comprises a lower housing 12 and an upper housing 14 which generally separate along parting line 13 . A suction nozzle 16 and a suction inlet 18 are part of the upper housing 14 similar to that taught in the above referenced co-owned patent. A floating carpet scrubbing brush assembly 20 is suspended in the lower housing 12 . As depicted in FIG. 3, the brush assembly 20 may be powered by an air driven turbine 15 , or any suitable motive power means typically used in the industry, through a suitable gear drive train or transmission 54 .
[0015] As shown in FIG. 2, the brush assembly 20 comprises a brush support beam 22 having five spaced apart integrally molded, cylindrical bearings 24 A, 24 B, 24 C, 24 D, and 24 E. Rotatingly received within bearings are axial shafts (not shown but illustrated in previously mentioned U.S. Pat. No. 6,009,593; the disclosure of which is incorporated herein by reference) of gear brushes 25 A, 25 B, 25 C, 25 D, and 25 E. The beam 22 further includes troughs 71 A, 71 B, 71 C, 71 D, and 71 E, for receiving a cleaning solution. The cleaning solution flows through supply conduits 74 A, 74 B, 74 C, 74 D, and 74 E, of the beam and then outward toward the surface being cleaned through openings in the bottom of brush cups (not shown but also illustrated in U.S. Pat. No. 6,009,593). Gear guards 32 A and 32 B are attached to the brush support beam 22 and are identical in construction so as to be interchangeable on either side of brush support beam 22 . A gear brush rotation indicator 44 is fixedly attached to shaft extension 29 (FIG. 5 of U.S. Pat. No. 6,009,593) of gear brush 25 E.
[0016] Integral to and extending upward from the opposite lateral ends of brush support beam are “T” shaped rails 42 and 43 . As best seen in FIG. 3, T-rails 42 and 43 are slidably received within vertical guide slots 46 and 47 integrally molded into the lower base modular housing 12 whereby brush assembly 20 may freely move or float in the vertical direction within the brush assembly cavity 48 of housing 12 . As also shown in FIG. 3, gear brush rotation indicator 44 extends upward through opening 56 in the top 45 of brush cavity 48 of lower housing 12 .
[0017] Referring to FIG. 4, to facilitate “snap together” assembly of each of the gear guards 32 A, 32 B to the brush support beam 22 , each of the gear guards 32 A and 32 B is provided with three integrally formed, horizontally extending, locking tabs 34 extending parallel to and below the top cover plates 36 A and 36 B of gear guards 32 A and 32 B. Further, each gear guard ( 32 A and 32 B) is provided guide and alignment openings 38 (FIG. 2) for receipt therein (upon assembling the brush assembly) of extended tabs 39 of brush support beam 22 . As the gear guards are brought together about brush support beam 22 , tangs 34 , on both gear guards 32 A and 32 B, slide under extended tabs 39 , of brush support beam 22 , engaging slots 41 (FIG. 5 of U.S. Pat. No. 6,009,593) thereby locking gear guards 32 A and 32 B to brush support beam 22 .
[0018] A plurality of downwardly projecting tangs 151 extend from the top cover plates 36 A and 36 B of gear guards 32 A and 32 B, respectively as best seen in FIGS. 2 and 4. These figures illustrate that the tangs 151 are attached to the top cover plates 36 A and 36 B of gear guards 32 A and 32 B. However, it should be noted that the tangs 151 can be integrally formed with the top cover plates 36 A and 36 B of gear guards 32 A and 32 B. Each of the tangs 151 has one end 93 attached to the top cover plate 36 A or 36 B and the other end 95 extending freely. Each of the tangs 151 has a hook portion 91 located approximately midway between its ends, dividing the tang 151 into an upper portion 153 and a lower portion 155 .
[0019] As depicted in FIG. 2, grooves 154 are formed in the side of the gear guards 32 A, 32 B directly across from the tangs 51 to provide more area for the tangs 151 to be flexed inwardly. A ledge 157 is provided on the bottom edge of each groove 154 .
[0020] Referring to FIG. 4, as brush assembly 20 is inserted into cavity 48 , the tangs 151 on gear guards 32 A and 32 B snap into vertically elongated grooves or slots 53 and 57 , respectively, of housing 12 . The tangs 151 projecting from gear guard 32 A slidingly engage vertical slots 53 of housing 12 and tangs 151 projecting from gear guard 32 B slidingly engage slots 57 thereby floatingly retaining brush assembly 20 within cavity 48 . A lower limit of brush assembly 20 , as illustrated in FIG. 4, is controlled by the hook portions 91 of the tangs 151 which engage the bottom ledges 49 and 50 of slots 53 , 57 . Each hook portion 91 is located a distance from the free end 95 of the tang 151 to allow sufficient room between the hook portion 91 and free end 95 of the tang 151 for engagement by a user to flex the tang 151 inwardly, as shown by the phantom lines, and disengage the hook portion 91 from the bottom ledges 49 , 50 of the slots 53 , 57 . The upper travel of brush assembly 20 is limited by abutment of the brush assembly 20 against the top portion 45 of cavity 48 as illustrated in FIG. 1.
[0021] To remove the brush assembly 20 from the cavity 48 illustrated in FIG. 4, a user (not shown) first grasps the brush assembly 20 with his hands such that the thumb is placed on the lower portion 155 of a tang 151 of gear guard 32 A and a finger is placed on the lower portion 155 of the tang 151 of gear guard 32 B. The user then flexes the tangs 151 inwardly to move them a sufficient distance to disengage the hook portions 91 from the bottom ledges 49 , 50 of the slots 53 , 57 as illustrated by the phantom lines of FIG. 4. The brush assembly 20 can then be pulled out of the cavity 48 .
[0022] Because the tangs 151 are pressed near their free ends, the tangs require less force to move or flex them inwardly to remove them from the bottom ledges 49 , 50 of slots 53 , 57 , respectively, than that of the tangs of previously mentioned U.S. Pat. No. 6,009,593.
[0023] The present invention has been described by way of example using the illustrated embodiment. Upon reviewing the detailed description and the appended drawings, various modifications and variations of the preferred embodiment will become apparent to one of ordinary skill in the art. All such obvious modification and variations are intended to be included in the scope of the present invention and of the claims appended hereto. For example, the tangs 151 could be attached to the lower housing 12 of the base module 10 and the slots 53 , 57 could be formed in the gear guards 32 A and 32 B.
[0024] In view of the above, it is intended that the present invention not be limited by the preceding disclosure of a preferred embodiment, but rather be limited only by the appended claims. | A cleaner for cleaning a surface is provided comprising a main body and a brush assembly for engaging the surface being cleaned. An engaging member on the main body or brush assembly and a retaining portion on the other main body or brush assembly. The engaging member and retaining portion are releasably connected to each other such that the engaging member or retaining portion is accessible for engagement by a user to disengage the engaging member from the retaining portion. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to a method for producing a manganese oxide octahedral molecular sieve (OMS). More particularly, this invention relates to a method for producing a manganese oxide octahedral molecular sieve which is carried out in an open system, e.g., under refluxing conditions.
Manganese oxide octahedral molecular sieves (OMS) possessing mono-directional tunnel structures constitute a family of molecular sieves wherein chains of MnO 6 octahedra share edges to form tunnel structures of varying sizes. Such materials have been detected in samples of terrestrial origin and are also found in manganese nodules recovered from the ocean floor. Manganese nodules have been described as useful catalysts in the oxidation of carbon monoxide, methane and butane (U.S. Pat. No. 3,214,236), the reduction of nitric oxide with ammonia (Atmospheric Environment, Vol. 6, p.309 (1972)) and the demetallation of topped crude in the presence of hydrogen (Ind. Eng. Chem. Proc. Dev., Vol. 13, p.315 (1974)).
Pyrolusite, β-MnO 2 , is a naturally occurring manganese oxide characterized by single chains of MnO 6 octahedra which share edges to form (1×1) tunnel structures which are about 2.3 Å square. Ramsdellite, MnO 2 , is a naturally-occurring manganese oxide characterized by single and double chains of MnO 6 octahedra which share edges to form (2×1) tunnel structures which are about 4.6 Å by about 2.3 Å square. Nsutite, γ-MnO 2 , is a naturally-occurring manganese oxide characterized by an intergrowth of pyrolusite-like and ramsdellite-like tunnel structures. Pyrolusite, ramsdellite and nsutite do not possess cations in their tunnel structures.
The hollandites are naturally occurring hydrous manganese oxides with tunnel structures (also described as "framework hydrates") in which Mn can be present as Mn+ 4 and other oxidation states, the tunnels can vary in size and configuration and various mono- or divalent cations can be present in the tunnels. The hollandite structure consists of double chains of MnO 6 octahedra which share edges to form (2×2) tunnel structures. The average size of these tunnels is about 4.6 Å square. Ba, K, Na and Pb ions are present in the tunnels and coordinated to the oxygens of the double chains. The identity of the tunnel cations determines the mineral species. Specific hollandite species include hollandite (BaMn 8 O 16 ), cryptomelane (KMn 8 O 16 ), manjiroite (NaMn 8 O 16 ) and coronadite (PbMn 8 O 16 ).
The hydrothermal method of synthesizing a manganese oxide octahedral molecular sieve possessing (2×2) tunnel structures such as those possessed by the naturally-occurring hollandites is described in "Hydrothermal Synthesis of Manganese Oxides with Tunnel Structures," in Synthesis of Microporous Materials, Vol. II, 333, M. L. Occelli, H. E. Robson Eds. Van Nostrand Reinhold, N.Y., 1992 and R. Giovanili and B. Balmer, Chimia, 35 (1981) 53. Such synthetic octahedral molecular sieves having (2×2) tunnel structures are referred to in the art by the designation OMS-2. The (2×2) tunnel structure of OMS-2 is diagrammatically depicted in FIG. 1.
The hydrothermal method of synthesizing OMS-2 involves autoclaving an aqueous solution of manganese cation and permanganate anion under acidic conditions, i.e., pH<3, at temperatures ranging from about 80° to about 140° C. in the presence of counter cations having ionic diameters of between about 2.3 and about 4.6 Å. The counter cations can serve as templates for the formation of OMS-2 product and be retained in the tunnel structures thereof. Based on analytical tests, OMS-2 produced via this method is thermally stable up to about 600° C.
Alternatively, OMS-2 can be produced by the method disclosed in R. Giovanili and B. Balmer, Chimia, 35 (1981) 53. Thus, when manganese cation and permanganate anion are reacted under basic conditions, i.e., pH>12, a layered manganese oxide precursor is produced. This precursor is ion exchanged and then calcined at high temperatures, i.e., temperatures generally exceeding about 600° C., to form OMS-2 product. Analytical tests indicate that OMS-2 produced via this method is thermally stable up to about 800° C. and the average oxidation state of manganese ion is lower.
SUMMARY OF THE INVENTION
In accordance with the present invention a manganese oxide octahedral molecular sieve is produced by the method which comprising:
a) forming an aqueous reaction medium containing manganese cation and permanganate anion, the reaction medium being maintained at a pH of not greater than about 4.5;
b) refluxing the reaction medium under conditions effective to produce solid crystalline manganese oxide octahedral molecular sieve product; and,
c) recovering the solid crystalline product.
Unlike the hydrothermal method of producing OMS-2 which involves the use of a closed-system reactor, i.e., an autoclave, and the application of autogenous pressure, the method of this invention is carried out in an open system, i.e., in a reflux condenser, which does not involve the application of pressure. OMS-2 produced by the refluxing method herein is thermally stable up to about 600° C.
BRIEF DESCRIPTION OF THE DRAWINGS
In the attached figures of drawing:
FIG. 1 is a diagrammatic representation of the three dimensional tunnel structure of OMS-2.
DETAILED DESCRIPTION OF THE INVENTION
The aqueous reaction medium containing manganese cation and permanganate anion is preferably formed by first dissolving a manganese salt in aqueous medium, e.g., distilled deionized water, which is maintained at an initial pH of not greater than about 4.5 to provide a first solution. The concentration of manganese cation in the first solution is not narrowly critical and can range from about 0.5 to about 1M, preferably from about 0.1 to about 0.5M. Preferably, the pH of the first solution ranges from about 0 to about 4.0, and more preferably from about 1.0 to about 3.0. Suitable acids for adjusting the pH of the solution include the mineral acids, e.g., HCl, H 2 SO 4 , HNO 3 , and strong organic acids such as toluene sulfonic acid and trifluoroacetic acid. A permanganate-salt is then dissolved in a separate aqueous medium, e.g., distilled deionized water, to provide a second solution. The concentration of permanganate anion in the second solution is likewise not narrowly critical and can range from about 0.05 to about 1M preferably, from about 0.1 to about 0.5M. Thereafter, the first solution and second solution are combined to form the aqueous reaction medium containing manganese cation and permangante anion. In another embodiment, the permanganate salt can be co-dissolved with the manganese salt in aqueous medium to provide the aqueous reaction medium containing manganese cation and permanganate anion. After formation of the reaction medium, the pH of the reaction medium can be adjusted to its initial level, if necessary, by the addition of an appropriate amount of a suitable acid such as one or more of the aforementioned pH-adjusting acids.
In general, any manganese salt, whether inorganic or organic, can be employed herein so long as it is soluble in aqueous medium. Suitable salts include, for example, the sulfate, nitrate and perchlorate salts and salts of organic acids such as acetates.
The permanganate salt is likewise not limited so long as it remains soluble in the aqueous reaction medium. In general, the permanganate salt can be an alkali or alkaline earth metal permanganate such as a permanganate of sodium, potassium, cesium, magnesium, calcium and barium. Ammonium or tetraalkylammonium permanganates can also be employed. The counter ions of the aforementioned permanganates, i.e., alkali metal cations, alkaline earth metal cations, ammonium cations and tetraalkylammonium cations, often enhance solubility of the permanganate anion in the aqueous reaction medium. In some cases, the counter ions, especially in the case of the larger counter ions such as potassium and barium, serve as templates for crystallization of OMS product and can remain in the tunnel structures of OMS as tunnel cations. Counter cations having ionic diameters of less than about 2.3 Å produce a nsutite structure, while those having ionic diameters ranging from about 2.3 to about 4.6 Å produce a (2×2) tunnel structure, i.e., OMS-2. Therefore, the particular permanganate salt employed in the practice of this invention can be selected for its ability to facilitate the formation and stabilization of the desired OMS product. Where a smaller counter ion, for example, sodium cation and/or magnesium cation, is utilized, the counter ion can have the desirable effect of allowing template materials other than the counter ion to affect the formation of OMS. The ionic diameters of some alkali and alkaline earth metal cations which can be employed are listed below:
______________________________________Cation Li.sup.+ Na.sup.+ K.sup.+ Cs.sup.+ Mg.sup.2+ Ca.sup.2+ Ba.sup.2+r(Å) 1.36 1.96 2.66 3.78 1.30 1.98 2.70______________________________________
Template materials which can be employed in producing OMS include tetraakylammonium salts in which the alkyl groups can contain from 1 to about 5 carbon atoms, can be the same or different and can be normal or branched in structure. Methyl, ethyl and propyl groups are representative of those alkyl groups which can advantageously be employed herein. The counter ion of the tetraalkylammonium salt can be any suitable inorganic or organic anion which will dissolve and remain in solution without interfering with the reaction or, optionally, form a precipitate with the counter ion of the permanganate salt employed in the method herein. Examples of such anions include the halides, hydroxides, bisulfates, sulfates, perchlorates, acetates and the like.
Also useful as organic templates are polymer chains containing synthetic polymers such as those described as cationic polymers, quaternary ammonium polymers and ionene polymers by Daniels et al. in "Cationic Polymers as Templates in Zeolite Crystallization," J. Am. Chem. Soc. 100, pp. 3097-3100 (1978) and Davis et al. in "Synthesis of Gmelinite and ASM-12 Zeolites with a Polymer Template," J. Chem. Soc., Chem. Commun. 1988, pp. 920-921.
The molar ratio of manganese cation to permanganate anion, [Mn +2 ]/[MnO 4 - ], which can be expressed as [Mn 2+ ]/[Mn 7+ ] for convenience, is one of the critical factors or parameters in determining the nature of the product obtained via the method of this invention. The [Mn 2+ ]/[Mn 7+ ] ratio will generally be about 0.05 to about 3, preferably about 0.1 to about 2. When a ratio of about 0.1 to about 1.5 is employed, OMS-2 is formed. When a ratio of greater than about 2.5 is employed, OMS corresponding to the nsutites are formed.
The temperatures at which the reaction medium is refluxed can range broadly from about 40° C. to about 255° C. with the lower end of this temperature range tending to produce slower reactions. Temperatures in the range of from about 40° to about 70° C. will tend to produce the nsutite structures which have generally low crystallinities but contain structures characterized by tunnels of dimension l×n where the basic unit dimension is a manganese oxide octahedron and can be an integer of 1 or 2. Given an appropriate pH, the process of the invention can be carried out to produce materials of the OMS-2 structure at temperatures ranging from about 70° C. to about 155° C., preferably from about 80° to about 120° C. and more preferably from about 90° to about 110° C. For the production of pyrolusite (1×1) structures, the temperature preferably ranges from about 155° C. to about 255° C.
Generally, the reaction medium is refluxed in an open system, e.g., a condenser, for a period of time ranging from about 2 to about 48, preferably from about 12 to about 36, hours. The refluxing operation will result in the formation of a crystalline product characterized by three dimensional mono-directional tunnel structures formed by chains of edge-sharing MnO 6 octahedra. Following the refluxing step, the crystalline product can be recovered from the reaction medium by any suitable technique. In general, the product will be filtered, e.g., in a filter funnel under vacuum, washed with purified water and dried, preferably in an oven at about 120° C. for about 12 hours.
The octahedral molecular sieve produced by the method of this invention possesses acid sites, including Lewis and Bronsted sites. Applications include catalyzed reactions, e.g., isomerization and polymerization, and adsorption. Specific examples of catalysis and adsorption applications of OMS include the decomposition of alcohol, oxidation of CO, dehydrogenation of hydrocarbons, reduction of NO, hydrogenation of olefins, demetallation of petroleum residua, decomposition of organic sulfur compounds, decomposition of organic nitrogen compounds, decomposition of asphalt, adsorption of noxious gases and adsorption of heavy metal ions.
The following example is presented to illustrate specific embodiments of the practice of this invention and is not intended to be a limitation upon the scope of this invention.
EXAMPLE 1
Preparation of K-OMS-2 by Refluxing Method
MnSO 4 ·H 2 O (8.8 g) was dissolved in 30 mL water containing 3 mL concentrated HNO 3 to provide an aqueous reaction medium having a pH of 1.0. A solution of KMnO 4 (5.89 g) in 100 mL water was added to the solution to provide an aqueous reaction medium containing manganese cation and permanganate anion. The reaction medium was refluxed at 100° C. for 24 hours to result in the formation of OMS-2 product containing potassium tunnel cations. The product was filtered, washed and dried at 120° C. The sample constituted 4.34% K and 56.4% Mn. X-ray powder diffraction data shows OMS-2 structure. | Manganese oxide octahedral molecular sieve (OMS) is produced by the method comprising:
a) forming an aqueous reaction medium containing manganese cation and permanganate anion, the reaction medium being maintained at a pH of not greater than about 4.5;
b) refluxing the aqueous reaction medium under conditions which are effective to produce solid crystalline manganese oxide octahedral molecular sieve product; and,
c) recovering the solid crystalline product.
The method of this invention is carried out in an open system, i.e., a reflux condenser, and results in the formation of OMS which is thermally stable up to about 600° C. | 2 |
BACKGROUND OF THE INVENTION
[0001] b 1 . Field of the Invention
[0002] The invention relates generally to method and apparatus for non-invasive measurement of a change of the temperature inside a living body, from the outside or a cavity of the living body.
[0003] When an ultrasound wave passes through a material such as body tissue energy of the ultrasonic wave is absorbed and the wave is attenuated. The part of the ultrasonic wave that is absorbed is converted substantially to heat energy. Therapeutic ultrasound i. e. high intense ultrasound is used for heat treatment of i. a. muscles and other structures in the living body mostly in order to increase the blood flow through the structure and to speed up the healing thereof. The heating by therapeutic ultrasound is effected up to about 3 W/cm 2 . The temperature of the heated structure and the surrounding tissue is not controlled. Recently the MR-technique has been used, but it is an expensive a slow technique. Therefore, in this case as when tissue is destructed by local heating to a temperature of 42 to 95° or when a stent inserted into a blood vessel is heated for heat treatment of abnormalities in the vessel reliable control of the temperature change in the tissue or the stent during the treatment is desired in order to effect the treatment without injuring tissue surrounding the region to be treated by ultrasound heating.
[0004] 2. Description of the Prior Art
[0005] It is known in the art to provide temperature control during non-invasive treatment of a target area inside a living body. Thus, JP-A-1233337 describes method and apparatus for measuring temperature of an object which cannot be approached from the outside, such as tissue inside a human body, which is heated by external heater, wherein an ultrasonic wave is transmitted to the object. A reflected wave therefrom is subjected to A/D conversion and the sensed wave is cut out at each one wavelength for frequency analysis. The temperature of the object is calculated therefrom on the basis of a predetermined relationship between a peak frequency of a frequency distribution obtained by the analysis, or a half-width thereof, and the temperature of the object.
[0006] U.S. Pat. No. 5,370,121 describes method and apparatus for non-invasively measuring a temperature change between two points in a region of interest in the inside of a living subject which is treated with heating radiation. A first ultrasound wave form, containing at least one ultrasound pulse is emitted into the subject at a first point of time and is incident on the region of interest which reflects a corresponding first set of echo signals from which a first ultrasound image is generated and stored. A second ultrasound waveform identical to the first ultrasound wave form is emitted into the subject at a second point in time incident on said region which reflects a corresponding second set of echo signals. A second ultrasonic image is generated therefrom. From the first and second ultrasonic images a differential ultrasound image is generated. A temperature change, if any, in the region of interest is identified during the course of producing ultrasound images of the region by determining the change of the acoustic impedance of the region of interest between the first and second points in time, a temperature change being allocated to the impedance change.
[0007] U.S. Pat. No. 4,807,633 describes method and apparatus for non-invasive thermometry which is based on the observation that attenuation of a transmitted or reflected beam of ultrasound in tissue changes measurably as tissue temperature changes. The prior art method and apparatus comprise periodic amplitude measurement of back-scattered ultrasound.
[0008] U.S. Pat. No. 6,050,943 relates to a combined imaging, therapy and temperature monitoring system comprising an acoustic transducer assembly configured to enable the ultrasonic system to perform the imaging, therapy and temperature monitoring functions. The transducer assembly includes a single transducer which is operatively connected to an imaging subsystem, a therapy subsystem and a temperature monitoring subsystem. The therapy subsystem can generate high power acoustic energy to heat a treatment region, and the temperature monitoring subsystem can map and monitor the temperature of tissue in said region and display the temperature on a display. Mapping of the temperature distribution in tissue in the treatment region is accomplished by measuring the time-of-flight and amplitude data of acoustic pulses through said region while exploiting the temperature dependence of the speed of sound and acoustic attenuation in the tissue of the treatment region. Imaging, temperature heating and temperature monitoring of the treatment region can be conducted substantially simultaneously.
[0009] U.S. Pat. No. 4,566,460 describes method and apparatus for measuring a non-linear parameter A/B of an acoustic medium or its distribution, and the application of the parameter to non-invasive measurement of internal temperature of a sample. A continuous wave ultrasonic probing beam is radiated through the sample, and a pumping wave which is an ultrasonic pulse is superposed on the probing beam. A phase change in the probing beam caused by the pumping wave is detected and from this phase change the non-linear parameter (B/A) is obtained. From the information concerning the variation of the measured value of said parameter the inner temperature of the sample is obtained.
[0010] U.S. Pat. No. 5,360,268 describes an ultrasonic temperature measuring apparatus measuring the temperature of a medium, which includes a transmitter for transmitting ultrasonic waves and a receiver for receiving the ultrasonic waves and providing a received signal. An operation unit calculates the propagation time of the ultrasonic waves, and the temperature in the medium is determined according to the propagation time of the ultrasonic waves.
[0011] U.S. Pat. No. 4,817,615 describes an ultrasonic diagnostic apparatus which includes an ultrasonic transducer for transmitting an ultrasonic wave into a body to be examined and receiving the reflected ultrasonic wave, phase variations being detected to obtain fluctuation of the temperature within the body.
[0012] A similar ultrasonic pulse temperature determination method and apparatus are described in U.S. Pat. No. 4,754,760 wherein ultrasound pulses are transmitted into a specimen and the attenuation of the ultrasound pulses between different depths in the specimen is determined before and after heating of the specimen. The change in temperature of the specimen is determined from the obtained attenuation values.
[0013] JP 61280533 describes an apparatus for measuring internal temperature of a living body by reflected ultrasonic wave delivered to the interior of the living body. Spectral analysis is applied to the frequency of the reflected wave and the change quantity of the frequency spectrum of the reflected wave is calculated and is converted to a temperature change quantity.
[0014] The prior art methods and apparatuses do not provide the precision in measuring the temperature of the target as is required in order to provide an accurate temperature control for an adequate therapeutic treatment, and/or require use of several measuring points, which makes the use of the prior art methods and apparatuses rather complicated.
BRIEF SUMMARY OF THE INVENTION
[0015] The object of the invention is to overcome the drawbacks mentioned above and to provide method and apparatus for accurate measuring of the temperature in a very small area of a target within a region which is ultrasonically heated, especially for treating a vessel using stent material or for destructing tissue such as cancer tissue, by using back scattered ultrasound from the target for the temperature measurements.
[0016] More particularly the invention provides method and apparatus allowing control of the temperature in a target heated by pulsed therapeutic high intense ultrasound, after each therapeutic pulse in order to produce a well adjusted energy dose for creating an adequate temperature of a confined small area of the target.
[0017] In order to achieve the above object the invention provides a method according to claim 1 and an apparatus according to claim 9 .
[0018] Further features of the invention are defined in the dependent claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a block diagram of an apparatus of the invention,
[0020] FIG. 2 is a time diagram of the procedure applied when using the apparatus of FIG. 1 ,
[0021] FIG. 3 is a frequency spectrum of a pulse of back scattered ultrasound, and
[0022] FIGS. 4 and 5 are diagrams illustrating the frequency peaks of the harmonics of the back scattered pulse.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Referring to FIG. 1 the apparatus for practising the method of the invention comprises a control unit 10 including a transmitter 11 for generating low intense (diagnostic) ultrasound energy for temperature measuring, and a transmitter 12 for generating high intense therapeutic ultrasound energy, the ultrasound energy being transmitted by a transducer 13 comprising a number of ultrasound emitters formed by thin ceramic plates 14 mounted to a reflecting bowl shaped mounting system 15 focusing the transmitted ultrasound energy. The two transmitter circuits can also be combined to form a single circuit for therapeutic as well as diagnostic purposes. Therapeutic ultrasound energy generated by the transmitter 12 is emitted from the transducer 13 which is applied against an outside surface of the body tissue, for treatment of the tissue in a target region T of body tissue e. g. cancer tissue, to be treated, or to a stent located in a blood vessel. It is also possible to use phased array transducer systems both for treating and temperature measuring instead of the described bowl shaped transducer arrangement. The target region T is located between first and second tissue surfaces A and B. The thickness of the target region T between surfaces A and B is defined by applying one or the other of prior art methods developed for said purpose. Transducer 13 is adjusted in focus the emitted ultrasound energy on an area F located in the target region T. In FIG. 1 the focused area F in the target region T has an ellipsoid form of a size which is substantially the same as that of a grain of rice but can be smaller or larger depending on the construction. A sensor 17 is provided in transducer 13 for picking up back scattered ultrasound echo signals. A receiver 18 including a wide band amplifier with controlled amplification is provided for receiving and amplifying the picked up ultrasound echo signals. Receiver 18 is connected to an analogue/digital converter 19 with memory and with a high sampling frequency fs ranging from >3×fo to about 20×fo where fo is the fundamental frequency (first harmonic) of the echo signal, for converting signals received by the receiver from analogue form to digital form in order to facilitate subsequent signal processing. fo can be of different frequency with a variation in bandwidth for optimal temperature sensitivity. Output signals from the receiver are transmitted via the converter to an analyser 20 which can be an FFT (fast Fourier transform) analyser or a Doppler analyser or wavelet technique or an analyser correlating echoes from different types and configuration of transmitted ultrasound pulses. A single analyser of one of the types mentioned or a combination thereof can be provided. The output signal from the analyser (or each analyser) is transferred to a complex comparing circuit 21 herein referred to as a comparator wherein the signal is compared with a reference stored therein. As an optional (used or not used) feature comparator 21 is operatively connected to transmitter 10 . When a comparison indicates that the input signal equals a pre-set reference value the comparator shuts of transmitter 12 . Analyser 20 is connected to a calculator 22 including programs for processing the received back scattered echo signals. A display 23 is connected to comparator 21 and a calculator 22 for visually presenting the parameters of interest.
[0024] Parameters of the treatment such as ultrasound intensity, type of pulse sequence, depth of target region T, frequency of the ultrasound, and selected temperature are programmed or set on control unit 10 and measure the temperature in every focal point.
[0025] With reference to FIG. 2 which illustrates diagrammatically a typical sequence for effecting a non-invasive treatment by means of therapeutic high intense ultrasound the several steps being marked on a time axis.
[0026] A therapeutic ultrasound pulse 1 is emitted from the apparatus for about 1.3 seconds and then there is a pause to the next therapeutic ultrasound pulse 1 ′ for a period of 8.7 seconds. This can also be scaled down by approximately a factor of 10, and also the pulse duration quote can be changed. During the pause of 8.7 seconds between pulses 1 and 1 ′ a temperature diagnostic pulse 2 from transmitter 11 is emitted by transducer 13 and the result of the treatment is checked by using the back scattered echo E 2 from pulse 2 and the back scattered echo E 2 ′ from pulse 2 ′ or, generally, by using the back scattered echo E 2 n from pulse 2 n.
[0027] The signal representing the back scattered echo from the target region T under treatment by means of the therapeutic high intense ultrasound is presented as a frequency spectrum as disclosed in FIG. 3 by analyser 20 . This spectrum comprises a first harmonic (fundamental frequency) Al, a second harmonic A 2 , a third harmonic and possibly further high order harmonics. The first, second and third harmonics have the frequency f 0 , 2 f 0 and 3 f 0 , respectively. The amplitudes of these frequencies is represented by analyser 20 as shown in FIG. 2 .
[0028] Measurement of echo E 2 is the first measurement and is designated 0, and the amplitude of three harmonics included in said echo are designated A 10 at the frequency f 0 , A 20 at the frequency 2 f 0 , and A 30 at the frequency 3 f 0 .
[0029] The measurement of echo E 2 ′ is the second measurement and is designated 1. The corresponding three harmonics are designated A 11 , A 21 and A 31 .
[0030] At measurement n of an echo caused by a diagnostic temperature measurement pulse 2 n the three harmonics are designated A 1 n, A 2 n and A 3 n.
[0031] The echo of the tracking end of the therapeutic pulse 1 , 1 ′ and in are indicated in FIG. 2 at E 1 , E 1 ′ and E/n and can be used as measurement pulses but it is preferred to use separate pulses 2 , 2 ′ and 2 n for this purpose. Referring to FIG. 2 the first simplest quotient is calculated for each measuring point at E 1 and E 2 and for the E 1 n and E 2 n by the formula:
quotient=(Amplitude of second harmonic/Amplitude of first harmonic)
or
quotient=(Intensity integral of second harmonic/Intensity integral of first harmonic)
as illustrated in FIG. 3 .
[0032] By means of a program in the calculator 22 the quotient,
A 1 n - A 10 A 10
[0033] is calculated, wherein A 10 is the amplitude of the first harmonic before start of treatment and A 1 n is the amplitude of the first harmonic at measurement n after start.
[0034] An other quotient,
A 2 n - A 20 A 20
[0035] is calculated, wherein A 20 is the amplitude of the second harmonic before start of treatment and A 20 is the amplitude of the second harmonic at measurement and A 2 n is the amplitude of the second harmonic at measurement n after start.
[0036] Calculations can be made for following measurements the measurement to provide the quotient for the second harmonic and the quotient between second harmonic and first harmonic
A 2 n - A 2 ( n - 1 ) A 2 ( n - 1 )
[0037] were n−1 is the measurement just before measurement nr n. The invention is based on the findings that the amplitude quotient of harmonics (as well as intensity, quotient based on the square of the amplitude) is dependent of the temperature change in the target region during heating thereof. Thus it has been found that there is an almost linear relationship between the temperature change and the quotient
Δ T=C ×the quotient
[0038] wherein C is a constant factor that is determined empirically and is specific for tissue type, depth of target region T, ultrasound, intensity and frequency and the sensor system applied.
[0039] With reference to FIG. 4 as an alternative to the amplitude quotient an integral quotient can be used the area of the peaks in the diagram down to the horizontal axis for the amplitude zero being used for the calculation of the quotient
Y 21 - Y 20 Y 20
[0040] or as shown in FIG. 5 the quotient is calculated by taking into account only the area above a noise level N which in many cases can be neglected if the signal to noise ratio (SNR) is large enough. The quotients based on the FFT calculations can be based on the amplitude from the echoes or the intensities from the echoes which is the square of the amplitude. The temperature of the target area relating to the measurements made is calculated on the basis of one of said quotients or a combination of several quotients.
[0041] In experiments the inventor has based the calculations on all types of quotient using all harmonics in different combinations to find the most sensitive combination of one or many quotients. The above given examples are the most frequently used quotients. However this is tissue dependent and must be experimentally investigated from cases to cases. Depending on the result the non-invasive treatment is repeated under temperature control according to the procedure described until the desired temperature in the target area T (tissue or inserted artificial material) or a shell around the target area has been developed.
[0042] Other non-linear calculation systems can be proposed in order to increase the precision of the calculation of the temperature change such as
ΔT=function (quotient)
[0043] wherein the function has to be determined from case to case.
[0044] In heating a stent covered by an ultrasound absorbing and reflecting material such as polytetrafluoro ethylene, polyurethane or elastomer it should be possible to measure in the range from 37 to about 55° C. and in connection with treatment of cancer up to 85° C. For therapeutical treatment of e.g. muscles it is desired to measure up to 41° C. in order to avoid a higher temperature.
[0045] Preferred embodiments have been described in order to illustrate the invention but it is obvious to the man skilled in the art that these embodiments are examples only and that modifications thereof can be made without departing from the scope of the invention as defined in the claims. | Method and apparatus for non-invasive measuring of the temperature change of a target inside a body by transmitting an ultrasonic pulse to the target, subjecting a pulse reflected from the large( to frequency analysis, and calculating the temperature change of the large therefrom. A frequency spectrum of the reflected pulse is produced and the calculation of the temperature change is effected on the basis of harmonics appearing in said spectrum. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
This patent application is a Continuation-in-Part of U.S. Ser. No. 746,541 filed Jan. 19, 1991, now abandoned, which is a Continuation-in-Part of U.S. Ser. No. 556,243 filed Jul. 23, 1990, now U.S. Pat. No. 5,057,564.
FIELD OF THE INVENTION
The present invention relates to novel adducts of cyclic carbonyl compounds or their derivatives with unsaturated organic molecules containing functional groups.
BACKGROUND OF THE INVENTION
In copending application U.S. Ser. No. 746,541, filed Jan. 19, 1991, now abandoned novel adducts of cyclic carbonyl compounds and alkenes and cycloalkenes are disclosed and claimed. These adducts are produced by reacting a cyclic carbonyl monomer having an ene-reactive carbonyl group with an unsaturated hydrocarbon to form a novel adduct having a molecular weight of about 500 or less. These novel adducts are useful as viscosity modifying agents.
SUMMARY OF THE INVENTION
The present invention relates to novel adducts of cyclic carbonyl monomers with substituted olefins, which also are useful as solution viscosifiers.
GENERAL DESCRIPTION
The novel compounds of this invention are adducts of cyclic carbonyl monomers and derivatives thereof, with substituted alkenes which have from about three to eighteen carbon atoms, and one or more substituents. The novel adducts are produced by contacting selected cyclic carbonyl monomers (shown as A and/or B in the equations hereinafter) with substituted olefins for a time and a temperature sufficient to form an ene adduct.
Typical chemical reactions to produce these novel adducts of cyclic carbonyl monomers and alkenes containing functional groups are represented by the equations: ##STR1## wherein Ra, Rb, Rc, Rd, and Re are independently selected from the group consisting of H, alkyl and substituted groups having from 1 to 15 carbon atoms, provided that at least one of Ra, Rb, Rc, Rd and Re is a substituted alkyl group containing one or more of substitutents selected from the group consisting of halo, hydroxy, (Oalkylene) x OH, wherein alkylene is ethylene, propylene or butylene, and x=1-30; RO-wherein R=is an alkyl group of from 1 to 18 carbons; aryloxy, R 2 N-wherein R=is an alkyl group having 1-18 carbon atoms; cyano, sulfo, sulfono, RS--where R is an alkyl group of 1-18 carbons; arylthio, formyl; acyl, aroyl, carboxy, carboalkoxy wherein alkoxy contains 1-18 carbon atoms; carboxamido; carboaryloxy; aryl wherein aryl is phenyl, substituted phenyl, naphthyl, substituted naphthyl; heterocyclic radicals; silyl, silyoxy; and wherein Q=water or an alcohol, especially methanol, ethanol, butanol; n=0, 1, >1; and X or Y are independently selected from the group consisting of methylene, C=O; U, V, and W are independently selected from the group consisting of methylene, C=O, C=NH, C=NR, wherein R=1-18 carbons; O, NH, NR, S, C=S, CMe2, CHPh, CH-CHOH-CH20H; and U and V are dependently selected such that U and V taken together are selected from 1,2-phenylene, 1,8-naphthalene-diyl; and 1,2-dihydroxyethylene-1,2-diyl.
An especially useful group of alkenes useful in the present invention is cited in "McCutcheon's Emulsifiers and Detergents", 1991 North American Edition, McCutcheon Division, MC Publishing Company, N.J. Accordingly, a variety of unsaturated anionic, nonionic, cationic, and amphotheric emulsifiers and detergents having a range of HLB values from 0.8 to about 42.0 can be functionalized with the ene reactive carbonyl monomers of the present invention. Included are unsaturated alkanolamides, amine oxides, sulfonated amides, betaines, ethoxylated alcohols, amines, amides, fatty acids, and fatty esters; fatty esters, glycerol esters, glycol esters, imidazolines, lecithins, monoglycerides, phosphates, phosphate esters, propoxylated and ethoxylated fatty acids and alcohols; sarcosine derivatives, sorbitan derivatives, sucrose esters, sulfates and sulfonate derivatives, and sulfosuccinates.
Examples of these unsaturated emulsifiers and detergents include lecithin, glycerol trioleate, sorbitan trioleate, diethylene glycol dioleate, glycerol monooleate, glycerol dioleate, glycerol ricinoleate, polyethylene glycol (100) monooleate, polyoxyethylene (2) oleyl ether, N,N-dimethyl oleamide, linoleamidopropyl dimethylamine, oleyl dimethylamine oxide, oleyl alkanolamide, oleic imidazoline, oleic isopropanolamide, oleic hydroxyethyl imidazoline, N,N-bis(2-hydroxyethyl)oleamide, castor oil diethanolamide, ethoxylated oleylamine, linolenic diethanolamide, castor oil amidopropyl dimethylamine, phosphated oleyl esters, sulfosuccinate of undecylenic acid alkanolamide, ricinoleic acid sulfosuccinate, undecylenic sulfo-succinate, oleamide sarcosine, undecylenamide, sulfated castor oil, pentaerythritol monooleate, PEG 400 dioleate, PEG 200 monooleate, oleamidopropyl dimethylamine oxide, triglycerol monooleate, sucrose ricinoleate, propylene glycol monoricinoleate, PEG 600 dioleate, polyoxyethylene (5) sorbitan monoleate, polyoxyethylene (10) aleyl alcohol, tall oil monooleate, polyoxyethylene glycerol monoricinoleate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) oleyl alcohol, and sodium oleyl sulfate.
In the foregoing the halo group may be fluoro, chloro, bromo or iodo. Also, the heterocyclic radicals typically will be radicals of 5 or 6 membered rings having heteroatoms selected from O, N and S. Examples include radicals of the following heterocyclic compounds: furan, thiophene, imidazole, triazole oxazole, thiazole, thiadiazole indole, benzofuran, benzimidazole, benzoxazole, benzotriazole, benzothiazole, purine, xanthine pyridine, pyrimidine, pyrazine, triazine quinoline, isoquinoline, phthalazine quinazoline, quinoxaline and phenanthroline.
Typical cyclic carbonyl monomers include alloxan, 1,3-di-methylalloxan, indantrione, tetralintetrone, dehydroascorbic acid, rhodizonic acid, croconic acid, triquinoyl, leuconic acid, isopropylidene ketomalonate, tetrahydrofuran-2,3,4-trione, 1,2-benzopyran-2,3,4-trione, quinoline-2,3,4-trione, cyclopentane-1,2,3-trione and cyclohexane-1,2,3-trione.
Useful substituted olefins include halo alkenes such as 4-bromo-buteneol-1, 5-bromo-1-pentene, 1-chloro-1-methyl-2-butene, 4-bromo-2-methyl -2-butene, 6-bromo- 1-hexene, 5-bromo-2-methyl -2-pentene, 8-bromo-1-octene, citronellyl bromide, geranyl chloride, geranyl bromide, farnesyl bromide, oleyl chloride, oleyl bromide, and cholesteryl chloride; unsaturated alcohols such as 2-propen-1-ol, 2-methyl -2-propen-1-ol, 2-methylene-1,3-propanediol, 3-buten-1-ol, 2-buten-1,4-diol, 3-methyl -3-buten-1-ol, 4-penten-1-ol, 3-penten-1-ol, 4-methyl -3-penten-1-ol, 5-hexen-1-ol, 1-hexen-3-ol, 4-hexen-1-ol, 5-hexen-1,2-diol, 1,5-hexadiene-3,4-diol, 3-methyl-2-penten-4-yn-1-ol, 5-hexene-1,2-diol, 1-heptadien-1-ol, 1-octen-3-ol, 2-octene-4-ol, 7-octen-1,2-diol, 3-nonen-1-ol, 1-nonen-3-ol, beta-citronellol, geraniol, nerol, nerolidol, dihydromyrcenol, 5-decene-1-ol, 9-decen-1-ol, 2,4,6-trimethyl-1,6-heptadien-4-ol, 10-undecen-1-ol, 12-bromo-2-dodecen-1-ol, 7-dodecen-1-ol, 8,10-dodecadien-1-ol, 11-tetradecen-1-ol, 7-tetradecen-1-ol, 9-tetradecen-1-ol, farnesol, 11-hexadecen-1-ol, 9-octadecen-1-ol, oleyl alcohol, 13-docosen-1-ol, 1,1-diallyl-1-docosanol, phytol, 2-cyclohexen-1-ol, para-menth-1-en-9-ol, alpha-terpinol, dihydrocarveol, isopulegol, carveol, 3-cyclohexen-1,1-dimethanol, paramenth-6-ene-2,8-diol, 3,5-cyclohexadiene-1,2-diol, retinol, myrtenol, nopol, verbenol, cholesterol, stigmasterol, and ergosterol; unsaturated ethers, acetals, and epoxides: allyl ether, allyl glycidol ether, allyl butyl ether, allyl phenyl ether, 3-butenal diethyl acetal, citral dimethyl acetal, 2-butenyl ether, 2,6-dimethyl-8-(1-methoxyethoxy)-2-octene, methyl 10-undecen-1-yl ether, 2-methyl-4,6,9-trioxa-1-decene, tetraethylene glycol diallyl ether, Brij 92, Brij 99, safrole, 1,2-epoxy-5-hexene, and 1,2-epoxy-7-octene; carboxylic acids, esters and amides such as vinylacetic acid, tiglic acid, itaconic acid, citraconic acid, muconic acid, aconitic acid, 4-pentenoic acid, 3-hexenoic acid, 6-heptenoic acid, 2-ethyl-2-hexenoic acid, citronellic acid, undecenylic acid, 2-dodecenyl succinic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, vaccenic acid, arachidonic acid, erucic acid, abietic acid, and kainic acid; 4-penten-1-yl acetate, 5-decen-1-yl acetate, 7-docen-1-yl acetate, 7-tetradecen-1-yl acetate, 11-hexadecen-1-yl acetate, linalyl acetate, neryl acetate, geranyl acetate, 8,10-dodecadien-1-yl acetate, 7,11-hexadecadien-1-yl acetate, farnesyl acetate, ethyl-3-hexenoate, ethyl undecenylate, methyl 9-hexadecenoate, methyl oleate, vaccenic acid methyl ester, methyl 11-eicosenate, ethyl sorbate, methyl linoleate, methyl linolinate dimethyl brassylate, triolein; N,N-dimethyl 10-undecenamide, N,N-bis-(2-hydroxy-ethyl)-oleamide, erucamide, 2-dodecenylsuccinimide, and 2-octadecenyl-succinimide; unsaturated aldehydes and ketones such as citronellal, 4-decenal, undecylenic aldehyde, 11-hexadecenal, 13-octadecenal, 2,4-hexadienal, and citral; 5-hexen-2-one, 5-methyl-5-hexen-2-one, 3-nonen-2-one, nerylacetone, geranylacetone, dihydrocarvone, 8-cyclohexadecen-1-one, and progesterone; unsaturated nitriles such as 3-pentenenitrile , 3-7-dimethyl,-2,6-octadienitrile, and 2-methyleneglutaronitrile, oleylnitrile; sulfides, sulfur-oxygen, and phosphorus compounds such as allyl ethyl sulfide, 7-octenyl methyl sulfide, 10-undecenyl methyl sulfide, diallyl sulfide, methyl oleyl sulfide, benzyl oleyl sulfide and phenyl oleyl sulfide; methyl 7i-octenyl sulfone, ethyl oleyl sulfone, phenyl 10-undecenyl sulfone; oleyl methanesulfonate, dioleyl sulfosuccinate sodium salt, and N-oleyl-3-amino-1-propanesulfonic acid; diethyl 7-octenylphosphonate, dimethyl oleylphosphonate, and trioleyl phosphate; alkene-substituted aromatics, and heteroaromatics such as indene, 4-phenyl-1-butene, 2-methyl-1-phenyl-1-propene, 10-undecenyl benzene, oleylbenzene, 1,2-dihydronaphthalene, 2-methyl-1-(2-naphthyl)-1-propene, oleyl 2-furoate, 10-undecen-1-yl 2 thiophenecarboxylate, 1-allylimidazole, 10-undecen-1-yl 3-indolecarboxylate, 5-hexenylbenzofuran, 2-(10-undecen-1-yl)amino-benzimidazole, 2-oleylthiobenzothiazole, 2-(3-pentenyl)pyridine,5-(4-pyridyl)-2,7-nonadiene, 4-(10-undecen-1-yl) pyridine, 2-oleylaminopyrimidine, 10-undecenylpyrazine, 8-(3-butenylamino)quinoline, and 5-(10-decenyl)amino-1,10-phenanthroline.
The substituted alkene and cyclic carbonyl compounds are combined and heated at a temperature and for a time sufficient to form the adduct. For example, they are heated at about 20° C. to about 200° C., more preferably at about 40° C. to about 180° C., and most preferably about 60° C. to about 160° C. for about 2 to about 24 hours.
Typically, the reaction is conducted in a solvent capable of dissolving the substituted olefin and the cyclic carbonyl compound. Examples of suitable solvents include alcohols such as ethanol, and butanol, glyme, diglyme, triglyme, cyclic ethers such as tetrahydrofuran, dioxane; aromatics such as toluene, chlorobenzene, xylene and dichlorobenzene.
If necessary, products can be isolated by solvent removal via evaporation or distillation and if desired purified by crystallization or preparative chromatography.
If desired, the reaction of the substituted olefin and cyclic carbonyl monomer can be conducted in the presence of acid catalysts selected from the group consisting of kaolin, montmorillonite, silicates, ferric chloride, and boron trifluoride, and related catalysts. Typically, 0.1 to about 1 gram of catalyst per 0.01 to 1.0 moles of reactants can be used.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples illustrate the present invention without, however, limiting the same hereto.
EXAMPLE 1
Eight grams (0.05 mole) of alloxan hydrate were added to 60 ml of dioxane in a nitrogen-blanketed reactor fitted with thermometer, magnetic stirrer, addition funnel, and reflux condensor. The reaction mixture was heated to reflux, and 18.5 ml of oleyl alcohol (85%) were added dropwise over a 15 minute span. Refluxing the mixture for about an hour produced a clear solution which was heated at reflux for about 24 hours. Rotoevaporation of the reaction mixture afforded a residue, which was filtered and analyzed. A supercritical fluid chromatogram of the residue confirmed the presence of product. The residue featured an infrared spectrum with characteristic hydroxyl, and amido carbonyl absorption bands, and a mass spectrum consistent wtih one or more isomeric ene adducts of oleyl alcohol and alloxan (M+1=411) as typified by the pair of isomeric 5-substituted dialuric acids shown below: ##STR2##
EXAMPLE 2
In the same manner as described in Example 1, 8 grams of alloxan, 15.9 grams of oleic acid, and 60 ml of dioxane were combined in a reactor, and stirred at reflux temperature for 8 hours. The reaction mixture completely dissolved after a hour, and refluxing was continued for another 24 hours. Evaporation of the mixture gave a residue which was filtered and analyzed. A supercritical fluid chromatogram of the residue showed a broad product peak. The residue also featured an infrared spectrum with carbonyl absorption bands ascribable to carboxy and carboxamido carbonyl functionality, and a mass spectrum (M+1=425) consistent with the ene adduct of alloxan and oleic acid.
EXAMPLE 3
A mixture of 4.8 grams (0.03 mole) of alloxan, 10 ml of methyl oleate, and 50 grams of dioxane was combined in a nitrogen-blanketed reactor, and stirred at reflux for 24 hours. Rotoevaporation afforded a residue which featured a supercritical fluid chromatogram with a product peak, an infrared spectrum with strong ester and amide carbonyl absorption bands, and a mass spectrum (M+1=439) consistent with a mixture of isomeric ene adducts.
EXAMPLE 4
Eight grams (0.05 mole) of alloxan hydrate and 50 ml of n-butanol were combined in a nitrogen-blanketed reactor, and stirred at reflux temperature until a clear solution was obtained (about an hour). Nineteen ml of oleyl alcohol ethoxylated with about two moles of ethylene oxide was added, and the mixture was refluxed for 8 hours. The reflux temperature was then increased to about 130° C. by distilling off some of the butanol. Heating at 130° C. was continued for about 24 hours. Evaporation gave a residue which featured an infrared spectrum with a strong amide carbonyl, and ether absorption bands, a supercritical fluid chromatogram with about 10 adduct peaks, and a thermospray mass spectrum a multiplicity of peaks including prominent (M+1) peaks at 411, 455, 499, 543, 587, 631, 675, 719, 763, 807 and 851. These major peaks correspond to isomeric alloxan adducts of oleyl alcohol ethoxylated with 0 to 10 moles of ethylene oxide, respectively as depicted in part, by the structures featured below: ##STR3## In another series of experiments similar to those illustrated in Examples 1 to 4, a wide spectrum of novel ene adducts were produced to demonstrate the ene reactivity of the cyclic carbonyl monomers of the present invention such as indantrione, alloxan, 1,3-dimethylalloxan, and dehydroascorbic acid with oleyl chloride, oleyl alcohol, methyl oleate, methyl linoleate, methyl linolenate, oleic acid, linoleic acid, linolenic acid, ethoxylated oleyl alcohol, and methyl oleyl ketone. | The present invention relates to novel adducts of cyclic carbonyl monomers with substituted olefins, which also are useful as solution viscosifiers. | 2 |
FIELD OF THE INVENTION
This invention relates to precipitation-hardenable martensitic stainless steels and in particular to a precipitation-hardenable martensitic stainless steel that provides a unique combination of machinability, processability, and toughness.
BACKGROUND OF THE INVENTION
The known precipitation-hardenable stainless steels provide high hardness and strength through an age-hardening heat treatment in which a strengthening phase is formed in the relatively, more ductile matrix of the alloy. Such alloys have been used principally in components for aerospace applications. Another type of stainless steel that is designed to provide relatively high strength is the so-called “straight” martensitic stainless steel. An example of such a steel is AISI Type 416 alloy. Such steels achieve high strength when they are quenched from a solution or austenitizing temperature and then tempered. Although there are free-machining grades of the straight martensitic stainless steels, there has not been any known martensitic precipitation-hardenable stainless steel that could be classified as a truly “free-machining” grade. In other words, none of the known grades of precipitation-hardenable martensitic stainless steels contain more than about 0.15% of a free-machining additive such as sulfur or selenium. Because of the simplicity of heat treating the precipitation-hardenable martensitic stainless steels compared to the straight martensitic stainless steels, it would be desirable to have a precipitation-hardenable martensitic stainless steel that provides true free-machining capability.
Hitherto, attempts have been made to produce martensitic precipitation-hardenable stainless steels that provide “enhanced machinability” relative to the standard grades. Such attempts have included the use of limited amounts of free-machining additives such as sulfur or selenium. Alloys have been described that may contain up to relatively high amounts of such additives, e.g., up to 0.40 weight percent, up to 0.5 weight percent, or up to 0.15 weight percent of sulfur or selenium. However, there has not been a commercially produced precipitation-hardenable martensitic stainless steel that actually contains more than about 0.036 weight percent of sulfur or selenium.
The principal reason for the unavailability of a true free-machining precipitation-hardenable martensitic stainless steel is that the presence of the usual free-machining additives such as sulfur and selenium adversely affects important properties of the precipitation-hardenable grades of stainless steels. For example, the presence of sulfur in a known grade of precipitation-hardenable stainless steel has resulted in poor processability, such that the steel tears or splits during hot working or cracks during cold processing or quenching. Also, the presence of sulfur adversely affects the toughness and ductility of the alloy.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a free-machining, precipitation-hardenable martensitic stainless steel, having a unique combination of machinability, processability, and toughness. The broad, intermediate, and preferred compositional ranges of the steel alloy of the present invention are as follows, in weight percent:
Broad
Intermediate
Preferred
C
0.030 max.
0.025 max.
0.020 max.
Mn
0.75 max.
0.50 max.
0.50 max.
Si
0.75 max.
0.50 max.
0.50 max.
P
0.040 max.
0.035 max.
0.030 max.
S
0.15-0.35
0.15-0.30
0.17-0.25
Cr
14.0-15.5
14.0-15.5
14.5-15.0
Ni
5.0-6.0
5.0-6.0
5.0-5.5
Mo
0.50-1.2
0.50-1.0
0.70-1.0
Cu
3.0-4.0
3.0-4.0
3.2-3.8
Nb
0.10-0.30
0.10-0.25
0.10-0.20
N
0.030 max.
0.025 max.
0.020 max.
B
0.010 max.
0.005 max.
0.005 max.
The balance of the alloy is essentially iron, except for the usual impurities found in commercial grades of martensitic, precipitation-hardenable stainless steels and trace amounts of other elements which may vary from a few thousandths of a percent up to larger amounts that do not objectionably detract from the desired combination of properties.
The foregoing tabulation is provided as a convenient summary and is not intended to restrict the lower and upper values of the ranges of the individual elements of the alloy of this invention for use in combination with each other, or to restrict the ranges of the elements for use solely in combination with each other. Thus, one or more of the element ranges of the broad composition can be used with one or more of the other ranges for the remaining elements in the preferred composition. In addition, a minimum or maximum for an element of one preferred embodiment can be used with the maximum or minimum for that element from another preferred embodiment. Throughout this application, the term “percent” or the symbol “%” means percent by weight, unless otherwise indicated.
DETAILED DESCRIPTION
The precipitation hardenable alloy according to this invention contains at least about 14.0% and preferably at least about 14.5% chromium in order to provide the desired level of corrosion resistance. Too much chromium promotes the formation of an undesirable amount of ferrite in this alloy, which adversely affects the toughness and ductility provided by the alloy. Accordingly, the alloy contains not more than about 15.5% and preferably not more than about 15.0% chromium.
Sulfur benefits the machinability of this alloy and at least about 0.15%, preferably at least about 0.17%, sulfur is present in order to obtain a significant improvement in machinability, particularly form-tool machinability. The alloy contains not more than about 0.35%, better yet not more than about 0.30%, and preferably not more than about 0.25% sulfur because too much sulfur adversely affects the processability, toughness, and the corrosion resistance of this alloy.
Nickel promotes the formation of austenite when the alloy is heated at an elevated temperature so that the alloy will readily form martensite during quenching from the elevated temperature. Nickel also contributes to corrosion resistance and toughness in this alloy. Good toughness is important not only for cold processability, but also to inhibit cracking of the alloy when it is quenched, a problem that typically arises in stainless steels containing elevated amounts of sulfur. Nickel also promotes the formation of reverted austenite during the age-hardening process. The presence of a limited amount of reverted austenite in the alloy is beneficial to the toughness of the alloy. For these reasons, the alloy according to this invention contains at least about 5.0% nickel.
Excessive nickel depresses the martensite transformation temperature, which leads to retained austenite after the alloy is quenched. The presence of retained austenite adversely affects the strength capability of the alloy. Therefore, the alloy contains not more than about 6.0% nickel and preferably not more than about 5.5% nickel.
Molybdenum contributes to the corrosion resistance of the alloy, particularly resistance to pitting-type corrosion. Molybdenum also benefits the toughness and ductility provided by this alloy. Accordingly, the alloy contains at least bout 0.50%, and preferably at least about 0.70% molybdenum. Molybdenum promotes the formation of ferrite, too much of which, as noted above, adversely affects the toughness and ductility of this alloy. Therefore, the alloy contains not more than about 1.2% and preferably not more than about 1.0% molybdenum.
At least about 3.0%, preferably at least about 3.2%, copper is present in this alloy as a precipitation hardening agent. During the age hardening heat treatment, the alloy achieves substantial strengthening through the precipitation of fine, copper-rich particles from the martensitic matrix. Too much copper adversely affects the hot workability of the alloy. Therefore, the alloy contains not more than about 4.0% and preferably not more than about 3.8% copper.
At least about 0.10% niobium is present in this alloy primarily as a stabilizing agent against the formation of chromium carbonitrides which are deleterious to the corrosion resistance of the alloy. Too much niobium causes excessive formation of niobium carbides, niobium nitrides, and/or niobium carbonitrides which adversely affect the good machinability provided by this alloy. Too many niobium carbonitrides also adversely affect the alloy's toughness. Furthermore, excessive niobium results in the formation of an undesirable amount of ferrite in this alloy. Therefore, the alloy contains not more than about 0.30%, better yet not more than about 0.25%, and preferably not more than about 0.20% niobium. Those skilled in the art will recognize that tantalum may be substituted for some of the niobium on a weight percent basis. However, tantalum is preferably restricted to not more than about 0.05% in this alloy.
A small but effective amount of boron may be present in amounts up to about 0.010%, preferably up to about 0.005%, to benefit the hot workability and toughness of this alloy.
The balance of the alloy composition is iron except for the usual impurities found in commercial grades of martensitic precipitation-hardenable stainless steels intended for similar use or service. For example, the interstitial elements carbon and nitrogen are restricted to low levels in this alloy in order to benefit the machinability and processability of the alloy, especially during cold processing and quenching. Therefore, the alloy contains not more than about 0.030%, better yet, not more than about 0.025%, and preferably not more than about 0.020% of each of carbon and nitrogen. Other elements such as manganese, silicon, and phosphorus are also maintained at low levels because they adversely affect the good toughness provided by this alloy. More specifically, this alloy contains not more than about 0.75% and preferably not more than about 0.50% manganese because manganese combines with sulfur to form manganese sulfides which adversely affect the corrosion resistance of the alloy. Silicon is typically added to provide deoxidation of the alloy during refining. However, silicon promotes the formation of ferrite in this alloy. Therefore, the alloy contains not more than about 0.75% and preferably not more than about 0.50% silicon. This alloy contains not more than about 0.040%, better yet, not more than about 0.035%, and preferably not more than about 0.030% phosphorus because it adversely affects the toughness and the machinability of this alloy.
The alloy according to this invention is preferably arc-melted in air (ARC), but can also be melted by vacuum induction melting (VIM). The alloy can be refined by vacuum arc remelting (VAR). The alloy may be produced in various product forms including billet, bar, rod, and wire. The alloy is preferably hot worked from a temperature of about 2150-2350° F. The alloy is solution treated by heating at about 1800-2000° F. for about one-half to one hour and then rapidly quenched, preferably with water. The alloy is then aged to final strength by heating at about 900-1150° F. for up to about 4 hours, followed by cooling in air. The alloy may be used to fabricate a variety of machined, corrosion resistant parts that require high strength and good toughness. Among such end products are valve parts, fittings, fasteners, shafts, gears, combustion engine parts, components for chemical processing equipment and paper mill equipment, and components for aircraft and nuclear reactors.
The unique combination of properties provided by the alloy according to the present invention will be appreciated better in the light of the following examples.
WORKING EXAMPLES
To demonstrate the unique combination of properties provided by the alloy according to the present invention, two experiments were carried out. In the first experiment, Example I, the machinability of the alloy was compared to two known commercial grades of stainless steels. In the second experiment, Example II, the impact toughness of the alloy was compared to a known precipitation- hardenable stainless steel.
Example I
For this experiment two 400 lb. heats having weight percent compositions according to the present invention were vacuum induction melted under a partial pressure of argon gas. The weight percent compositions of the two examples of the present alloy, Alloy 1 and Alloy 2, are set forth in Table 1 below together with the weight percent compositions of a commercial heat of Type 303 stainless steel, and a commercial heat of a 17Cr-4Ni precipitation-hardenable stainless steel.
TABLE 1
Type
Elmt./Alloy
Alloy 1
Alloy 2
303
17Cr—4Ni
C
0.018
0.020
0.061
0.025
Mn
0.30
0.30
1.74
0.62
Si
0.40
0.39
0.59
0.40
P
0.020
0.019
0.035
0.020
S
0.16
0.31
0.34
0.026
Cr
14.79
14.83
17.49
15.32
Ni
5.02
5.00
8.54
4.48
Mo
0.75
0.75
0.52
0.27
Cu
3.52
3.51
0.35
3.49
Nb
0.21
0.21
0.05
0.21
N
0.020
0.021
0.038
0.013
B
0.003
0.003
—
0.0020
The balance of each composition is iron and usual impurities. The Type 303 stainless steel was selected because it is a known free-machining grade of austenitic stainless steel. The 17Cr-4Ni precipitation-hardenable stainless steel was selected for the comparison because it is a known precipitation-hardenable stainless steel with enhanced machinability relative to other precipitation-hardenable stainless grades.
Alloys 1 and 2 were cast as 7½ inch square ingots. After solidification, the ingots were forged to 4 inch square billets from a temperature of 2300° F. The forged billets were then aged by heating at 620° C. for 4 hours and then cooled in air. The aged billets were then cogged to 2.125 inch round bars from a temperature of 2000° F. and hot rolled to 0.6875 inch round from a temperature of 2300° F. The 0.6875 inch bars of each heat were then solution annealed by heating at a temperature of 1040° C. for 1 hour and then water quenched. The annealed bars were straightened, turned to 0.637 inch round, restraightened, and then surface ground to 0.625 inch round. Inspection of the bars revealed a single isolated surface crack in one bar of the lower-sulfur heat, Alloy 1. No such problems were encountered with the higher sulfur heat, Alloy 2. Those results indicate a low and acceptable propensity for cracking during cold processing and quenching from the annealing temperature.
The 17Cr-4Ni material was obtained as 10 inch x 8 inch continuously cast billet which was hot rolled to 0.6875 inch round bar from 1950° F. The bar material was aged at 620° C. for 4 hours and then cooled in air. It was then solution annealed at 1040° C. for 1 hour and quenched in water. The bar material was then straightened, cut, and further processed to 0.625 inch round.
The Type 303 material was obtained as coiled rod which was hot rolled and then quenched in water from the hot rolling temperature. The resulting bar was shaved and then cold drawn to 0.625 inch round.
The machinability of each alloy was evaluated on an automatic screw machine. Two sets of tests were conducted. The first compared the machinability of Alloy 1 to the sample of the 17Cr-4Ni precipitation-hardenable stainless steel. The second test compared the machinability of Alloys 1 and 2 to the Type 303 austenitic stainless steel.
In the first machinability test, duplicate tests were conducted on the 0.625 inch round bars of Alloy 1 and the 17Cr-4Ni precipitation-hardenable stainless steel. A form tool was used to machine the bars of each composition to provide parts having a contoured surface. This test was conducted with a spindle speed of 150.6 surface feet per minute (SFM) and a tool feed rate of 0.002 inches per revolution (ipr). A given trial was terminated for one of two reasons (i) growth of the part diameter exceeding 0.003″ as a result of tool wear or (ii) at least 300 parts were machined without exceeding 0.003″ part growth. Tool failure, a third reason for test termination, was not experienced in this testing. The results of the first machinability test are set forth in Table 2 below, including the number of parts machined (Parts Machined) and the amount of growth in the diameter of the machined parts when the test was terminated (Part Growth).
TABLE 2
Alloy
Parts Machined
Part Growth
Alloy 1
300
0.0002 in.
300
0.0004 in.
17Cr—4Ni
90
0.0037 in.
80
0.0044 in.
In the second machinability test, duplicate tests were conducted on the 0.625 inch round bars of Alloys 1 and 2 and the Type 303 stainless steel. As in the first test, a form tool was used to machine the bars of each composition to provide parts having a contoured surface. This test was conducted at a spindle speed of 178.5 SFM and a feed rate of 0.002 ipr. A given trial was terminated for one of the following reasons: (i) growth of the part diameter exceeding 0.003″ as a result of tool wear, (ii) at least 300 parts were machined without the 0.003″ part growth, or (iii) tool failure. The results of the second machinability test are set forth in Table 3 below, including the number of parts machined (Parts Machined).
TABLE 3
Parts Machined
Alloy
1
240
250
2
400
470
Type 303
330
270
The data presented in Table 2 show that the precipitation-hardenable stainless steel according to this invention provides clearly superior machinability relative to the enhanced-machinability grade of precipitation-hardenable stainless steel. In addition, the data of Table 3 show that the alloy of this invention provides machinability that is comparable to that of Type 303 alloy. Thus, the alloy of this invention can be readily used in place of that alloy for those applications requiring higher strength, without sacrificing machinability or corrosion resistance.
Example II
For this experiment four small heats having the weight percent compositions set forth in Table 4 below were vacuum induction melted under a partial pressure of argon gas. Alloys 3-5 are examples of the alloy according to the present invention. Heat A is a comparative composition of a known precipitation-hardenable stainless steel alloy.
TABLE 4
Elmt./Alloy
Alloy 3
Alloy 4
Alloy 5
Heat A
C
0.019
0.020
0.018
0.014
Mn
0.49
0.49
0.50
0.49
Si
0.43
0.43
0.44
0.44
P
0.022
0.024
0.022
0.023
S
0.15
0.16
0.15
0.024
Cr
15.51
15.51
15.02
15.49
Ni
5.03
5.06
5.04
4.86
Mo
0.51
0.71
0.71
0.27
Cu
3.15
3.14
3.21
3.16
Nb
0.20
0.20
0.19
0.18
N
0.014
0.014
0.013
0.011
B
0.002
0.0025
0.003
0.002
The balance of each composition is iron and usual impurities.
Each of the heats was cast as a 2¾ inch ingot. The ingot of each heat was heated at 2300° F. for 2 hours and then press forged to 13/4 inch square bar. The bar was reheated to 2300° F. and press forged to 1⅛ inch square bar. Standard 0.394 inch square Charpy V-notch (CVN) specimens were prepared from the 11/g inch square bars as follows. The bar was solution treated at 1900° F. for 1 hour and then quenched in water. The as-quenched bar material was then machined to form the CVN specimens. The specimens were then aged at 900° F. for 4 hours and then cooled in air.
Four impact specimens from each heat were tested in accordance with ASTM E 23. The results of the impact testing are presented in Table 5 below including the impact strength (IMPACT STRENGTH) in foot-pounds (ft-lbs). The four individual readings (1, 2, 3, 4) and the average (Average) of the four readings are presented.
TABLE 5
IMPACT STRENGTH (ft-lbs)
1
2
3
4
Average
Alloy 3
12.25
14.5
14.25
14.0
13.8
Alloy 4
11.5
13.25
14.25
14.5
13.4
Alloy 5
12.0
11.75
12.5
12.5
12.2
Heat
7.5
5.75
4.75
6.5
6.1
A
The data in Table 5 show that the alloy according to the present invention does not have reduced impact toughness compared to the known alloy, even though the alloy of this invention contains significantly more sulfur than the known alloy.
The terms and expressions that have been employed herein are used as terms of description and not of limitation. There is no intention in the use of such terms and expressions to exclude any equivalents of the features described or any portions thereof. It is recognized, however, that various modifications are possible within the scope of the invention claimed. | A free-machining, precipitation-hardenable, martensitic stainless steel is described that provides a unique combination of machinability, processability, and toughness. The broad compositional range of the steel alloy of the invention is as follows, in weight percent:
C
0.030 max.
Mn
0.75 max.
Si
0.75 max..
P
0.040 max.
S
0.15-0.35
Cr
14.0-15.5
Ni
5.0-6.0
Mo
0.50-1.2
Cu
3.0-4.0
Nb
0.10-0.30
B
0.010 max.
N
0.030 max.
The balance of the alloy is iron and the usual impurities found in commercial grades of martensitic precipitation-hardening stainless steels intended for similar use or service. | 2 |
RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No. 07/336,739 filed on Apr. 12, 1989.
TECHNICAL FIELD OF THE INVENTION
This invention relates to the general field of composite wall or roof foam panels. These panels employ concealed fastening means used in conjunction with structural foam cores which are sandwiched between two facing metal skins.
BACKGROUND OF THE INVENTION
Composite foam panels have been widely used in the building of wall and roof structures due to their high strength to weight ratio and insulative properties. These panels generally range in thickness from one inch to eight inches, depending upon load and thermal insulation requirements. Such panels commonly are fabricated in widths ranging generally from twelve inches to forty-eight inches.
Composite foam panels are generally fastened to building frame members such as horizontal wall girts and roof purlins in a side by side fashion to form the wall or roof surface. Obviously, concealed fastening systems are preferred by architects in order to present a smooth exterior surface.
Concealed fastening systems are generally of two types. The first, commonly designated as a metal skin interlocking design employs interlocking male and female side joints which are profiled along the side edges of the metal skins. The interior side joint is offset from the side edge of the exterior skin giving open accessibility for applying fasteners from the exterior side of the panel. The fastening system is then concealed by the exterior panel surface of the adjacent panel upon side joint engagement. In this type of design, each panel is fastened to the building frame along one side and engaged along the other side. In order to facilitate ease of engagement, a side joint cavity is provided for hiding the fastening system and for providing clearance within the engaged side joints.
The major drawback of the metal skin interlocking side joint design of the prior art is that thermal leakage through the side joint is inevitable. This is due to the presence of the side joint cavity, relative side joint movement under load and the through-conductivity of the fastening system. As such, this type of design is not suitable where thermal efficiency is the primary design function such as in a refrigeration building design.
The second commonly employed configuration is known as the foam core interlocking side joint design. Interlocking tongue and groove elements are provided along the side edges of the foam core. Spaced apart metal straps with mechanical interlocking devices are buried within the foam core of the panel for tightly interlocking the side joints. The panels are fastened to the building frame from the interior side using rivets.
Thermal leakage through panels constructed employing the referenced foam core interlocking side joint design is minimal and, as such, this type of panel is widely used in the construction of refrigeration buildings. However, this design is not without its drawbacks. More specifically, high construction costs are incurred and, in addition, extremely rigid tolerance control must be exercised during erection. These panels also present potential water leakage problems due to the lack of shielded pressure equalized cavities while, often times, interior accessability is not available for driving the rivets. Obviously, high erection costs result which is a problem exacerbated by the need for split crews, one outside crew for handling and placing the panels and one inside crew for interlocking side joints and fastening the panels to the appropriate supports.
Prior art panel designs have also been found to be extremely difficult to replace in situations where individual panel members are damaged for it is difficult to dismount and reassemble the panels in light of the interlocking side joints and lack of accessibility to the concealed fasteners.
Thus, an object of the present invention is to provide building panel members and building panel assemblies which do not suffer from the disadvantages recited previously.
It is still a further object of the present invention to provide panel members and building panel assemblies which are easy to erect while displaying excellent insulative properties, are resistent to water penetration and which employ concealed fasteners.
These and further objects will be more readily appreciated when considering the following description and appended drawings, wherein:
FIG. 1 is a cross sectional view of the composite foam panel of the present invention, and
FIG. 2 a cross sectional view of the installed composite foam panel side joint design of this invention.
SUMMARY OF THE INVENTION
The present invention is to a panel member and building panel assembly. The assembly comprises two or more individual panel members which individually comprise an outer metal facing sheet forming an exterior panel surface, an inner metal facing sheet forming an interior panel surface and a structural foam core.
The inner metal facing sheet is characterized as having a width of specific dimension defined by two parallel edges. The outer metal facing sheet is also characterized as having a width defined by two parallel edges which is less than the width of the inner metal facing sheet.
The structural foam core is characterized as having top and bottom surfaces adhesively connected to the outer metal and inner metal facing sheets. The structural foam core is further characterized by noting that the top surface is of a width substantially coincident with the width of the outer metal facing sheet while the bottom surface is of a width substantially coincident with the width of the inner metal facing sheet. As such, this structural foam core possesses sloping side walls.
The individual panel members are caused to abut substantially at the edges of the inner metal facing sheets. The panel members are placed upon a substantially planar support and attached thereto by securing means passing through the inner metal facing sheet in an area proximate the parallel edges thereof.
Once the panel members are secured to the planar support, a foam plug having a top surface and sloping side walls is frictionally caused to engage the sloping side walls of the structural foam cores of adjacent panel members.
An exterior joint cover is provided over the top surface of said foam plug and is sized to contact the outer metal facing sheets of adjacent panel members.
DETAILED DESCRIPTION OF THE INVENTION
It was the design goal of the present invention to provide a composite foam panel system having the following attributes:
(1) Easiness in replacing an individual panel of an installed panel assembly.
(2) Easiness of erecting a panel in a non-directional and non-sequential manner.
(3) Having a concealed fastening system which is applied from the building exterior.
(4) Displaying minimal thermal leakage from the side joint.
(5) Displaying watertight performance of the side joint.
(6) Displaying a forgiveness in erection tolerances.
Turning to FIG. 1, a cross-sectional view of the composite foam panel typical of the present invention is provided. The panel 10 consists of structural foam core 11 bonded to interior metal skin 12 and exterior metal skin 13. The bond between the exterior and interior metal skins, on the one hand, and the structural foam core, on the other, can be created by curing the foam core in contact with the metal skins or by adhesive bonding the elements together.
Inner metal facing sheet 12 is characterized as having a width "A" of specific dimension defined by two parallel edges. Ideally, each edge displays a lip 14 composed of inner metal facing sheet turned upwardly and toward the outer metal facing sheet.
Outer metal facing sheet 13 is also characterized as having a width shown as "B" in FIG. 1 as defined by two parallel edges. It must be noted that width B is smaller than width A which is a design characteristic of the present invention, the utility of which will be more readily apparent in the following discussion.
The profile of the side edges of the outer metal facing sheet can be of virtually any configuration to facilitate engagement with the exterior joint cover, the purpose of which will be discussed hereinafter. However, as an example of a typical configuration, and as a preferred embodiment, reference is made to FIG. 1 wherein outer metal facing sheet 13 is provided with a first segment 31 composed of outer metal facing sheet material bent forward inner metal facing sheet 12. Second segment 35 is bent substantially parallel to inner metal facing sheet 12 while third segment 32 is bent away from inner metal facing sheet 12 to form a substantially u-shaped member.
Structural foam core 11 is generally characterized as possessing top and bottom surfaces which are defined and which are adhesively connected to outer metal and inner metal facing sheets 13 and 12, respectively. The structural foam core 11 further possesses a width at its top surface which is substantially coincident with width B which, is noted previously, is the width of the outer metal facing sheet. The bottom surface of structural foam core 11 is substantially coincident with width A, the width of inner metal facing sheet 12. As such, in gross appearance, the side walls of individual structural foam core member 11 slopes diagonally and outwardly from top to bottom.
As a preferred embodiment, the side edge or profile of structural foam core 11 is configured as shown, in detail, as in FIG. 2. More specifically, structural foam core 11 is provided with the profile defined by the first and second segments 31 and 35 of outer metal facing sheet 13, a substantially straight edge 16 preceding toward the inner metal facing sheet 12, terminating substantially at a distance from the inner metal facing sheet as defined by lips 14. At that point, the profile extends towards the lip edge of inner metal facing sheet 12.
As noted by viewing FIG. 2, the building panel of the present invention is created by abutting two or more individual panel members substantially at the parallel edges of their inner metal facing sheets. Ideally, lips 14 are created which form somewhat of a "V" between adjacent members. The panel members can be fastened to any appropriate substantially planar support through the use of securing means 18, such as screw members which pass through the inner metal facing sheet in an area approximate the parallel edges thereof.
The space which is formed between lips 14 can be substantially filled with a joint sealant 19 such as silicone caulking. This substantially prevents the passage of water through this abutment seam and creates a substantially waterproof member.
After the attachment of the panel members has been made to the supporting structure, foam plug 20, having top surface 40 and sloping side walls 41 as defined by the slope of structural foam core members 11 at edges 16 is inserted. It is contemplated that a slightly oversized plug 20 is to be employed so that it may be wedged tightly between adjacent panel members. As is quite evident, this plug resides over attachment means 18 to enhance the thermal insulating properties of the assembly. In addition, the plug can be readily removed thus exposing attachment means 18 in the event that individual panel members must be removed from the structural side wall and replaced.
After foam plug 20 is inserted, exterior joint cover 21 is installed. The exterior joint cover can be of virtually any configuration having a top exterior surface and side edges sized such that its side edges engage the edges of outer metal facing sheets of adjacent panel members. When the outer metal facing sheets are provided with profiles as shown in the appended figures, the exterior joint cover is sized such that s-shaped segments 36 frictionally fit over u-shaped members 32 of adjacent panel members. In installing exterior joint cover 21, top exterior surface 37 is substantially parallel to outer metal facing sheet 13.
For roof applications, it is contemplated that the space formed between first segment 31 of outer metal facing sheet 13 and at least a segment of the interior leg portions of exterior joint cover 21 be substantially filled with joint sealant 22 capable of substantially preventing the passage of water therethrough. Obviously, for wall applications, sealant 22 can be eliminated.
It can be visually appreciated from viewing FIG. 2 that the insulating value of the panel assembly is maintained by providing foam plug 20 as there is no metal part in the fastening system to bridge between the exterior and interior surfaces. As such, the design of the present invention provides minimal thermal leakage through the joint. This is achieved while providing a ready access for panel removal for, as noted previously, panels can be removed by simply removing joint cover 21 and foam plug 20 to gain access to fastening elements 18. Since both structural foam core 11 and exterior and interior metal facing sheets 13 and 12 are not interlocking at the side joints, erection can be done in any direction and in any sequence.
In the preferred embodiment, in the event that sealants 19 and 22 are not employed or, if they are employed but are imperfect, cavities 23 are formed between joint cover 21 and the first, second and third segments, 31, 35 and 32, respectively of outer facing sheet 13. Generally, cavities 23 are open to the external environment at their ends so that free space 23 is at substantially ambient pressure. Similarly, cavity 24 which is formed between exterior joint cover 21, third segment 32, structural foam core 11 and foam plug 20 is open to the external environment and thus at ambient pressure.
These cavities, in particularly, cavities 23 are used for water path control. In wall applications, cavities 23 act as downspouts directing exterior rain water to drain downwardly preventing the water from entering into cavity 24. In roofing applications, cavities 23 act as gutters directing any water which may have infiltrated through sealant 22 to flow to the eves of the roof. Since cavities 23 are pressure equalized to the exterior air, only a small amount of water is expected to get into these cavities under imperfect sealant conditions. Therefore, there is little or no concern of overflow in cavities 23.
Cavity 24 should generally be dry under normal conditions and it is this cavity which is connected to the interior side joint through the contacting surface between foam plug 20 and structural foam core 11. As such, any imperfection in interior sealant 19 is likely to only produce air leakage without water leakage problems. In the event that a joint gap must be adjusted according to the dimensional tolerance of the building, foam plug 20 can be reshaped to provide a tight fit without substantial reworking of individual panel members. It is noted that most foam products are highly compressible and, as such, an oversized foam plug 20 can tolerate a range of joint gap variations without reshaping. As such, the objectives of providing a thermally tight side joint and maintaining the adjustability for erection tolerance is achievable only in the practice of the present invention.
Throughout this discussion, various facing sheets and joint covers have been referred to as being composed of metal. Broadly, it is contemplated that these sheets can be commonly painted carbon steel, aluminum or stainless steel. It is further contemplated that the invention employ metal facing materials ranging from approximately 0.013 inches to 0.036 inches although the functionality of the present invention is not deemed to be at all limited by these dimensions. | A building panel assembly comprising two or more individual panel members. The panel members in turn are comprised of an outer metal facing sheet forming an exterior panel surface, an inner metal facing sheet forming an interior panel surface and a structural foam core. Once the individual panel members are secured to a structural support, a foam plug is inserted between the panel members to enhance the insulated properties of the assembly. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims foreign priority to and is a National Stage Application of International Application No. PCT/CN2010/001359, entitled, “SOLVENT SPUN BAMBOO FIBER WITH HIGH WET MODULUS AND PRODUCING METHOD THEREOF,” filed Sep. 7, 2010, which claims priority to Chinese Application No. 200910196861.0, entitled, “SOLVENT SPUN BAMBOO FIBER WITH HIGH WET MODULUS AND PRODUCING METHOD THEREOF,” filed Sep. 30, 2009, which are both hereby incorporated by reference in their entirety.
TECHNICAL FIELD
The present invention relates to a bamboo fiber and a method for producing the same, in particular, to a solvent spun bamboo fiber with high wet modulus and a method for producing the same.
BACKGROUND
Bamboo fiber products closely follow the market and take a distinctive route since they needs high technique and has the following unique properties: smooth, soft, cool and comfortable feelings, bacteriostasic and anti-biotic activities, and environmentally friendly, natural and healthcare natures.
Bamboo fiber fabrics can keep its original characters in naturally anti-biotic bacteriostasic and anti-UV activities after washed and sunned repeatedly for many times, which is different from other fabrics in which finishing agents such as antimicrobial and anti-UV agent are added during the post treatment, so it is a real skin-closed healthcare product with a wide application field since it has healthcare activity and sterilization effect for the human skin without causing any allergic untoward effect on the skin.
The application of bamboo fiber fabric in beddings brings the consumers a health, comfortable and cool summer. The bamboo fiber fabric is also praised as a healthy fabric which has the most developing prospect in 21 st century.
Viscose process is generally used to produce bamboo fiber. However, this process has problems such as over long producing process, serious environmental pollution, etc., wherein the environmental problem is the most obstacle to develop the regenerated bamboo fiber. Meanwhile, the natural properties of bamboo are destroyed during the processing, for example, the deodorizing, anti-biotic and anti-UV activities of the fiber are greatly decreased. In addition, the various finished fibers produced by viscose process have remained sulfur which will form hydrogen sulfide during high temperature dying, thus resulting in peculiar smell during the processing.
To overcome the above technical problems in viscose process, solvent spun process is used to produce bamboo cellulose fiber.
Chinese invention patent publication CN1190531C disclosed a method for producing a solvent spun bamboo cellulose fiber, which has the following disadvantages: 1. the polymerizing reactor has a volume of 5-300 cubic liter, but in general, the polymerizing reactor with a volume of 5-300 cubic liter is not in the industrial scale; 2. this prior art shows a step of pulp dehydration in which the dehydration need a long time up to 8 hours, which is time-consuming and energy-consuming.
Chinese invention patent application publication CN1760412A disclosed a method for producing a solvent spun regenerated bamboo cellulose fiber, which has the following disadvantages. 1. The producing process is complicated, for example, there are three steps of hydrolysis, acidolysis and enzymolysis during the pretreatment of pulp. The pretreatment needs a long time to perform a hydrolysis of 3-14 hours, an acidolysis of 3-11 hours and an enzymolysis of 2.2-14 hours. In addition, the pretreatment will produce a large amount of industrial waste water because of the hydrolysis and acidolysis. 2. The technical solution will result in a unstable pulp solution since it lacks a process of pre-dissolving.
Chinese invention patent application publication CN1851115A disclosed a method for producing a regenerated bamboo fiber directly from a papermaking bamboo pulp, in which high energy radiation is used to treat the pulp. However, this method suffers a high device cost and large energy consumption, requires high quality producing environment and may result in potential damage to the worker.
SUMMARY OF THE INVENTION
One technical problem of the present invention is to provide a method for producing a solvent spun bamboo fiber with high wet modulus. The said method is easy to operate, free of industrial pollution, low energy consuming and highly safe, and thus suitable to the industrial and continual production of the solvent spun bamboo fiber in large scale.
Another technical problem of the present invention is to provide a solvent spun bamboo fiber with high wet modulus, which is produced by the above said method.
To solve the above technical problems, the present invention is achieved by the following technical solutions.
A method for producing a solvent spun bamboo fiber with high wet modulus, comprising the following steps:
(1) activating a bamboo pulp with a polymerization degree of 400-1000 is added into de-ionized water, and the pH is adjusted to 4-6; cellulase is added therein to perform the activating, and then pH is adjusted to 10-13 by adding an alkali to terminate the activating and yield a pulp paste;
(2) squeezing the above pulp paste is squeezed by vacuum dehydration to yield a cellulose having a water content of 10-60% by mass;
(3) pre-dissolving an aqueous solution containing 50-88% by mass of N-methylmorpholine-N-oxide is added into the above squeezed aqueous cellulose to yield a pre-dissolved pulp;
(4) dissolving the above pre-dissolved pulp is put into a dissolver, heated, vacuumized, dehydrated, dissolved, homogenized, and defoamed to yield a pulp solution;
(5) spinning the above pulp solution is delivered into a flow control pump by a pressure pump and sprayed through a spinneret, then bamboo fiber is spun by dry-wet spinning;
(6) water washing;
(7) bleaching;
(8) oiling;
(9) drying.
Further, in present invention, in the above said step (1), the de-ionized water has a conductivity of less than 5 μs/cm 2 a pH value of 6-8, and a temperature of 50° C.;
the cellulase in the above said step (1) is a liquid cellulase;
the outlet temperature in the above said step (3) is at 50-80° C.;
in the above said step (3), the pre-dissolved pulp has a cellulose content of 8-12% by mass and a pH value of 8-12;
in the above said step (3), the mass ratio between the aqueous cellulose and the aqueous solution containing 50-88% by mass of N-methylmorpholine-N-oxide ranges from 1:2 to 1:12;
in the above said step (4), vacuum degree is 1.0 kpa-15.0 kpa and the temperature is at 60-120° C.;
in the above said step (4), the pulp solution has a cellulose content of 11-15% by mass;
in the above said step (5), the spinning velocity is 35-100 m/min, the spinning air space is 5-50 mm, the spinning blowing temperature is 10-25° C., the spinning blowing flow is 100-500 L/H, the blowing relative humidity is 50-80%, the concentration of spinning bath is 10-30% and the spinning bath temperature is at 5-30° C.;
the water washing temperature in the above said step (6) is at 25-60° C.;
in the above said step (7), the bleaching is performed using hydrogen peroxide, wherein the circulating hydrogen peroxide has a concentration of 0.05-1.0% and a pH value of 8-13;
in the above said step (8), the circulating oil has a concentration of 0.5-5%, a pH value of 6-9 and a temperature of 50-70° C.;
the drying temperature in the above said step (9) is at 80-150° C.
In addition, the present invention provides a solvent spun bamboo fiber with high wet modulus produced by the above said method.
Among others, the present invention has the following major advantages:
the present method is easy to operate, free of industrial pollution, low energy consuming, highly safe and suitable for industrial and continuous production of solvent spun bamboo fiber in large scale;
the present method will not destroy the natural properties of the bamboo, so the bamboo fiber produced by the present method can efficiently keep its original functions such as deodorization, anti-bacterium and UV-screening;
the bamboo fiber produced by the present method ensures dress safety because it not only keeps the natural physical and chemical properties of bamboo fiber, but also has no harmful chemical remains;
the bamboo fiber produced by the present method has a high wet modulus of 15 cN/dtex or more, and the finished product made therefrom has a good dimensional stability and is not easy to deform when wet-finishing, washing and laundering, which is suitable for continuous dying, convenient for printing, and advantageous for producing high end fabrics.
DETAILED DESCRIPTION
A method for producing solvent spun bamboo fiber with high wet modulus, comprising the following steps:
(1) activating the activating process is simple and little additive agents are added, and the whole procedure only takes about one hour, and thus the time consumed is short and the process is easy to operate. The specific process is performed as follows:
Preparing process water→adding pulp→adjusting pH value→adding cellulase→terminating the activation, wherein,
when preparing process water, de-ionized water was used,
parameters: conductivity: <5 μs/cm 2 , pH: 6-8, temperature: 50° C.;
when adding pulp, a bamboo pulp was added,
parameter: polymerization degree: 400-1000;
when adjusting pH, an acid or alkali was used,
parameter: pH: 4-6;
when adding cellulase, a liquid cellulase was added,
parameters: name: CelluPract® AL70, product number: IPL 5B06610, supplier: BIOPRACT;
when terminating the activation, an alkali was added to adjust the pH value,
parameter: pH: 10-13.
(2) squeezing the above pulp paste is squeezed by vacuum dehydration to a required water content,
parameters: the aqueous cellulose has a water content of 10-60% by mass and the pulverized aqueous cellulose has a size of 3 cm*3 cm.
(3) pre-dissolving the present invention specially incorporates a step of pre-dissolving which is advantageous not only for stabilizing the quality of the pulp solution, but also for dissolving. The improved pulp solution quality leads to a finished filament with a higher quality. The specific procedures are as follows:
an aqueous solution containing 50-88% by mass of N-methylmorpholine-N-oxide is added into the squeezed aqueous cellulose, wherein the mass ratio of the aqueous cellulose and the aqueous solution containing 50-88% by mass of N-methylmorpholine-N-oxide ranges from 1:2 to 1:12, to swell the pulp, which is more favorite for dissolving uniformly and stabilizing the pulp solution;
parameters: outlet temperature: 50-80° C.; composition of the pre-dissolved pulp: 8-12% by mass of cellulose; pH value: 8-12.
(4) dissolving after passing through the pre-dissolver, the mixture enters into a dissolver, and is then heated, vacuumized, dehydrated, dissolved, homogenized and defoamed to yield an amber transparent uniform pulp solution;
parameters: vacuum degree: 1.0 kpa-15.0 kpa; temperature: 60-120° C.; composition of pulp solution: 11-15% by mass of cellulose.
(5) spinning the pulp solution was delivered into a flow control pump by a pressure pump and sprayed through a spinneret, to spin a fiber by dry-wet spinning;
parameters: spinning velocity: 35-100 m/min; spinning air space: 5-50 mm; spinning blowing temperature: 10-25° C.; spinning blowing flow: 100-500 L/H; blowing relative humidity: 50-80%; concentration of spinning bath: 10-30%; spinning bath temperature: 5-30° C.
(6) water washing the fiber was washed by water to recover the solvent, N-methylmorpholine-N-oxide, so as to increase the recovery of the solvent.
parameter: water washing temperature: 25-60° C.
(7) bleaching the washed fiber was bleached by hydrogen peroxide and stabilizer to reach the required whiteness;
parameters: concentration of circulating hydrogen peroxide: 0.05-1.0%; pH value of circulating hydrogen peroxide: 8-13; temperature of circulating hydrogen peroxide: 75° C.; stabilizer: LAVATEX9188 and DELINOL 9258; manufacturer: Dr. Th. bohme KG, Chem. Fabrik Gmbh & Co.
(8) oiling the bleached fiber was oiled to reach the required oiling rate;
parameters: concentration of circulating oil: 0.5-5%; pH value of circulating oil: 6-9; temperature of circulating oil: 50-70° C.; oil: Lemin OR, Lemin WG and Lemin AN; manufacturer: CLARIANT.
(9) drying.
After oiled, the fiber was heated to reach the required water content;
parameter: drying temperature: 80-150° C.
EXAMPLE 1
Cotton-Like Fiber
A bamboo pulp with a polymerization degree of 500 was added into a process water with a conductivity of less than (<) 5 μs/cm 2 , a pH value of 6.8 and a temperature of 50° C. Then the pH value thereof was adjusted to 4.5, followed by adding cellulase therein to perform an activation for one hour. After that, sodium hydroxide was added therein to terminate the activation and adjust the pH value to 11. After the termination of the activation, the pulp paste was squeezed by vacuum dehydration to obtain an aqueous cellulose with a water content of 45% by mass, and then the aqueous cellulose was pulverized till its grains had a size of 3 cm*3 cm. An aqueous solution containing 78% by mass of N-methylmorpholine-N-oxide was added therein, wherein the mass ratio of the aqueous cellulose to the aqueous solution of N-methylmorpholine-N-oxide was 1:4, to swell the pulp, the outlet temperature was 70° C., the pre-dissolved pulp comprised 11.5% of cellulose and the pH value thereof was 9.5. After passing through the pre-dissolver, the mixed solution entered into a dissolver, and was controlled at a vacuum degree of 5.0 kpa, and the pulp solution comprised 13.8% of cellulose.
The pulp solution was delivered by a pressure pump, sprayed through a spinneret and spun by dry-wet spinning, wherein the spinning velocity was 50 m/min, the spinning air space was 15 mm, the spinning blowing temperature was 14° C., the spinning blowing flow was 200 L/H, the blowing relative humidity was 50%, the concentration of the spinning bath was 15% and the spinning bath temperature was 8° C. After the fiber was washed by water at a washing temperature of 60° C., the washed fiber was bleached by hydrogen peroxide and stabilizer, in which the concentration of the circulating hydrogen peroxide was 0.20%, the pH value of the circulating hydrogen peroxide was 10.8 and the temperature of the circulating hydrogen peroxide was 75° C. Then the bleached fiber was oiled, in which the concentration of the circulating oil was 1.8%, pH value of the circulating oil was 6.5 and the temperature of the circulating oil was 50° C. After oiled, the fiber was dried at 125° C. to yield a finished fiber which has a denier of 1.58 dtex, a dry breaking strength of 3.5 cN/dtex, a wet breaking strength of 3.0 cN/dtex, a dry breaking elongation of 14.8%, a wet breaking elongation of 17.2%, a wet modulus of 17.9 cN/dtex, a coefficient of dry strength variation of 10%, a whiteness of 58%, an oil content of 0.23% and a moisture regain of 11.2%.
EXAMPLE 2
Medium Length Fiber
A bamboo pulp with a polymerization degree of 550 was added into a process water with a conductivity of less than (<) 5 μs/cm 2 , a pH value of 6.0 and a temperature of 50° C. Then the pH value thereof was adjusted to 4.2, followed by adding cellulase therein to perform an activation for one hour. After that, sodium hydroxide was added therein to terminate the activation and adjust the pH value to 12. After the termination of the activation, the pulp paste was squeezed by vacuum dehydration to obtain an aqueous cellulose with a water content of 55% by mass, and then the aqueous cellulose was pulverized till its grains had a size of 3 cm*3 cm. An aqueous solution containing 85% by mass of N-methylmorpholine-N-oxide was added therein, wherein the mass ratio of the aqueous cellulose to the aqueous solution of N-methylmorpholine-N-oxide was 1:3, To swell the pulp, the outlet temperature was 68° C., the pre-dissolved pulp comprised 9.5% of cellulose and pH value thereof was 9.0. After passing through the pre-dissolver, the mixed solution entered into a dissolver, and was controlled at a vacuum degree of 7.0 kpa, and the pulp solution comprised 11.2% of cellulose.
The pulp solution was delivered by a pressure pump, sprayed through a spinneret and spun by dry-wet spinning, wherein the spinning velocity was 40 m/min, the spinning air space was 25 mm, the spinning blowing temperature was 16° C., the spinning blowing flow was 350 L/H, the blowing relative humidity was 60%, the concentration of the spinning bath was 15% and the spinning bath temperature was 10° C. After the fiber was washed by water at a washing temperature of 40° C., the washed fiber was bleached by hydrogen peroxide and stabilizer, in which the concentration of the circulating hydrogen peroxide was 0.35%, the pH value of the circulating hydrogen peroxide was 10.5 and the temperature of the circulating hydrogen peroxide was 75° C. Then the bleached fiber was oiled, in which the concentration of the circulating oil was 2.5%, the pH value of the circulating oil was 7.0 and the temperature of the circulating oil was 60° C. After oiled, the fiber was dried at 110° C. to yield a finished fiber which has a denier of 2.18 dtex, a dry breaking strength of 3.33 cN/dtex, a wet breaking strength of 2.98 cN/dtex, a dry breaking elongation of 15.2%, a wet breaking elongation of 17.4%, a wet modulus of 16.8 cN/dtex, a coefficient of dry strength variation of 10%, a whiteness of 55%, an oil content of 0.25% and a moisture regain of 10.5%.
EXAMPLE 3
Wool-Like Fiber
A bamboo pulp with a polymerization degree of 600 was added into a process water with a conductivity of less than (<) 5 μs/cm 2 , a pH value of 7.3 and a temperature of 50° C. Then the pH value thereof was adjusted to 5.8, followed by adding cellulase therein to perform an activation for one hour. After that, sodium hydroxide was added therein to terminate the activation and adjust the pH value to 12.5. After the termination of the activation, the pulp paste was squeezed by vacuum dehydration to obtain an aqueous cellulose with a water content of 25% by mass, and then the aqueous cellulose was pulverized till its grains had a size of 3 cm*3 cm. An aqueous solution containing 60% by mass of N-methylmorpholine-N-oxide was added therein, wherein the mass ratio of the aqueous cellulose to the aqueous solution of N-methylmorpholine-N-oxide was 1:7, to swell the pulp, the outlet temperature was 75° C., the pre-dissolved pulp comprised 9.1% of cellulose and the pH value thereof was 10. After passing through the pre-dissolver, the mixed solution entered into a dissolver, and was controlled at a vacuum degree of 2.5 kpa, and the pulp solution comprised 12% of cellulose.
The pulp solution was delivered by a pressure pump, sprayed through a spinneret and spun by dry-wet spinning, wherein the spinning velocity was 35 m/min, the spinning air space was 40 mm, the spinning blowing temperature was 20° C., the spinning blowing flow was 500 L/H, the blowing relative humidity was 68%, the concentration of the spinning bath was 23% and the spinning bath temperature was 20° C. After the fiber was washed by water at a washing temperature of 50° C., the washed fiber was bleached by hydrogen peroxide and stabilizer, in which the concentration of the circulating hydrogen peroxide was 0.6%, the pH value of the circulating hydrogen peroxide was 11.5 and the temperature of the circulating hydrogen peroxide was 75° C. Then the bleached fiber was oiled, in which the concentration of the circulating oil was 4.0%, the pH value of the circulating oil was 7.9 and the temperature of the circulating oil was 65° C. After oiled, the fiber was dried at 105° C. to yield a finished fiber which has a denier of 3.21 dtex, a dry breaking strength of 3.28 cN/dtex, a wet breaking strength of 2.85 cN/dtex, a dry breaking elongation of 15.4%, a wet breaking elongation of 17.8%, a wet modulus of 15.2 cN/dtex, a coefficient of dry strength variation of 10%, a whiteness of 50%, an oil content of 0.3% and a moisture regain of 11%.
Each physical index of the bamboo fiber produced in examples 1-3 of the present invention was compared with the data disclosed in CN1190531C and CN1851115A, and the index of the first class product in the Cotton-like Bamboo Viscose Staple Fiber Standard FZ/T52006-2006. The detailed data were shown in table 1.
TABLE 1
denier
Dry strength
Wet strength
Dry breaking
Wet modulus
(dtex)
(cN/dtex)
(cN/dtex)
elongation %
(cN/dtex)
CN 1190531C
Example 1
1.80
3.4
—
12
—
Example 2
70 dtex/100 F
3.5
—
10
—
CN 1851115A
Example 1
1.90
3.5
—
10
—
Example 2
1.90
2.8
—
9
—
Example 3
150 dtex/36 F
3.6
—
10
—
Example 4
1.90
3.4
—
10
—
Present
Example 1
1.58
3.5
3.0
14.8
17.9
invention
Example 2
2.18
3.33
2.98
15.2
16.8
Example 3
3.21
3.28
2.85
15.4
15.2
the index of the first class
≧1.67
≧2.1
≧1.1
≧17
—
product in Cotton Bamboo
Viscose Staple Fiber Standard
FZ/T 52006-2006,
It can be seen from examples 1-3 that the bamboo fiber produced in present invention has a high wet modulus of 15 cN/dtex or more.
EXAMPLE 4
Shrinkage Test
Test conditions: (1) the fabric was a woven fabric; (2) at the same atmospheric conditions, the temperature was 20° C. and the relative humidity was 58%; (3) the used shrinker model M988 was used.
The fabrics woven by the bamboo fiber produced in examples 1-3 were compared with that woven by viscose bamboo fiber, and the detailed data were shown in table 2.
TABLE 2
fabric
fabric
fabric
Viscose
woven
woven
woven
bamboo
by the
by the
by the
fiber
bamboo fiber
bamboo fiber
bamboo fiber
Property index
fabric
in example 1
in example 2
in example 3
shrink-
longi-
6.24
1.3
1.9
1.6
age (%)
tudinal
trans-
1.26
0.4
0.2
0.3
verse
It can be seen from the above data that the fabric using the bamboo fiber produced by the present invention has a much lower shrinkage than that of the viscose bamboo fiber fabric, and thus has a good dimension stability.
EXAMPLE 5
Shrinkage Test of the Yarn in Boiling Water
When testing, the yarn was 32 s.
The yarns spun by the bamboo fiber produced in examples 1-3 were compared with that spun by viscose bamboo fiber and the detailed data are shown in table 3.
TABLE 3
viscose
Yarn spun
Yarn spun
Yarn spun
bamboo
by the
by the
by the
fiber
bamboo fiber
bamboo fiber
bamboo fiber
Property index
yarn
in example 1
in example 2
in example 3
Shrinkage of the
7.0
0.56
0.49
0.53
yarn in boiling
water (%)
It can be seen from the above data that the shrinkage of the yarn using the bamboo fiber produced in present invention is only about 0.5% which is far lower than that of viscose bamboo fiber.
Undoubtedly, the present invention is not restricted to the examples in the above embodiment and may also include various modifications and variations. In sum, the scope of the present invention may include those modifications or alternatives and variations that are obvious to an ordinary person skilled in the art. | A solvent spun bamboo fiber with a high wet modulus and a producing method thereof are disclosed. The producing method includes: activating by adding a bamboo pulp into de-ionized water, adjusting the pH value, adding cellulase and adjusting the pH value by adding alkali; squeezing by vacuum dehydration; pre-dissolving by adding an aqueous solution containing 50-88% by mass of N-methylmorpholine-N-oxide; then dissolving by putting the above pre-dissolved mixture into a dissolver, heating, vacuumizing, dehydrating, dissolving, homogenizing and defoaming; spinning by spraying through a spinneret and forming a bamboo fiber by dry-wet spinning; water washing; bleaching; oiling; and drying. The present method is simple to operate, free of industrial pollution, low energy consuming, and highly safe. The bamboo fiber produced by the present method not only keeps the natural physical and chemical properties of bamboo fiber, but also has a high wet modulus without harmful chemical residues. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to a heat exchanger within a suction accumulator particularly adapted for use in a refrigeration system.
Most compressors used in refrigeration systems are designed for the compression of gaseous refrigerant. Under some circumstances, however, a certain amount of liquid may flow from the evaporator into the inlet of the compressor so as to cause a condition known as slugging. If this occurs after the system is shut down, large quantities of condensed refrigerant return through the suction line to the crankcase of the compressor, and when the compressor is restarted, the large quantity of liquid refrigerant present therein results in abnormally high pressures which frequently causes blown gaskets, broken valves, and the like.
Suction accumulators prevent this from occurring by providing a reservoir for the liquid refrigerant at the inlet to the compressor, and serve to separate the gaseous and liquid components of the refrigerant so that only the gaseous component and a controlled amount of liquid is admitted to the inlet of the compressor. One type of accumulator comprises a vessel having a generally U-shaped tube mounted therein, wherein one end of the tube is connected to an outlet tube leading from the vessel, and the other end of which is open to the interior of the vessel. As the incoming liquid refrigerant flows into the vessel, it collects in the bottom thereof whereas the gaseous component is carried off through the tube to the outlet. This type of suction accumulator is disclosed in U.S. Pat. No. 3,420,071, for example.
Another type of suction accumulator comprises a storage vessel having a generally vertical weir member located between the vessel inlet and outlet and which forms, in conjunction with the confronting walls of the vessel, a storage reservoir and an outlet flume on opposite sides of the weir. The vessel fluid inlet is located on the reservoir side of the weir member and the fluid outlet on the flume side thereof. This type of accumulator is disclosed in U.S. Pat. No. 4,041,728.
In order to improve the efficiency of refrigeration systems, it has been found desirable to cool the refrigerant leaving the condenser prior to its entering the high pressure side of the evaporator. In order to accomplish this, the prior art teaches providing a heat exchanger coil within the suction accumulator so that the relatively warm refrigerant from the condenser can be cooled through heat exchange with the relatively cool liquid refrigerant in the accumulator. In most cases, the heat exchanger simply comprises a coil disposed within the accumulator. In other cases the coil is in close proximity or in contact with the gaseous refrigerant tube, or mounted in a more remote location. Such an arrangement results in an inefficient transfer of heat between the respective fluids, and causes manufacturing problems. Prior art patents disclosing such heat exchangers include U.S. Pat. Nos. 2,393,854, 2,467,078, 2,472,729, 2,530,648, 3,021,693, 2,270,934, and 3,765,192.
SUMMARY OF THE INVENTION
The suction accumulator heat exchanger of the present invention overcomes the disadvantages of the prior art by virtue of the fact that the heat exchange fluid passageway is formed as a jacket around at least a portion of the gaseous refrigerant passageway, thereby resulting in optimum heat exchange between the respective fluids. In one embodiment of the invention, the heat exchange passageway is formed as an annular passageway around the U-shaped gaseous refrigerant conduit. In another embodiment, the heat exchange passageway is formed within the weir member, which divides the vessel into the storage and outlet flume portions. In the latter embodiment, easily manufactured and assembled metal stampings can be utilized for the weir-heat exchanger.
The advantage of arrangement described above is that the refrigerant flowing through the heat exchange passageway comes into direct heat exchange contact both with the incoming liquid and the gaseous refrigerant within the storage portion of the vessel, and with the gaseous refrigerant flowing through the outlet flume or U-shaped tube, as the case may be. As opposed to many prior art heat exchangers which are disposed within the lower portion of the accumulator so that they are submersed in the relatively placid liquid refrigerant, the heat exchanger of the present invention is always subjected to moving refrigerant, either gaseous or liquid.
Specifically, the present invention relates to a heat exchanger integrated with a suction accumulator including a storage vessel having a refrigerant inlet, and means defining a first fluid passageway in the vessel having an inlet in communication with the interior of the vessel and an outlet extending out of the vessel. The heat exchanger comprises a jacket disposed over at least a portion of the surface of the means defining a first fluid passageway and being spaced therefrom so as to form a second fluid passageway between the jacket and the surface. The second fluid passageway is sealed from a first passageway and from the interior of the vessel and has a fluid inlet and a fluid outlet each leading to the exterior of the vessel.
It is an object of the present invention to provide a suction accumulator having a heat exchanger wherein the heat exchange passageway is formed as a jacket around at least a portion of the gaseous refrigerant passageway within the accumulator vessel.
It is a further object of the present invention to provide a suction accumulator heat exchanger wherein the refrigerant flowing through the heat exchanger comes into direct heat exchange contact both with the incoming liquid and gaseous refrigerant and with the gaseous refrigerant flowing through the gas-liquid separation flume or conduit.
A still further object of the present invention is to provide a suction accumulator heat exchanger which is simple in design and economical to manufacture.
These and other objects of the present invention will become more apparent from the detailed description together with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially sectioned elevational view of one embodiment of the suction accumulator and heat exchanger according to the present invention;
FIG. 2 is a perspective view of the weir member of the suction accumulator and heat exchanger of FIG. 1;
FIG. 3 is a sectional view taken along line 3--3 of FIG. 1;
FIG. 4 is a sectional view taken along line 4--4 of FIG. 1;
FIG. 5 is an elevational view of the suction accumulator and heat exchanger with portions of the outer vessel cut away;
FIG. 6 is a longitudinal sectional view of a second embodiment of the invention;
FIG. 7 is a transverse sectional view taken along line 7--7 of FIG. 6;
FIG. 8 is a fragmentary sectional view taken along line 8--8 of FIG. 7;
FIG. 9 is a fragmentary sectional view taken along line 9--9 of FIG. 7; and
FIG. 10 is a sectional view taken along line 10--10 of FIG. 6.
DETAILED DESCRIPTION
With reference to FIGS. 1-4, suction accumulator 12 comprises a pressure vessel 14, which is preferably formed of two identical half sections 16 and 18 produced from sheet metal by a stamping process. Vessel 14 has a generally cylindrical midsection with convex top 20 and bottom 22 ends. Preferably, sections 16 and 18 are joined together by overlapping seams 24 and 26, which are copper brazed in a hydrogen atmosphere furnace, thereby creating a strong, fluid tight seam. It should be noted that the seams 24 and 26 extend lengthwise of the vessel 14 and lie within a plane coinciding with the longitudinal axis of the vessel, which is preferably vertically disposed when the suction accumulator 12 is installed.
A vertically disposed outlet pipe fitting 26 is sealed in an extrusion-pierced, collared aperture in the top portion of vessel section 16, with the outer end 28 thereof being enlarged to form the female member of a sweat connection with the suction line of a mechanical compressor (not shown). Inlet fitting 30 is also received within an extrusion-pierced, collared aperture extending through a bulbous portion 32 of vessel wall section 18, and is horizontally disposed and tangentially positioned with respect to the arcuate inner surface 34 of vessel section vessel section 18. This is so that the incoming refrigerant will impinge on a surface which is shaped to cause the fluid to flow round the vessel axis with a swirling motion. This swirling motion causes the liquid refrigerant to flow to the lower portion of the accumulator and the gaseous component to flow upwardly, thereby providing improved gas-liquid separation. Furthermore, as the refrigerant flows around surface 34, it will impinge on weir member 36, which contains the heat exchanger, as will be described in greater detail below. It will be appreciated that by having the incoming refrigerant from the evaporator impinge on the heat exchanger containing weir member 36 prior to settling in the lower portion of vessel 14, improved heat transfer between it and the liquid flowing through the heat exchanger is realized. The outer end 38 of inlet fitting 30 is enlarged to form the female member of a sweat connection with the compressor return line from the refrigerant evaporator.
Weir member 36 is a non-planar sheet metal plate formed by a stamping process, and is so formed that when it is positioned vertically within vessel 14, its bottom edge 40 and side edges 42 and 44 sealingly attach to the inner surface of the vessel as by copper brazing. Preferably, weir member 36 is wholly contained within one side section 16 of vessel 14, and is shaped such that a generally U-shaped outlet flume having two upright passageways 46 and 48 are formed between it and vessel section 16. Passageways 46 and 48 are formed by two generally planar rectangular panel sections 50 and 52 integrally connected together along a vertical ridge 54 which abuts the vessel wall 56. Panel sections 50 and 52 terminate above the bottom end of the vessel but have integrally connected triangular panel extensions 58 and 60 which are angled away from the vessel wall and integrally joined together in the shape of a half pyramid. Two coplanar wing sections 62 and 64, depending from panel extensions 58 and 60, span the spaces between the lower ends of the panel extensions 58 and 60 and the adjacent wall of vessel half section 16. The wing sections 62 and 64 and panel extensions 58 and 60 jointly define the inner wall of the connecting leg 61 of the U-shaped outlet flume.
In addition to defining the outlet flume, weir member 36 also defines storage reservoir 66, which is formed between weir member 36 and the inner wall 34 of vessel half section 18.
A liquid bleed-through aperture 68 having a diameter of 1/16", for example, is located at the bottom end of weir member 36 in wing section 62. Preferably, aperture 68 and the area around it is recessed away from the reservoir 66 so that when a screen 70 is welded over the recessed area, a plurality of screen openings are available to the recessed area and will prevent clogging of the fluid path leading from one side of weir member 36 to the other.
The top portion 72 of outlet flume leg 48 is enlarged by forming a bulbous section 74, which extends under and slightly beyond the vertically disposed outlet fitting 26. Preferably, this bulbous section 74 is streamlined as much as possible so that the incoming refrigerant liquid does not splash excessively in a vertical direction either upwardly or downwardly. The top of panel 50 defining the inlet leg 46 of the flume has a narrow lip 76 which extends over an edge of a horizontally disposed baffle plate 78. A vertically projecting twist tab 80 is provided on the top edge of outlet leg panel 52 to locate and hold baffle plate 78 in position on weir member 36 during assembly.
Baffle plate 78 is shaped to conform to the cross sectional shape of the inside of vessel 14 level with the top of weir member 36 but excluding the area over the top of the inlet leg 46 of the flume which is left open. A large diameter opening 82 adjacent the center of baffle plate 78 forms the primary fluid outlet from the reservoir 66 to the flume inlet leg 46. Preferably, this opening is not centered on the vessel axis but is offset towards the inlet fitting 30 so that the entire opening is upstream from the inlet to reservoir 66. The area of opening 82 as well as the cross sectional areas of the outlet flume are sized so that they are all larger than the area of the vessel inlet or outlet. A second aperture 84 extends through baffle plate 78 for the purposes of pressure equalization. Up to this point, the suction accumulator 12 described is identical to that disclosed in U.S. Pat. No. 4,041,728.
The heat exchanger according to the present invention is formed against one side 86 of weir member 36 and comprises a non-planar sheet metal stamping, which is generally in the shape of an angled piece of sheet metal 88 having raised portions, which define the tortuous fluid passageways for the liquid refrigerant flowing therethrough. More specifically, sections 90 and 92 lie in respective planes which intersect along the fold line 94. Ridges 96 and 98, which extend from one edge of section 90 to the opposite edge of section 92, form a pair of generally parallel, tortuous fluid passage ways leading from the raised manifold 100 in communication with inlet 102 to the raised manifold 104 in communication with outlet 106. The planar portions of sections 90 and 92 and the respectively coplanar portions between raised ridges 96 and 98 are copper brazed against the facing side of weir member 36. Inlet 102 and outlet 106 extend through half section 18 for connection to the condenser outlet (not shown) and evaporator inlet (not shown), respectively.
When suction accumulator 12 is connected in a refrigerant compressing-evaporating system between the compressor and evaporator, the incoming refrigerant liquid, which may be substantially liquid, substantially gaseous, or a mixture of liquid and gas including some lubricating oil, enters vessel 14 through the tangentially disposed inlet fitting 30 at the top of the reservoir 66 immediately beneath the baffle plate 78.
The incoming refrigerant is projected against the confronting cylindrical surface 34 of the vessel 14 and caused to flow around the vessel in a generally circular or helical path, past the angularly disposed weir plate 36 and the similarly angularly disposed heat exchanger surface 88, and around the remaining cylindrical section of the vessel 14. The swirling action of the liquid-gaseous refrigerant creates a vortex in the reservoir 66 and slings the heavier liquid portion of the refrigerant toward the outer wall of the reservoir 66 away from the vicinity of the opening 88 in baffle 78. The lighter, relatively dry refrigerant gas in the vortex area is free to pass out of the reservoir 66 via opening 82 and enter the upper chamber of the accumulator 12 with a minimum of pressure drop. The liquid is temporarily retained in reservoir 66 as the gaseous portion flows out through the opening 82, then over the top of weir member 36 down flume inlet leg 46, across connecting leg 61, up flume outlet leg 48 and then vertically out of the vessel 14 through outlet fitting 28.
As the gaseous refrigerant follows this course, it first contacts the confronting side 88 of the heat exchanger while it is in the reservoir 66, and then contacts panel sections 50 and 52 and triangular extensions 58 and 60 of weir member 36, as it flows through the outlet flume. It will be appreciated that the panel sections 50 and 52 of weir member 36 form the rear walls for the heat exchange passageways. This arrangement permits the gaseous component of the refrigerant to come into direct heat exchange contact with the refrigerant flowing through the heat exchanger on both sides of weir member 36.
Since the compressor lubricant entrained in the liquid or gaseous refrigerant entering accumulator 12 tends to collect as a liquid in the bottom of reservoir 66, the metering aperture 68 in conjunction with the pressure differential existing between the reservoir 66 and the outlet flume induces a metered flow of liquid lubricant into the gaseous refrigerant stream flowing through the flume, thereby ensuring that the lubricant is continually fed from the accumulator 12 to the compressor.
As mentioned previously, the heat exchange inlet 102 connects to the condenser outlet, and the heat exchange outlet 106 connects to the inlet of the evaporator. The refrigerant flowing through the heat exchanger, which, as it will be noted, flows against the flow of incoming refrigerant to the suction accumulator 12, will be cooled. Additionally, the refrigerant flowing through the accumulator 12 will be heated, thereby resulting in more efficient operation of the compressor.
Referring now to FIGS. 6-10, a modified form of the suction accumulator and heat exchanger of the present invention will be described.
The accumulator 108 comprises a vessel 110 having a cylindrical midsection 112 and end caps 114 and 116, the latter having a mounting lug 118. Refrigerant inlet fitting 120 and outlet fitting 122 are received in suitably dimensioned openings in upper end cap 114 and are copper brazed thereto. Baffle plate 124 is brazed to midsection 112 and is cut away to form a pair of arcuate spaces 126 and 128 between it and the inner wall 130 of vessel midsection 112. A raised ridge 132 serves to deflect the incoming refrigerant from inlet fitting 120 toward the inner wall 130 of vessel midsection 112 and toward openings 126 and 128.
Received within the lower portion of vessel 110 and brazed to vessel midsection 112 is a partition member 134 having a bleed-through orifice 136 formed therein. Also formed in partition member 134 are a pair of pierced and drawn openings 138 and 140, which extend upwardly as shown in FIG. 6. A screen 142 is welded to partition member 124 and prevents bleed-through orifice 136 from becoming clogged.
A pair of vertically oriented tubes 144 and 146 are positioned around and brazed to drawn openings 140 and 138, respectively. Inlet tube 146 has a flared top 148, and the top 150 of tube 144 is drawn down so that it may be snugly received within outlet fitting 122. An opening 152 in tube 144 provides for pressure equalization between tube 144 and the interior of vessel 110.
The heat exchanger of this embodiment of the invention is formed by a pair of tubes 154 and 156 concentrically positioned around tubes 144 and 146, respectively, such that a pair of annular passageways 158 and 160 are formed therebetween. The upper ends 162 and 164 of tubes 154 and 156 are drawn down into snug engagement with tubes 144 and 146 and brazed thereto. A flange member 166 having openings 168 and 170 is brazed to partition member 134 and to the lower ends of outer tubes 154 and 156. It will be noted that a pass over duct 172 is formed between annular heat exchange passageways 158 and 160. Thus, a completely sealed heat exchange passageway is formed between the suction accumulator tubes 144 and 146 and partition member 134 and outer tubes 154 and 156 and flange member 166.
An inlet tube 173 is brazed to an appropriate fitting portion 174 on tube 154 and is also brazed at its other end to inlet fitting 176. In a similar fashion, the outlet tube 178 for the heat exchanger is brazed to a fitting portion 180 on tube 156 and is brazed at its other end to heat exchange outlet fitting 182. As can be seen, the heat exchange system is completely sealed from the accumulator system so that no intermixing of fluids is possible.
As the incoming liquid-gas refrigerant flows into accumulator 108 through inlet fitting 120, it strikes baffle plate 124 and is deflected outwardly toward openings 126 and 128 by ridge 132. It drops down through openings 126 and 128 and continues to flow in a swirling motion around the midsection 112 of vessel 110, with the liquid refrigerant accumulating in the lower portion of vessel 110 and the gaseous, lighter refrigerant rising. As was the case with the previous embodiment, the swirling motion imparted to the incoming refrigerant improves the liquid-gas separation.
The gaseous refrigerant rises and passes into tube 146 whereupon it flows downwardly into the manifold 184 formed between partition member 134 and end cap 116. After picking up the proper amount of lubricant, which flows into manifold 184 through bleed-through orifice 136, the gaseous refrigerant flows upwardly through tube 144 and out outlet fitting 122.
The heat exchange refrigerant from the outlet of the condenser (not shown) flows in through inlet fitting 176 through tube 173 into the annular passageway 158 formed between tubes 154 and 144. It flows downwardly into the space between partition member 134 and flange member 166, across duct 172, and upwardly through the annular passageway 160 formed between tubes 146 and 156. From there it flows out through tube 178 and outlet fitting 182 to the inlet of the evaporator (not shown). As can be seen, the heat exchange liquid flows in the opposite direction of the flow of gaseous refrigerant in the suction accumulator. This results in the most efficient transfer of heat from the refrigerant in the suction accumulator system to the refrigerant in the closed heat exchange system.
While this invention has been described as having a preferred design, it will be understood that it is capable of further modification. This application is, therefore, intended to cover any variations, uses, or adaptations of the invention following the general principles thereof and including such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and fall within the limits of the appended claims. | A heat exchanger in a suction accumulator for the compressor of a refrigeration system wherein the suction accumulator comprises a storage vessel having a liquid and gaseous refrigerant inlet, and means within the vessel defining a fluid passageway for separating the gaseous and liquid components and conducting the gaseous component and a controlled amount of liquid out of the storage vessel to the inlet of the compressor. This fluid passageway may comprise a generally U-shaped conduit or, alternatively, a U-shaped flume formed by a vertical weir member. The heat exchanger comprises a jacket disposed over at least a portion of the surface of the gaseous refrigerant conduit or weir member and is spaced therefrom so as to form a second fluid passageway, which is sealed from the gaseous refrigerant passageway and the interior of the vessel. An inlet and outlet lead from the second fluid passageway out of the storage vessel. | 5 |
CROSS REFERENCE TO RELATED PATENT APPLICATION
This patent application is a continuation-in-part of U.S. patent application Ser. No, 08/703,342, filed Aug. 26, 1996, now U.S. Pat. No. 5,737,187, entitled "Apparatus, Method and System for Thermal Management of an Unpackaged Semiconductor Device," by Minh H. Nguyen and Mark S. Tracy, and is incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to an apparatus, method and system for thermal management of a semiconductor device, and, more particularly, to an apparatus, method and system for mechanical isolation combined with removal and dissipation of heat generated by a high clock frequency, high circuit density unpackaged chip-on-board semiconductor device.
2. Description of the Related Technology
Ever increasing market pressure for smaller, faster, and more sophisticated end products using integrated circuits has driven the electronics industry to develop integrated circuits which occupy less volume yet operate at heretofore unheard of clock frequencies employing incredible circuit densities. For example, two current production integrated circuits which serve as microprocessors are manufactured by the Intel Corporation called the PENTIUM (PENTIUM is the registered trademark of the Intel Corporation) and the PENTIUM II (PENTIUM II is the registered trademark of the Intel Corporation). The PENTIUM has over 3 million circuits in a single semiconductor die using 0.6 to 0.35 micron technology, operates at speeds ranging up to 266 MHz. The PENTIUM II has over 10 million circuits in a single semiconductor die and operates at speeds ranging up to 333 MHz, and is projected to soon exceed 400 MHz.
Because of the fragility of integrated circuit dice, and their susceptibility to environmental influences and mechanical trauma, individual or multiple integrated circuit dice have traditionally been enclosed in a protective "package" such as Pin Grid Array ("PGA") or Ball Grid Array ("BGA"). These packages may be made of plastic or ceramic materials, and provide electrical leads so that the enclosed die (or dice) may be electrically connected to a substrate, such as a printed circuit board ("PCB").
As the end products which utilize these increasingly powerful integrated circuits continue to shrink in size, such as laptop computers and other consumer, commercial, and military electronics, the space available for mounting the packaged integrated circuit die (or dice) is also reduced. Unfortunately, as integrated circuits grow in complexity and circuit density, the number of package leads needed to connect the packaged die (or dice) to the substrate also increases, thereby requiring more, not less, area to provide reliable electrical interconnections between the surface mount package to the substrate. Further, as the number of package leads increases, so does the capacitance, inductance and resistance of the package leads, which can degrade signal fidelity to and from the die (or dice).
In an effort to eliminate the above problems associated with modern packaging, some integrated circuit manufacturers have eliminated packages, and placed the unpackaged integrated circuit die (or dice) directly on the substrate. This practice of connecting unpackaged die (or dice) directly on a substrate is generically referred to as "chip-on-board" packaging.
An example of chip-on-board technology which is currently being manufactured and sold is the Intel Corporation's TCP PENTIUM ®. The TCP PENTIUM ("TCP" stands for Tape Carrier Packaging) is a version of the PENTIUM in which the microprocessor integrated circuit die is an unpackaged die mounted face up on a PCB substrate and electrically connected to the PCB substrate using tape automated bonding technology. The PCB substrate also has numerous other integrated circuit packages directly connected to the substrate. When multiple dice are mounted on the same substrate, whether some or all are packaged or unpackaged, the combination is usually referred to as a multi chip module ("MCM").
Chip-on-board die leads may be electrically connected to the substrate face down using solder ball bonding (also known as "flip-chip") or in either a face down or face up arrangement using tape automated bonding ("TAB"). The exposed face of the die (i.e. the face opposite the face directly connected to the substrate) may be covered with a mechanically protective encapsulent.
The move to unpackaged chip-on-board technology has overcome some of the problems associated with higher clock speeds and circuit densities, but as is often the case, a successful solution to one problem often creates one or more new problems which must be addressed. One problem with unpackaged dice is that although advances in passivation allow unpackaged dice to withstand normal environmental influences better, unpackaged dice are still fragile and easily damaged by very minor external mechanical trauma, whether or not the dice are topped with an encapsulent. Although traditional component boards and MCM's (i.e. those having only packaged dice) have always been regarded and treated as delicate, this has usually been due to the risk of static electric discharge during handling which could damage the integrated circuits, not the mere accidental touching of a packaged die on a substrate board. An unpackaged die (or dice) with an encapsulent cap generally should not be subjected to more than 4.5 kilograms (9.9 pounds) of force on the center of the exposed face, however, lower forces may be damaging depending on the specific design parameters of a given die (or dice). A human hand in the mere act of touching an object, typically can and will exert forces greater than 4.5 kilograms.
Component boards and MCM's are usually fabricated at one location and then transported to either a component assembly location of either the original equipment manufacturer or a third party assembler. Sometimes, the component boards and/or MCM's are sold directly to end users who either need to repair or upgrade existing end products. This presents component manufacturers with the dilemma of shipping factory tested known good boards and MCM's having unpackaged dies, only to experience a higher than acceptable mortality rate in the course of normal shipping, and more often than not, normal handling by third party assemblers or end users.
Another problem with an unpackaged die (or dice) is related to the dissipation of waste heat generated by the die (or dice), also known as thermal management. As clock frequency and circuit density increase and die size decreases, the die power density and resulting production of waste heat also increase. As the quantity of waste heat increases, the effective steady state operating temperature of the die may also increase. If the steady state operating temperature of the die becomes greater than the maximum functional operating temperature of the die, the integrated circuit die may suffer degraded performance and/or experience logic errors. If the steady state operating temperature of the die becomes high enough, the die may experience errors in clock timing potentially causing the chip and/or system to lock-up. If the temperature becomes extremely high, the die may become permanently damaged and fail.
In addition to thermal performance degradation and/or damage, another problem of chip-on-board technology associated with increased waste heat is caused by the differences in the thermal coefficients of expansion ("TCE") between the die and the substrate, commonly referred to as TCE mismatch. Integrated circuit dice are composed of silicon whereas most substrates are composed of organic materials. The TCE of organic substrates are much greater than the TCE of silicon dice, therefore as temperature increases the organic substrates expand more than the silicon dice. Further, in a powered state, unpackaged dice conductively transfer most of their generated waste heat to the substrate. Therefore when an end product containing a chip-on-board die is turned on, the die temperature rises from the ambient temperature to the steady state operating temperature, which also raises the temperature of the organic substrate. Because of the TCE mismatch, the substrate expands more than the chip-on-board die. This condition results in a large mechanical stress being placed on the mechanically fragile die and the electrical connections to the substrate. Repeated power cycling can result in mechanical fatigue and eventual failure of die or the electrical connections, thereby destroying the use and/or value of the end product.
The present accepted solution for thermal management and TCE mismatch of unpackaged dice is to use the substrate, with or without thermal vias at the die attachment site, as a heat sink wherein the waste heat generated by the unpackaged die (or dice) is conductively transferred from the die to the substrate where the heat is both conductively transferred away from the die in the substrate and also convectively and radiantly transferred from the substrate to the ambient environment. If additional thermal enhancements are required, such as an externally attached heat sink, the heat sink is attached to the side of the substrate opposite the side where the unpackaged die is mounted. If an external heat sink is attached to the substrate, this provides an additional conductive path to transfer heat away from the die to the substrate, and then on to the external heat sink, where the heat is radiantly and convectively transferred to the ambient environment. Unfortunately, with the current trend of increasing power densities and consequent increasing waste heat generation of unpackaged die (or dice), these thermal management techniques are limited at best and more likely unacceptably inadequate.
Another problem associated with increasing clock speeds of semiconductor devices is that of radio frequency interference ("RFI"), also known as electromagnetic interference ("EMI"). Current production semiconductor dice are operating at speeds which are the same as radio frequencies used in wireless communications. For example, United States television channel 13 operates at approximately the 210 MHz frequency, while at the other end of the spectrum analog cellular telephones both receive and transmit at frequencies centered at approximately 880 MHz. Further, semiconductor devices can both emanate (transmit) and intercept (receive) electromagnetic fields at the operating (fundamental) frequency of the semiconductor device, as well as, at other (harmonic) frequencies greater than the operating frequency. Both emanation and interception of electromagnetic fields is often undesirable. Emanation of undesired electromagnetic fields can interfere with proper operation of nearby electrical devices or radio signal reception/transmission, whereas interception of strong radio signal transmissions (such as from a nearby cellular phone) could possibly cause a semiconductor device to malfunction and produce erroneous output. Additionally, the Federal Communications Commission ("FCC") has issued regulations which require that semiconductor devices and electronic systems not emanate radio frequencies above certain very low power levels (Part 15 of FCC Rules).
What is needed is a apparatus, method and system to provide the necessary thermal management of high power density packaged or unpackaged dice during normal operation, which minimizes both emanation and interception of electromagnetic fields by packaged or unpackaged high frequency dice, and which also protects unpackaged dice from mechanical trauma during normal transportation, handling, installation, and operation.
SUMMARY OF THE INVENTION
Objects of the Invention
It is therefore an object of the present invention to create an apparatus, method and system to manage heat removal and dissipation from one or more packaged or unpackaged, high speed, high circuit density semiconductor dice mounted on a chip-on-board substrate.
Another object of the present invention is to create an apparatus, method and system to provide mechanical isolation and protection for one or more packaged or unpackaged, high speed, high circuit density semiconductor dice mounted on a chip-on-board substrate.
Another object of the present invention is to create an apparatus, method and system to provide electromagnetic shielding (isolation) for one or more packaged or unpackaged, high speed, high circuit density semiconductor dice mounted on a chip-on-board substrate.
A further object is to create an apparatus, method and system to modularize into a single unit one or more packaged or unpackaged, high speed, high circuit density semiconductor dice mounted on a chip-on-board substrate with a mechanically protective thermal management device.
A further object is to create an apparatus, method and system to modularize into a single unit one or more packaged or unpackaged, high speed, high circuit density semiconductor dice mounted on a chip-on-board substrate with a mechanically protective and electromagnetic isolating thermal management device.
Another object of the present invention is to create an apparatus, method and system to remove and dissipate heat produced by a semiconductor device having at least one unpackaged semiconductor die mounted on a chip-on-board substrate.
Another object of the present invention is to create an apparatus, method and system to isolate a semiconductor device having at least one unpackaged semiconductor die mounted on a chip-on-board substrate from electromagnetic fields external to the semiconductor device.
Yet another object is to create an apparatus, method and system to provide a single module semiconductor device having one or more unpackaged semiconductor dice on a substrate with improved thermal management in a mechanically protective enclosure which may be shipped, handled, installed in an end product and operated in an end product with minimized chance of mechanical and/or thermal damage of the one or more semiconductor dice.
Yet another object is to create an apparatus, method and system to provide a single module semiconductor device having one or more unpackaged semiconductor dice on a substrate with improved thermal management and electromagnetic shielding in a mechanically protective enclosure which may be shipped, handled, installed in an end product and operated in an end product with minimized chance of mechanical and/or thermal damage of the one or more semiconductor dice.
Yet another object is to create an apparatus, method and system to provide a single module semiconductor device having one or more unpackaged semiconductor dice on a substrate with improved thermal management in a mechanically protective enclosure which may be handled and installed in an end user's existing end product by an original component manufacturer, a third party or an end user to replace or upgrade a damaged or outdated semiconductor device in the end user's existing end product with minimized chance of mechanical damage of the one or more unpackaged semiconductor dice.
An advantage of the present invention is the ability to upgrade an existing end product such as a laptop computer by replacing an existing semiconductor device (not employing the invention) contained within an end product chassis with a higher speed and/or higher circuit density semiconductor device (which employs the invention) having a higher heat output without modifying, or with minimal modification, of the passive or active cooling system of the end product, by conducting the additional heat more uniformly throughout the existing available space within the chassis.
Another advantage of the present invention is the ability to upgrade an existing end product such as a laptop computer by replacing an existing semiconductor device (not employing the invention) contained within an end product chassis with a higher speed and/or higher circuit density semiconductor device (which employs the invention) which has electromagnetic shielding without modifying, or with minimal modification, of the end product.
A novel feature of the present invention is the ability to remove and dissipate the heat generated by one or more unpackaged semiconductor dice on a substrate by compliantly engaging the exposed face or faces of the one or more dice with minimal compressive force.
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects, advantages and novel features of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
Disclosure of the Invention
According to the present invention, the foregoing and other objects, advantages and features are attained by a thermal management structure which sandwiches both sides of a chip-on-board substrate. The thermal management structure provides an unpackaged die (or dice) and any packaged die (or dice) on the chip-on-board substrate with both a mechanical protective cover and maximum conductive heat transfer interface contacts to a heat sink mass. In an aspect of the invention, the thermal management structure also shields (isolates) the chip-on-board substrate from the electromagnetic environment external to the thermal management device.
The mechanical protective cover aspect of the invention allows the chip-on-board substrate to be shipped, handled, installed, and operated with minimal risk of the unpackaged die or dice, as well as any packaged dice, being physically damaged by an accidentally touching with a human hand, tool, shipping carton, end product component or other foreign object. The maximum conductive heat transfer interface aspect of the invention allows a heat sink mass to be compliantly thermally engaged to both the side of the substrate opposite the side where the packaged or unpackaged die is mounted (hereinafter "board side") as well as to the fragile exposed face of the die, whether or not the die has an encapsulent top (hereinafter "exposed face").
By providing the maximum conductive heat transfer interface with both the exposed face of the packaged or unpackaged die and the board side of the substrate, the thermal gradient across the die and the substrate immediately attached to the die is reduced, thereby reducing the ultimate steady state operating temperature of the die and the substrate for a given ambient temperature. By reducing the ultimate steady state operating temperature, the likelihood of thermal performance degradation, damage, or TCE mismatch induced failure of the packaged or unpackaged die is considerably reduced.
According to another aspect of the invention, the thermal management structure comprises a heat sink mass having a first heat sink piece and a second heat sink piece. Both heat sink pieces have corresponding offsetting mounting brackets (or tabs) which align with mounting sites in the chip-on-board substrate. The offsetting mounting brackets serve to align and fixedly attach the first and second heat sink pieces with the chip-on-board substrate in a predetermined configuration. The offsetting mounting brackets further act as spacers which define and maintain a predetermined minimum distance between an inside face of the respective heat sink piece with the corresponding side of the chip-on-board substrate and any packaged or unpackaged chips thereon.
Mechanically compliant and thermally conductive interface pads are interposed between the inside face of the respective heat sink piece and selected locations on either the packaged or unpackaged die exposed face or the substrate board side. Each interface pad has a predetermined thickness which corresponds to the distance between the inside face of the respective heat sink piece with the corresponding selected location on the die exposed face or the substrate board side between which the interface pad is interposed. For any selected location, by judiciously selecting the tolerances and allowances of the interface pad thickness and the offset of the mounting brackets, the interface pad will compliantly conform to surfaces of both the inside face of the heat sink piece and the selected locations on either the die exposed face or the substrate board side. This will allow maximum conductive thermal interface contact between the substrate or die exposed face with the heat sink piece while subjecting the selected location to minimum mechanical loading forces.
According to another aspect of the invention, one of the two heat sink pieces may have a lip which is shaped and sized to both encircle the edges of the substrate and electromagnetically seal against the inside surface of the other heat sink piece thereby providing an electromagnetic shield around the substrate. The lip may be fabricated to closely contour one or more edges of the substrate to further assist in the alignment of the substrate in a predetermined configuration with the one heat sink piece and its mounting brackets. The lip further acts as a spacer which defines and maintains a predetermined minimum distance between the inside faces of the two heat sink pieces.
According to another aspect of the invention, the first and second heat sink pieces may be shaped and sized to provide heat removal from the chip-on-board substrate via conduction to distant points in the heat sink, and by convection and radiation from the heat sink to the ambient environment, while conforming to the space available in the end product to install the chip-on-board substrate. Either or both of the first and second heat sink pieces may have projections which extend, and/or project out of, the main plane of the heat sink piece to enhance conductive heat removal to distant points. Either or both of the heat sink pieces may have extended surfaces, such as pins, fins or the like which increase the surface area to mass ratio of the heat sink piece to enhance passive or forced convective heat removal to the ambient environment. Further, either or both of the heat sink pieces may have heat pipe receptacles for holding heat pipes. The heat pipe receptacles may extend, and/or project out of, the main plane of the heat sink piece to enhance heat removal to distant points, or may be placed near the substrate to more evenly distribute waste heat across the heat sink piece.
According to another aspect of the invention, the thermal management structure may be used with a substrate assembly of two substrates arranged and interconnected as parallel planes (or bi-planar) which operate as a single unit.
According to another aspect of the invention, the thermal management structure may be used with a substrate or substrate assembly which has been enclosed in a thin walled enclosure.
According to another aspect of the invention, either or both of the first and second heat sink pieces may be designed to further compliantly and/or fixedly thermally engage other components in the end product capable of acting as heat spreaders to further conductively remove heat away from both the heat sink and the chip-on-board substrate. Such heat spreaders may be chassis or case components of the end product, for example a portable computer keyboard assembly, chassis, frame or case.
Other and further objects, advantages and novel features will be apparent from the following description of the presently preferred embodiments of the invention, given for the purpose of disclosure and taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of an embodiment of the thermal management structure;
FIG. 2 is an exploded front elevation view of an embodiment of the thermal management structure;
FIG. 2a is an bottom plan view of an aspect of an unpackaged die and an interface pad;
FIG. 3 is a perspective view of an embodiment of the thermal management structure;
FIG. 4 is a front elevation view of an embodiment of the thermal management structure;
FIG. 5 is a top plan view of an embodiment of the thermal management structure;
FIG. 6 is a bottom plan view of an embodiment of the thermal management structure;
FIG. 7 is a front elevation view of an embodiment of the thermal management structure;
FIG. 8 is an exploded perspective view of another embodiment of the thermal management structure;
FIG. 9 is an exploded front elevation view of another embodiment of the thermal management structure;
FIG. 10 is a perspective view of another embodiment of the thermal management structure;
FIG. 11 is an exploded front elevation view of another aspect of the thermal management structure;
FIG. 12 is an exploded front elevation view of an aspect of the thermal management structure.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A better understanding of the present invention and the preferred embodiments will be obtained when the following detailed description is read with reference to the drawings. Like elements in the drawings are represented by like number, and similar elements are represented by like numbers with a different lower case letter suffix.
Referring now to FIGS. 1 and 2, a thermal management structure 100 is illustrated in exploded perspective view and exploded front elevation view respectively. The thermal management structure 100 comprises four main parts: a first heat sink piece 102, a second heat sink piece 104, a plurality of thermal interface pads 106a, b and c, and a plurality of fasteners 108.
The thermal management structure 100 is in a thermal and mechanical functional cooperation with a chip-on-board substrate 150. The chip-on-board substrate 150 has a first side 152 and a second side 154, a plurality of packaged 15 dice 156a, b and c, an unpackaged die 158 (best viewed in FIG. 2), and a plurality of mounting sites 160 (best viewed in FIG. 1). For the purpose of illustrative clarity, and not limitation, the plurality of mounting sites 160 are illustrated as holes, however, it is contemplated and with in the spirit of the present invention that some or all of the mounting sites may be holes, slots, grooves, pins or the like.
For the purpose of illustrative clarity, and not limitation, the plurality of packaged dice 156a, b and c are mounted on the first side 152 of substrate 150 and the unpackaged die 158 is mounted on the second side 154 of substrate 150 (best viewed in FIG. 2). The selection, number and relative positioning of unpackaged and packaged dice on a given substrate is outside the scope of the present invention. It is contemplated, however, and within the scope of the present invention, that the thermal management structure 100 may be adapted to functionally cooperate with a wide variety of unpackaged and packaged dice mounted on either or both sides of a substrate.
Sites on the chip-on-board substrate 150 are selected which have sufficient waste heat generation so as to require thermal enhancement to remove the waste heat. It is contemplated and within the scope of the present invention, that a chip-on-board substrate may have only one site or a plurality of sites which may require thermal enhancement to remove generated waste heat. For the purpose of illustration, and not limitation, it should be assumed that the packaged die 156b and the unpackaged die 158 both generate sufficient waste heat and require thermal enhancement, whereas packaged dice 156a and c have minimal waste heat generation and do not require thermal enhancement.
Thermal interface pads 106a, b and c are selected and sized to engage the selected sites on the chip-on-board substrate 150 requiring thermal enhancement. Preferably the length and breadth of the thermal interface pads will be equal to or less than the corresponding length and breadth of the selected sites. If a selected site is an exposed face of a face up unpackaged chip, care should be exercised to not directly overlay or mechanically load the bond pads or electrical interconnections which typically are disposed along the outer periphery of the die, whether or not the exposed face is encapsulated. As best illustrated in FIG. 2a, a bottom plan view of the unpackaged die 158 is illustrated. Here unpackaged die 158 is in a face up configuration. The exposed face 164 has a plurality of bond pad locations 166 which are near the periphery of die 158. The interface pad 106a is centrally located and disposed on the exposed face 164 so that the interface pad 106a does not overlay or mechanically load the plurality of bond pad locations 166.
The interface pads 106a, b and c, are a mechanically compliant and thermally conductive material. Preferably the interface pads 106a, b and c are aluminum oxide filled silicone elastomer pads. It is contemplated and within the scope of the present invention, however, the interface pads 106a, b and c may be a thermally conductive grease, thermally conductive wax, thermally conductive elastomeric pad or the like, provided the interface pad is mechanically compliant and thermally conductive.
Referring again to FIGS. 1 and 2, the interface pads 106a, b, and c are interposed between the selected sites on the chip-on-board substrate 150 and either a first inside face 114 of the first heat sink piece 102 or a second inside face 116 of the second heat sink piece 104. Interface pad 106a is interposed between the exposed face 164 of unpackaged die 158 and the second inside face 116 of the second heat sink piece 104. Interface pad 106b is interposed between the "board side" of the unpackaged die 158 (i.e. the side of substrate 150 immediately opposite the side where the unpackaged die 158 is mounted), represented by the dotted line 168 in FIG. 1, and the first inside face 114 of the first heat sink piece 102. Interface pad 106c is interposed between the packaged die 156b and the first inside face 114 of the first heat sink piece 102.
The first and second heat sink pieces 102 and 104 preferably are fabricated from an aluminum alloy. It is contemplated and within the scope of the present invention, however, that the first and second heat sink pieces 102 and 104, respectively, may be fabricated from a magnesium alloy, a copper alloy, a beryllium copper alloy, a beryllium aluminum alloy, a carbon fiber composite, a thermal filled plastic or any other material with good thermal conductive properties and mechanical rigidity. It is further contemplated and within the scope of the present invention that either or both the first and second heat sink pieces 102 and 104 may be fabricated by die casting, stamping, extruding, molding, injection molding, powdered metal forming or the like.
Preferably the first heat sink piece 102 is fabricated by die casting and the second heat sink piece 104 is fabricated by stamping. Most preferably the first heat sink piece 102 is fabricated from die cast Aluminum 413 Alloy and the second heat sink piece 104 is fabricated from a stamped Aluminum 1100 Alloy.
It is contemplated and within the scope of the present invention, however, that the second heat sink piece 104 may be fabricated by die casting.
The first heat sink piece 102 has a plurality of first offsetting mounting brackets 110, and the second heat sink piece 104 has a plurality of second offsetting mounting brackets 112. The first plurality of offsetting mounting brackets 110 correspond and align with the plurality of mounting sites 160 on the substrate 150, which further correspond and align with the plurality of second offsetting mounting brackets 112.
Referring now to FIGS. 3, 4, 5, and 6, the thermal management structure 100 is illustrated in a perspective view, front elevation view, top plan view, and bottom plan view, respectively. Here the thermal management structure 100 is in an assembled form in functional cooperation with the chip-on-board substrate 150.
The first offsetting mounting brackets 110 align with the mounting sites 160 and rigidly engage the first side 152 of substrate 150. The second offsetting mounting brackets 112 align with the mounting sites 160 and rigidly engage the second side 154 of substrate 150. Fasteners 108 are used to fasten and firmly secure the first offsetting mounting brackets 110 to the second offsetting mounting brackets 112, thereby sandwiching the chip-on-board substrate in an unmoving relationship between the first heat sink piece 102 to the second heat sink piece 104, and also compressing the interposed interface pads 106a, b and c. By sandwiching and fixedly fastening the chip-on-board substrate 150 between the first and second heat sink pieces 102 and 104, the fragile unpackaged die 158 is mechanically isolated and therefore much less likely to be subjected to mechanical trauma during normal handling.
The fasteners 108 are preferably screws, however, it is contemplated and within the scope of the present invention that alternate fastening means may be employed, such as bolts and nuts, pins, clips, adhesives, glues, epoxies or the like.
As best viewed in FIG. 4, the thermal interface pad 106a compliantly engages and thermally interconnects the exposed face 164 of the unpackaged die 158 with the second heat sink piece 102. Similarly, thermal interface pad 106b compliantly engages and thermally interconnects the board side 168 of the substrate 150 with the first heat sink piece 104. Thermal interface pad 106c compliantly engages and thermally interconnects the packaged die 156b with the first heat sink piece 104.
The thicknesses of the respective interface pads 106a, b and c should each be slightly greater than the distances separating the respective surfaces which they each thermally interconnect. By so doing each interface pad will be provided with sufficient compressive force to conform the interface pad to the respective surfaces, while simultaneously not subjecting the unpackaged die 158 or substrate 150 to any damaging compressive force or deflection.
Referring to FIGS. 1, 2, 3, 4, and 5 an aspect of the present invention is illustrated. An outer face 118 of the first heat sink piece 102 is selectively populated with a plurality of extended surfaces 120 which are thermally conductive. The plurality of extended surfaces 120 increase the surface area to mass ratio, thereby increasing the convective and radiant transfer of heat to the ambient environment. Preferably the plurality of extended surfaces 120 are pins, and most preferably are cylindrical pins. It is contemplated and within the scope of the present invention, however, that the plurality of extended surfaces 120 may be ribs or pins, and the pins may have a non-circular cross-section (i.e. non-cylindrical) such as elliptical, rectangular, square or the like. It is contemplated and within the scope of the present invention that a plurality of extended surfaces may be selectively located on either, both, or neither the first heat sink piece 102 and/or the second heat sink piece 104.
Another aspect of the present invention is that the first heat sink piece 102 and the second heat sink piece 104 can each be shaped and sized independent of each other to conform to the space available in a specific end product while providing heat conduction pathways to cooler distant points in the end product. For the purposes of illustration, and not limitation, the first heat sink piece 102 has a first projection 122 which extends the heat sink mass in the plane of the first heat sink piece 102 (best viewed in FIGS. 1, 3, 5 and 6) and a second projection 124 which extends the heat sink mass out of the plane of the first heat sink piece 102 (best viewed in FIGS. 1, 2, 3 and 4).
It is further contemplated and within the scope of the present invention that a plurality of extended surfaces may be selectively located on the inside face of one or more projections extending from either the first heat sink piece 102 or the second heat sink piece 104. For example, referring to FIGS. 4 and 6, a plurality of extended surfaces 120 are selectively located on the first inside face 114 on the second projection 124 of the first heat sink piece 102.
The first heat sink piece 102 may have a thermal mass block 126 (best viewed in FIGS. 1, 2, 3, 4 and 5) which is located proximate to the board side 168 of the unpackaged die 158, and which also projects out of the plane of the first heat sink piece 102. The thermal mass block 126 provides a large cross-sectional area to conductively remove heat from the unpackaged die 158 to a supplemental thermal enhancement (not illustrated). The thermal mass block may be thermally connected to the supplemental thermal enhancement by using a mechanically compliant and thermally conductive external interface pad 128, such as a aluminum oxide filled silicone elastomer pad, or other thermal conductive interface means such as, but not limited to: thermally conductive grease, thermally conductive wax, thermally conductive epoxy, thermally conductive screws or the like.
Referring now to FIG. 7 the thermal management structure 100 is illustrated in a front elevation view inside an end product 700 (partially illustrated). The end product 700 has a plurality of electrical terminals and signal terminals (not illustrated) which are interconnected (not illustrated) to the chip-on-board substrate 150 and a chassis 708 for receiving and containing the thermal management structure 100. The end product 700 could be one of a number of end products which use semiconductor devices, including, but not limited to: a personal digital assistant, a lap top computer, a notebook computer, a sub-notebook computer, a desktop computer, a printer, a scanner, a modem or the like.
As discussed above a projection, such as the second projection 124, can be used to extend the heat sink mass into an available space 702 of the end product. Also as discussed above, the thermal mass block 126 may be thermally connected to a supplemental thermal enhancement. Here, a thermally conductive first end product component 704 may be thermally connected to the thermal mass block 126. The first end product component 704 is used to further conductively spread heat to distant points within the end product 700. Similarly, the second heat sink piece 104 may be thermally connected to a thermally conductive second end product component 706, also used to further conductively spread heat to other distant points within the end product 700. The first and second end product components 704 and 706 may be any end product component which will not be damaged by the conducted heat, such as, but not limited to: a chassis, frame, superstructure, case or the like.
Referring now to FIGS. 8 and 9, another embodiment of a thermal management structure 800 is illustrated in an exploded perspective view (partially illustrated in FIG. 8) and exploded front elevation view (FIG. 9). The thermal management structure 800 comprises four main parts: a first heat sink piece 802, a second heat sink piece 804, a plurality of thermal interface pads 806, and a plurality of fasteners 808. For the purpose of illustrative clarity, and not limitation, FIG. 8 only illustrates the first heat sink piece 802 and second heat sink piece 804 and a portion of a substrate 850 illustrated as a cutaway.
The thermal management structure 800 is in a thermal and mechanical functional cooperation with the substrate 850. The substrate 850 has a first side 852 and a second side 854, a plurality of packaged dice 856a and b (best viewed in FIG. 9), a plurality of unpackaged die 858a and b (best viewed in FIG. 9), and a plurality of mounting sites 860 (best viewed in FIG. 8). For the purpose of illustrative clarity, and not limitation, the plurality of mounting sites 860 are illustrated as holes, however, it is contemplated and with in the spirit of the present invention that some or all of the mounting sites may be holes, slots, grooves, pins or the like.
For the purpose of illustrative clarity, and not limitation, the plurality of packaged dice 856a and b are mounted respectively on the first side 852 and the second side 854 of substrate 850 and the plurality of unpackaged dice 858a and b are mounted respectively on the first side 852 and the second side 854 of substrate 850 (best viewed in FIG. 9). The selection, number and relative positioning of unpackaged and packaged dice on a given substrate is outside the scope of the present invention. It is contemplated, however, and within the scope of the present invention, that the thermal management structure 800 may be adapted to functionally cooperate with a wide variety of unpackaged and/or packaged dice mounted on either or both sides of a substrate.
Sites on the substrate 850 are selected which have sufficient waste heat generation so as to require thermal enhancement to remove the waste heat. It is contemplated and within the scope of the present invention, that a substrate may have only one site or a plurality of sites which may require thermal enhancement to remove generated waste heat. For the purpose of illustration, and not limitation, it should be assumed that the plurality of packaged dice 856a and b and the plurality of unpackaged dice 858a and b all generate sufficient waste heat and require thermal enhancement on both the board side and the exposed face side of each die.
The plurality of thermal interface pads 806 are selected and sized to engage the selected sites on the substrate 850 requiring thermal enhancement. Preferably the length and breadth of the thermal interface pads 806 will be equal to or less than the corresponding length and breadth of the selected sites. The interface pads 806 are a mechanically compliant and thermally conductive material. Preferably the interface pads 806 are aluminum oxide filled silicone elastomer pads. It is contemplated and within the scope of the present invention, however, the interface pads 806 may be a thermally conductive grease, thermally conductive wax, thermally conductive elastomeric pad or the like, provided the interface pad is mechanically compliant and thermally conductive.
Referring to FIG. 9, the interface pads 806 are interposed between the selected sites on the substrate 850 and either a first inside face 814 (best viewed in FIG. 8) of the first heat sink piece 802 or a second inside face 816 (best viewed in FIG. 9) of the second heat sink piece 804. The thicknesses of the interface pads 806 should each be slightly greater than the distances separating the respective surfaces which they each thermally interconnect. By so doing each interface pad will be provided with sufficient compressive force to conform the interface pad to the respective surfaces, while simultaneously not subjecting the packaged dice 856a and b, the unpackaged dice 858a and b, or substrate 850 to any damaging compressive force or deflection.
The first and second heat sink pieces 802 and 804 preferably are fabricated from an aluminum alloy, and most preferably fabricated from a beryllium aluminum alloy. It is contemplated and within the scope of the present invention, however, that the first and second heat sink pieces 802 and 804, respectively, may be fabricated from a magnesium alloy, a copper alloy, a beryllium copper alloy, a carbon fiber composite, a thermally conductive plastic or any other material with good thermal conductive properties and mechanical rigidity. Preferably the material also has electromagnetic shielding properties. It is further contemplated and within the scope of the present invention that either or both the first and second heat sink pieces 802 and 804 may be fabricated by die casting, stamping, extruding, molding, injection molding, powdered metal forming or the like.
Preferably both the first heat sink piece 802 and the second heat sink piece 804 are fabricated by die casting.
The first heat sink piece 802 has a plurality of first offsetting mounting brackets 810 (best viewed in FIG. 9), and the second heat sink piece 804 has a plurality of second offsetting mounting brackets 812 (best viewed in FIG. 8). The first plurality of offsetting mounting brackets 810 correspond and align with the plurality of mounting sites 860 on the substrate 850, which further correspond and align with the plurality of second offsetting mounting brackets 812.
The first offsetting mounting brackets 810 align with the mounting sites 860 and rigidly engage the first side 852 of substrate 850. The second offsetting mounting brackets 812 align with the mounting sites 860 and rigidly engage the second side 854 of substrate 850. Fasteners 808 are used to fasten and firmly secure the first offsetting mounting brackets 810 to the second offsetting mounting brackets 812, thereby sandwiching the substrate 850 in an unmoving relationship between the first heat sink piece 802 to the second heat sink piece 804, and also compressing the interposed interface pads 806. By sandwiching and fixedly fastening the substrate 850 between the first and second heat sink pieces 802 and 804, the fragile unpackaged dice 858a and b are mechanically isolated and therefore much less likely to be subjected to mechanical trauma during normal handling. The fasteners 808 are preferably screws, however, it is contemplated and within the scope of the present invention that alternate fastening means may be employed, such as bolts and nuts, pins, clips, adhesives, glues, epoxies or the like.
A first outer face 818 of the first heat sink piece 802 and a second outer face 830 of the second heat sink piece 804 are selectively populated with a plurality of extended surfaces 820a, b and c which are thermally conductive. The plurality of extended surfaces 820a, b and c increase the surface area to mass ratio, thereby increasing the convective and radiant transfer of heat to the ambient environment. Preferably the plurality of extended surfaces 820a, b and c are cylindrical pins 820a. It is contemplated and within the scope of the present invention, however, that the plurality of extended surfaces 820a, b and c may be cylindrical pins 820a, non-cylindrical pins 820b and/or ribs 820c. It is contemplated and within the scope of the present invention that a plurality of extended surfaces may be selectively located on either, both, or neither the first heat sink piece 802 and/or the second heat sink piece 804.
Another aspect of the present invention is that the first heat sink piece 802 and the second heat sink piece 804 can each be shaped and sized independent of each other to conform to the space available in a specific end product while providing heat pathways to cooler distant points in the end product. Either or both of the first and second heat sink pieces 802 and 804 may have projections which extend the plane and/or project out of the plane of the heat sink piece. For the purposes of illustration, and not limitation, the first heat sink piece 802 has a projection 822 which extends the heat sink mass in the plane of the first heat sink piece 802 (best viewed in FIG. 8).
Another aspect of the present invention is that the first heat sink piece 802 and/or the second heat sink piece 804 may have one or more heat pipe receptacles 832a, b and c for holding heat pipes 834. The heat sink receptacles may extend the main plane of the heat sink piece (such as 832a) and/or project out of the main plain of the heat sink piece (such as 832a and b) to enhance heat removal to distant points. The heat pipe receptacles may be positioned proximate to the substrate 850 (such as 832c) to more evenly distribute waste heat across the heat sink piece.
The heat pipes 834 are sealed cavities which are filled with a coolant (e.g. Water, HFC's , CFC's or the like). A partial volume of the cavity is occupied by the coolant in the liquid phase and the remaining cavity volume is filled with the coolant in the vapor phase. A heat pipe can efficiently and rapidly transfer large quantities of heat by convective heat transfer via boiling the liquid coolant (evaporative cooling) with the heat source and then condensing the vapor coolant back to a liquid with the cooler ambient environment. The heat pipe cavity may further contain a wicking material to move the liquid phase to the point of evaporation (i.e. the heat source) via capillary action. A wicking material eliminates the need for the heat pipe to be maintained in a specific orientation so that gravitational forces may transport the liquid to a low point near the heat source.
Another aspect of the present invention is that one of the two heat sink pieces may have a lip which is shaped and sized to both encircle the edges of the substrate and electromagnetically seal against the inside surface of the other heat sink piece thereby providing an electromagnetic shield around the substrate.
Referring to FIGS. 8 and 9, for the purpose of illustration, and not limitation, the second heat sink piece 804 has a lip 836 which extends away from the second inside face 816 and forms a cavity 838. It is contemplated and within the scope of the present invention, however, that the lip could be formed on the first heat sink piece 802. Here, the lip 836 is sized and shaped to allow the substrate 850 to be inserted into the cavity 838. The lip 836 also has a seal edge 840 which seals against the first inside face 814 of the first heat sink piece 802 to form an electromagnetic seal. When the substrate 850 is enclosed in the cavity 838, and the first and second heat sink pieces 802 and 804 have been fastened together, the two heat sink pieces 802 and 804 together with the lip 836 function as an electromagnet shield which isolates any electromagnet fields generated by the substrate 850 from the electromagnetic environment surrounding the thermal management structure 800. The second heat sink piece 804 also has an opening 842 which allows the electrical interconnection of the substrate 850 with a plurality of external electrical terminals (not illustrated) and external signal terminals (not illustrated).
The lip 836 may optionally serve two other useful functions. First the lip 836 may be fabricated to closely contour one or more edges or surfaces of the substrate 850 to further assist in the alignment of the substrate 850 in a predetermined configuration with the second heat sink piece 804 and mounting brackets 812. Second, the lip 836 may be used as a spacer, or offset, which defines and maintains a predetermined minimum distance between the first inside face 814 of the first heat sink piece 802 and the second inside face 816 of the second heat sink piece 802.
Referring now to FIG. 10, another embodiment of the thermal management structure 800 is illustrated in an exploded perspective view inside an end product 1000 (partially illustrated). The end product 1000 has a plurality of electrical terminals and signal terminals (not illustrated) which are interconnected (not illustrated) to the substrate 850 (not illustrated). The end product 1000 also has a chassis 1008 for receiving and containing the thermal management structure 800. The end product 1000 could be one of a number of end products which use semiconductor devices, including, but not limited to: a personal digital assistant, a lap top computer, a notebook computer, a sub-notebook computer, a desktop computer, a printer, a scanner, a modem or the like.
As discussed above a projection, such as the first projection 822, can be used to extend the heat sink mass into an available space of the end product. Also the heat pipe receptacles 832a and c having heat pipes 834 may be thermally connected to supplemental thermal sinks. Here, a thermally conductive first end product component 1004 may be thermally connected to the heat pipe receptacle 832a having a heat pipe 834. The heat pipe 834 contained in the heat pipe receptacle 832a convectively transfers waste heat from the thermal management structure 800 to the first end product component 1004. The first end product component 1004 then further conductively spreads the waste heat to distant points within the end product 1000.
Similarly, the second heat sink piece 804 may be thermally connected to a thermally conductive second end product component 1008 (the chassis), also used to further conductively spread heat to other distant points within the end product 1000. The heat sink receptacles 832c having heat pipes 834 convectively distribute the waste heat across the second heat sink piece 804, thereby providing maximum thermal communication with the second end product component 1008. The first and second end product components 1004 and 1008 may be any end product component which will not be damaged by the conducted heat, such as, but not limited to: a chassis, frame, superstructure, case or the like.
Referring now to FIG. 11, an aspect of the present invention is illustrated in exploded front elevation view. The thermal management structure 800 may be used with a bi-planar substrate assembly of two substrates 1150a and b arranged and interconnected as parallel planes which operate both electrically and mechanically as a single unit. The selection of a single substrate 850 or a biplanar substrate 1150a and b, and the relative positioning of the bi-planar substrates 1150a and b with respect to each other (i.e. the relative position of substrate 1150a with respect to substrate 1150b) is outside the scope of the present invention. It is contemplated, however, and within the scope of the present invention, that the thermal management structure 800 may be adapted to functionally cooperate with a wide variety of unpackaged and/or packaged dice mounted on either or both sides of a bi-planar substrate 1150a and b.
Referring now to FIG. 12, another aspect of the present invention is illustrated in exploded front elevation view. The thermal management structure 800 may be used with a substrate 1250 which has been enclosed in a thin walled enclosure 1262. The thin walled enclosure 1262 is a mechanically protective enclosure which has been placed around the substrate 1250 to prevent accidental touchings of the substrate 1250 and any packaged dice 1256 and/or unpackaged dice 1258 on the substrate 1250. Under circumstances where it is not desirable and/or not possible to remove the thin walled enclosure 1262 from the substrate 1250, the thermal management structure 800 can be easily adapted to accommodate the thin walled enclosure 1262.
As viewed in FIG. 12, the thermal interface pads 806 are positioned outside the thin walled enclosure 1262 proximate to the packaged dice 1256 and/or unpackaged dice 1258 which need thermal enhancement to remove waste heat. When the thin walled enclosure 1262 is fixedly mounted within the thermal management structure 800, the thermal interface pads 806 will engage the sites on the thin walled structure 1262 which need thermal enhancement in a mechanically compliant and thermally conductive manner.
The present invention, therefore, is well adapted to carry out the objects and attain the ends and advantages mentioned, as well as others inherent therein.
While presently preferred embodiments of the invention and various aspects thereto have been given for purposes of disclosure, numerous changes in the details of construction, interconnection and arrangement of parts will readily suggest themselves to those skilled in the art and which are encompassed within the spirit of the invention and the scope of the appended claims.
While the present invention has been depicted, described, and is defined by reference to particularly preferred embodiments of the invention, such references do not imply a limitation on the invention, and no such limitation is to be inferred. The invention is capable of considerable modification, alteration, and equivalents in form and function, as will occur to those ordinarily skilled in the pertinent arts. The depicted and described preferred embodiments of the invention are exemplary only, and are not exhaustive of the scope of the invention. Consequently, the invention is intended to be limited only by the spirit and scope of the appended claims, giving full cognizance to equivalents in all respects. | A thermal management structure to provide mechanical isolation and heat removal for an unpackaged semiconductor die mounted directly on a printed circuit board substrate. The thermal management structure sandwiches the unpackaged semiconductor die and substrate between two heat sink pieces which are rigidly mounted to the substrate, thereby mechanically isolating the unpackaged semiconductor die and preventing the die from being accidentally touched. The two heat sink pieces further compliantly thermally engage selected sites on the exposed face of the semiconductor die and the surface of the substrate to conductively remove heat away from the substrate. The thermal management structure may also provide electromagnetic shielding which isolates the electromagnetic fields generated by the substrate from electromagnetic fields external to the thermal management structure. The thermal management structure may also thermally engage selected thermally conductive components within an end product to spread the heat more uniformly throughout the system. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 11/025,156, filed on Dec. 29, 2004, titled “RECOVERY APPARATUS FOR BIOS CHIP IN A COMPUTER SYSTEM”.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention relates to a recovery method, and more particularly to a BIOS recovery method for recovering a basic input output system (BIOS) chip of a motherboard in a computer system.
[0004] 2. Description of Related Art
[0005] The use of computers, especially personal computers (PCs) is widespread. The computing power of the PC, whether coupled to a network or operating as a stand-alone device, has increased significantly as new computer designs move into production. In view of the fact that many computer users are relatively unfamiliar with the technical aspects of computer operation, computer manufacturers have made a concerted effort to simplify operation of the computer. For example, many computer systems are pre-loaded with computer software so that a purchaser simply plugs the computer in and turns it on. In addition, software manufacturers have attempted to simplify the operating system itself.
[0006] However, there are still certain aspects of computer operation that baffle the typical user, and can cause significant difficulties even for the more experienced user. For example, when the computer is first powered up or reset, a software program, typically designated as a “basic input-output system” (BIOS) initializes the computer and permits the startup of an operating system, such as Microsoft MS-DOS. The BIOS program typically resides in a nonvolatile memory such as a read-only memory (ROM), an electrically programmable read only memory (EPROM), electrically erasable programmable nonvolatile memory (EEPROM) and flash memory devices (e.g., flash EEPROM). If the BIOS chip is defective for any reason, the computer will not function properly. Therefore, the BIOS chip is firstly needed to be detached from a motherboard. Then it is reattached to the motherboard after being reprogrammed with a recovery disc. This operation is inconvenient and time-consuming and likely to damage the motherboard in attachment and/or detachment of the BIOS chip.
[0007] What is needed, therefore, is a BIOS recovery method to recover from a BIOS ROM failure that does not require BIOS ROM detached from the motherboard.
SUMMARY
[0008] A method for recovering a content of a basic input output system (BIOS) of a computing system, includes the steps of: providing an externally electrical connection to said BIOS and said computing system; providing an operable recovery source for said BIOS and connectable with said computing system via said externally electrical connection; recording recovery information from said recovery source via said externally electrical connection; and switching said externally electrical connection of said recovery source to another electrical connection between said BIOS and said computing system so as to replace said content of said BIOS by said recovery information.
[0009] Other advantages and novel features of the present invention will become more apparent from the following detailed description of a preferred embodiment when taken in conjunction with the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is an isometric view of a BIOS recovery apparatus in accordance with a preferred embodiment of the present invention;
[0011] FIG. 2 is a circuit diagram of the BIOS recovery apparatus of FIG. 1 ;
[0012] FIG. 3 is an isometric view of a BIOS recovery apparatus in accordance with a second embodiment of the present invention; and
[0013] FIG. 4 is a circuit diagram of the BIOS recovery apparatus of FIG. 3 .
DETAILED DESCRIPTION
[0014] Referring to FIGS. 1 and 2 , a BIOS recovery apparatus in accordance with the preferred embodiment of the present invention comprises a button switch 100 , insulated flexible cords 101 , 102 , 103 , and a connecting socket 106 .
[0015] The connecting socket 106 comprises a top socket 50 , a bottom socket 51 and a printed circuit board 52 . The top socket 50 and the bottom socket 51 are both plastic leaded chip carriers and symmetrically attached to opposite sides of the printed circuit board 52 respectively. Except pins 12 , all the pins of the top socket 50 are soldered with corresponding pins of the bottom socket 51 . A pin 32 and a pin 8 of the top socket 50 are soldered together, and a pin 32 and a pin 8 of the bottom socket 51 are soldered together. The bottom socket 51 is used to receive a primary BIOS chip (not shown) of a motherboard in a computer system. The top socket 50 is used to receive a secondary BIOS chip (not shown) therein.
[0016] The recovery procedure will be described in detail below. The secondary BIOS chip is inserted into the top socket 50 and the primary BIOS chip on the motherboard is inserted into the bottom socket 51 . Thus, pins of the primary BIOS chip and pins of the secondary BIOS chip are electrically connected with each other except the corresponding pins that correspond to the pins 12 of the top socket 50 and the bottom socket 51 via the connecting socket 106 . First terminals of the insulated flexible cords 101 , 102 , 103 are connected to nodes 2 , 3 , 1 of the button switch 100 , respectively. Second terminals of the insulated flexible cords 101 , 102 , 103 are connected to the pin 32 and the pin 12 of the bottom socket 51 , and the pin 12 of the top socket 50 . This time, a corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is floating so that it is in a state of low voltage. And the primary BIOS chip can be designated to work only when the corresponding pin is in a low voltage state. A corresponding pin of the secondary BIOS chip that corresponds to the pin 32 of the top socket 50 is connected to a power-supply of 3 . 3 V for being provided with a working voltage. Corresponding pins of the first and secondary BIOS chips that correspond to pins 8 of the top and bottom sockets are writing-protecting ports and are disabled in low voltage state.
[0017] The button switch 100 is firstly set in an initial state, that is, the node 2 is connected with the node 3 and this results in that the pin 12 and the pin 32 of the bottom socket 51 are connected together and the pin 12 of the top socket 50 is floating. So the corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is connected with the corresponding pin that corresponds to the pin 32 of the bottom socket 51 . The voltage of the corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is changed from low to high and a voltage of the corresponding pin of the secondary BIOS chip that corresponds to the pin 12 of the top socket 50 is low because of being floating. The motherboard is now started from the secondary BIOS chip. At the time, voltages of the corresponding pins that correspond to the pins 8 and the corresponding pins that correspond to the pins 32 of the top socket 50 and bottom socket 51 are high and they are permitted data to be written in.
[0018] In operation, the computer is firstly booted into a disk operation system (DOS) mode, and a burning software and a normal burning file of corresponding motherboard are copied to the DOS. The bottom switch 100 is then pressed to connect the node 2 and the node 1 together. Thus, the pin 12 of the top socket 50 is connected with the pin 32 of the bottom socket 51 and the pin 12 of the bottom socket 51 is floating. At the time, the corresponding pin of the secondary BIOS chip that corresponds to the pin 12 of the top socket 50 is connected to the corresponding pin of the primary BIOS chip that corresponds to the pin 32 of the bottom socket 51 and it is changed from low voltage to high voltage. The corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is floating and it is changed from high voltage to low voltage. As a result, the secondary BIOS chip does not work and the primary BIOS chip works. Then the BIOS burning software and the normal burning file are executed to reprogram the primary BIOS chip. The power of the motherboard is cut off and the BIOS recovery apparatus is taken out when the burning process is completed.
[0019] Referring to FIGS. 3 and 4 , showing a BIOS recovery apparatus in accordance with a second embodiment of the invention. The difference between the two embodiments is that the button switch 100 is displaced with a parallel port controller 200 . A first terminal of the insulated flexible cord 101 is connected with the pin 32 of the bottom socket 51 and a first terminal of the insulated flexible cord 102 is connected with the pin 12 of the bottom socket 51 . A first terminal of the insulated flexible cord 103 is connected with the pin 12 of the top socket 50 . The parallel port controller 200 comprises a parallel port 201 , a resistor 202 and a photoelectric coupling 203 . The parallel port 201 is communicated with a parallel port of a motherboard. A second terminal of the insulated flexible 101 is connected with a first terminal of the resistor 202 and a second terminal of the insulated flexible 102 is connected to a pin D 0 of the parallel port 201 . A second terminal of the resistor 202 is connected to the insulated flexible 102 . Terminals a, b of the photoelectric coupling 203 are connected to the pins D 1 , D 2 , respectively. Terminal c of the photoelectric coupling 203 is connected with a second terminal of the insulated flexible cord 103 and terminal d of the photoelectric coupling 203 is connected to the insulated flexible cord 101 .
[0020] The operating process of the BIOS recovery apparatus will be described in detailed below. The secondary BIOS chip is inserted into the top socket 50 and the primary BIOS chip on the motherboard is inserted into the bottom socket 51 . Thus, pins of the primary BIOS chip and pins of the secondary BIOS chip are shunt-wounded respectively except the pins 12 . The motherboard is powered on and an initial value of the data register of the parallel 201 is 0XFFH. At the time, the photoelectric coupling 203 does not work. The pin 12 of the bottom socket 51 maintains a high voltage because of effect of the resistor 202 , and the pin 12 of the top socket 50 is in a low voltage state because of floating. As a result, the corresponding pin of the secondary BIOS chip that corresponds to the pin 12 of the top socket 50 is in a low voltage state and the corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is in a high voltage state. The motherboard is started from the secondary BIOS chip now. And corresponding pins of the primary and secondary BIOS chips that correspond to the pins 8 and the pins 32 of the top and bottom sockets 50 , 51 are in high voltage states and they are permitted data written therein. The computer is booted into a DOS mode and the value of the data register of the parallel 201 is edited from 0XFFH to 0XFAH. The voltage of the pin 12 of the bottom socket 51 is changed from high to low and the photoelectric coupling 203 begins to work. The pin 12 of the top socket 50 is communicated with the pin 32 of the bottom socket 51 and voltage of the corresponding pin of the primary BIOS chip that corresponds to the pin 12 of the bottom socket 51 is changed from high to low. The corresponding pin of the secondary BIOS chip that corresponds to the pin 12 of the top socket 50 is communicated with the corresponding pin of the primary BIOS chip that corresponds to the pin 32 of the bottom socket 51 and its voltage is changed to high. So the secondary BIOS chip does not work and the primary BIOS chip works. The burning software and the normal burning file can be executed now to reload the primary BIOS chip.
[0021] It is to be understood, however, that even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and function of the invention, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. | A method for recovering a content of a basic input output system (BIOS) of a computing system, includes the steps of: providing an externally electrical connection to said BIOS and said computing system; providing an operable recovery source for said BIOS and connectable with said computing system via said externally electrical connection; recording recovery information from said recovery source via said externally electrical connection; and switching said externally electrical connection of said recovery source to another electrical connection between said BIOS and said computing system so as to replace said content of said BIOS by said recovery information. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
Provisional Patent Application No. 60/347,080; filed Jan. 9, 2002
Non-Provisional Utility patent application Ser. No. 10/161,942, and its Provisional Patent Application No. 60/295,887
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
REFERENCE TO MICROFICHE APPENDIX
Not Applicable
BACKGROUND OF THE INVENTION
The disclosed invention relates generally to mobile, integrated systems for highway traffic violation enforcement, and more specifically to a system modularly installed in a vehicle (together constituting a Mobile Enforcement Platform or MEP) for acquiring, integrating, displaying, archiving, and transmitting or downloading images and data that document multiple types of moving traffic violations as identified and determined by the trained and authorized MEP operator (generally assumed to be a police officer) from multiple lanes of moving vehicles while MEP, itself, is either moving or stationary. MEP enhances and automates the violation documentation process, which feeds into a citation-by-mail process, reducing police officer paperwork and the court-time per citation issued. MEP's capabilities also are suitable for certain mobile monitoring and documentation requirements supporting homeland security programs, objectives, and activities as well as other surveillance requirements.
Traffic violation enforcement typically has been and is an increasingly costly, inefficient, labor-intensive, labor-limited, and frequently ineffective process. Limited police resources are assigned across numerous competing duties and priorities, leaving relatively few police personnel for traffic enforcement where violators greatly outnumber the sparsely distributed enforcers.
Over the years, devices have been introduced to improve the detection, documentation, and prosecution of traffic violations. The use of radar and laser devices to detect and record vehicle speed began in the 1950s, first with fixed, manned systems at the roadside or in makeshift tower structures erected in the median. Later, the speed detection device was mounted on the police vehicle, initially for stationary use and subsequently for mobile use, permitting detection and pursuit by the same officer. Video cameras were introduced to capture sequential images to document violations and the apprehension/citation process, both to support the prosecution of the accused and to provide evidence in the event of legal counter-proceedings by the accused against the accusing officer. Computers were installed in police vehicles to improve the data access, communications capabilities, and integrated teamwork and use of mobile, field, and station personnel and equipment. However, all the devices and processes still required that an officer would identify, stop, detain, and process each violator sequentially, clearly establishing an upper limit on an officer's productivity.
Most recently, unmanned, fixed systems for detection and documentation of speeding and red-light running have been installed to monitor all traffic continuously and to generate and store the necessary composite visual and digital data imagery to support traffic violation citation processes. These devices develop documentary evidence, which is processed later by police, government, or private contractor personnel, producing citations, which are mailed to the registered owner(s) of the cited vehicle based on the associated license plate and vehicle images.
Global positioning satellite system data can be acquired and displayed via a monitor to show the map coordinates for the approximate location of the acquiring receiver and display monitor, essentially replacing the old LORAN system aid to navigation with a modern, more useful system. This technology has had little application in traffic enforcement because either the officer writes the approximate location on the citation or the detection and documentation device is at a fixed, known location.
BRIEF SUMMARY OF THE INVENTION
The disclosed system and methods are controlled and operated by a trained, authorized person in a vehicle operated by a trained, authorized driver. The driver's task is to drive the vehicle according to prevailing regulations and posted traffic signs along a pre-planned route. The system operator operates the entire enforcement system through mechanical and electronic means to identify a violator and the violation, enter the violation specifics, and then acquire, integrate, capture, archive, and transfer violation documentation (continuous and still) images and data as well as other traffic and vehicle information of customary interest to police and highway department personnel and their various missions.
The invention generally consists of integrated detection and imaging systems installed on a custom manufactured frame around a central work area from which a trained and authorized person operates the equipment to initiate and generate the violation documentation and other vehicle data that are central objectives of the invention. The invention can detect and document a variety of developing violations simultaneously in multiple lanes of traffic behind and in front of the MEP vehicle. The invention's capabilities dramatically increase the scope and credibility of traffic enforcement, which in turn will make the highways safer. Now, instead of telling it to the judge, an officer can show the violation to the judge and violator. MEP's comprehensive documentation of each violation charged eventually should reduce the cases contested, freeing up police officer and court time for other priorities.
The integrated detection and imaging units (one viewing traffic to the rear and/or one viewing traffic to the front of the MEP vehicle) consist of two high-resolution digital video cameras and a speed detection device (radar or laser) co-mounted on a single arm, which is mechanically or hydraulically aimed and operated by the MEP system operator. (Alternatively, the speed detection device may be co-mounted in fixed-aim position with the aft-facing and forward-facing fixed video cameras.) The operator points the arm and unit toward the potential violator, zooms on the license plate (and perhaps on the vehicle and driver) with the digital video camera(s), enters certain digitized information such as the license plate data and violation observed, and triggers the speed detection device. The cameras and speed detection device generate images and data, which are displayed together with other information for continuous videotaping and still-imaging on operator command.
Additional displayed information in the composite display include: the location coordinates displayed by a global positioning system receiver, the location description, and the posted speed limit and work zone status input by the driver. Other information displayed from the processing personal computer includes the driver's name and identifying number, the MEP operator's name and identifying number, and the date and time continuously updated.
The MEP operator has an alphanumeric touchscreen device for entry of the violation type and the violator's license plate number and state of registration to digitize the plate data immediately. Where permissible under prevailing laws and procedures, the positive license plate identification instead may be voice-recorded on the continuous video to facilitate documentation of high volumes of violations. Either process avoids the usual errors of optical character recognition, especially for widely varying character formats and can make the license information available for records management and for immediate law enforcement use. When the MEP operator is satisfied that the display is complete and correct (the digitized license plate data is an optional requirement here), the operator presses a trigger button on the handle of the combination detection and camera unit aiming device or on the touchscreen to capture a high resolution digital, still image of all the composite display's screens and displays. The operator may continue to track the violator and trigger and capture a second composite image some pre-set number of seconds after the first image (if this is required by the jurisdiction).
The captured composite still images are saved directly to an image storage device in the camera or a second high speed personal computer for 1) retention for later download and processing, 2) digitized license plate transmission with location, date, and time, and 3) high-speed radio transmission or land-line transfer of still images to a fixed site for immediate citation processing.
The composite display is continuously taped with a fixed digital video camera. A high-resolution camera co-mounted with the fixed video camera captures the digital still images. This video camera is the only one to save continuous images on tape or CD. The tapes or CDs and the still images are labeled and archived for data retrieval, as necessary. A unique identifying number combining the date and time and MEP unit identifies specific tapes or CDs. Still images are identified by the same identifying combination of information used for the video images for the moment the image is captured on the particular videotape together with the digitized license plate data, if entered. This correspondence facilitates rapid retrieval of video segments containing sequences that relate to respective still images.
A second comparable system may face the front of the MEP vehicle to permit identification and documentation of violations by vehicles without a front license plate as well as violations that occur in front of the MEP vehicle. The forward-facing system's equipment, capabilities, data capture, operation, and information display are the same as for the rear-facing system except that the violator's face cannot be captured.
All of the equipment together with the operator's seat are mounted on a strong, lightweight metal frame that is fastened to the vehicle floor in the space bounded by the backs of the driver's and front passenger's seats, the interior side-panels and rear wheel wells, and the rear door (through which the entire assembly is modularly installed and removed.
All equipment and the operator's seat are commercially available with the required specifications. However, the invention integrates the equipment and its operational flexibility to provide an innovative mobile traffic enforcement tool that has the potential to improve enforcement productivity and credibility by a factor of 100 times in many traffic settings. The invention also replaces some police officer paperwork with automated composites, which are the basis for issuance of a citation by mail.
The vehicle and its equipment will be checked at regular intervals including the start and end of each operating day or shift according to user agency procedures to ensure that the entire system is performing properly and that calibrations critical to violation measurement and adjudication are correct (and therefore indisputable) before and after each MEP operations interval. A zero defect citation process is achievable with the invention, enhancing its credibility and constructive impact on traffic safety.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the flexibility of the Mobile Enforcement Platform's Aimable Traffic Violation Detection and Documentation System
FIG. 2 shows the space in a generic van-type vehicle where the Mobile Enforcement Platform frame-mounted module would be installed and removed through the rear doorway.
FIG. 3 shows the equipment and workspace configuration of the frame-mounted, removable platform module.
FIG. 4 shows the view from above of the Mobile Enforcement Platform operator's aimable equipment for detecting speed and identifying and capturing traffic violations for documentation.
FIG. 5 shows the operator's view of the violation identification and image capture system elements in their mounts and the system hinge and pivot for aiming.
FIG. 6 shows the aimable, speed detector and video camera assembly (also optionally movable laterally) on its assembly support frame and optional carriage. Where required, the speed detection device may instead be co-mounted as fixed-aim units with the fixed-aim fore and aft video cameras.
FIG. 7 shows the optional foot-operated, lateral position-lock for the movable speed detection and violator identification equipment assembly.
FIG. 8 shows the operator's control for speed detection activation, license plate video camera zoom, and triggering the composite still image-taking for violation documentation.
FIG. 9 shows the elements displayed together in composite for continuous digital videotaping and digital still image capture.
FIG. 10 shows the system operator's touchscreen or keyboard data input device.
FIG. 11 shows the elements displayed on the system operator's screen display.
FIG. 12 shows the MEP vehicle driver's touchscreen or keyboard data input device.
FIG. 13 shows the MEP vehicle driver's screen display elements.
FIG. 14 shows the frame base upon which the MEP equipment assembly and operator work area are installed. The frame with all its assembly is installed and removed as a unit through the rear door of the MEP vehicle.
FIG. 15 shows a cut-away view of the frame base in installed position in a generic van-type vehicle.
FIG. 16 shows the MEP generic van-type vehicle with the frame-mounted equipment and operator workspace installed in the installed position.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is an overview showing the Mobile Enforcement Platform (MEP) in a multi-lane highway setting in the midst of traffic flowing from left to right. Although the invention is intended to support identification and documentation of traffic violations by vehicles driving in the same direction as the MEP vehicle, MEP can be used in a stationary mode detecting and documenting violations by either oncoming or overtaking vehicles. MEP's violation identification and documentation system is aimable so that the onboard operator can point it at a vehicle in any parallel lane as well as MEP's own lane. This flexibility overcomes the limitations of previous onboard systems which are fixed-aim, driver-operated (no second officer present to focus entirely on violation identification and documentation), and generally support the one-to-one police enforcement approach that greatly limits the effectiveness of current traffic enforcement.
As illustrated, the aimable equipment, which is situated to operate non-stop toward the cars behind and in front of MEP, which is in motion, can be aimed sequentially at a target vehicle in any of several lanes. MEP is designed to develop the necessary information and violation documentation to support citation-by-mail, greatly increasing the productivity of traffic officers and increasing the proportion of violators being identified and cited. MEP also will reduce police officer paperwork and court time for the average violation.
MEP is designed for identification and complete documentation of many types of moving violations, especially where it is too dangerous to attempt a traffic stop or where violations are too rapid and numerous for traditional traffic enforcement to be effective, including:
Failing to yield right-of-way Following too closely Unsafe lane changes Improper passing Speeding Disobeying traffic signals (including stop signs) Reckless driving
The system also is designed to support homeland security surveillance activities and highway use information needs for planning. The potential crash reduction, public health, and economic benefits are very large.
One set of speed detection and digital image violation documentation equipment faces the rear window of a van-type vehicle and/or another duplicate set faces the front window. The units are operated by a trained person (generally a police officer trained and experienced in traffic enforcement) seated in a chair installed in the middle of the removable MEP frame.
FIG. 2 shows the overview of the MEP vehicle with back seats removed to make space 1 for the MEP installable and removable module of equipment and integrated operator work area. The module is installed and removed through the rear door 2 of the van-type vehicle. Other vehicle-types may be used such as panel trucks or campers or recreational vehicles, the primary requirement being that the vehicle have a rear entrance and internal space, both sufficient to accommodate the complete module and workspace required. This vehicle flexibility is intended to give the police greater latitude in (a) purchasing vehicles through current contracts and vendors, (b) selecting a vehicle offered by their preferred manufacturer, and (c) choosing the vehicle which will blend in best in the local traffic.
FIG. 3 shows the equipment elements and their configuration with the workspace on the frame-mounted, removable platform. This description starts with the operator's work area, then describes the elements and operation of the rearward detection and documentation equipment operated by the operator, then describes the remaining equipment and documentation operations.
The operator enters the work area through an opening in the handrail 7 that surrounds the work area of the module. The opening is opened by temporarily removing a movable piece 8 of the handrail. The operator sits in an ergonomic operator's seat or captain's chair 3 that is attached to the center of the module frame and swivels 360 degrees in either direction for operating access to all equipment, in particular the speed detection and documentation equipment, input devices, and system controls facing the rear and/or the front. The seat 3 has restraining safety straps fully equivalent to approved seat belt and shoulder strap for any highway vehicle. The seat 3 has an armrest 4 across the front of the seat to support the operator's arms to reduce fatigue and stress during operation. The seat controls 5 allow the operator to adjust the chair height and angle (fore and aft) as well as the contour of the back, all for the operator's maximum comfort. Such seats, captain's chairs, and seat controls are readily available in various models of automobiles and vans sold in the United States. The seat 3 also has a seat brake 6 so the operator can lock the chair in position suitable for the current activity, be it using the rearward devices or the frontward devices or stopping while facing some intermediate side position.
There are matching sets of speed detection and video documentation equipment facing the rear and the front of the MEP for use as illustrated previously in FIG. 1 . The difference between the two sets is that the front system captures the rear of vehicles ahead of the MEP while the rearward system captures the front and driver of the vehicles it views. The frontward system cannot capture the driver's face, but is not subject to photographic interference from bright headlights and can capture license plates on cars that have no front license plate.
Using the rearward equipment for illustration, the operator's main devices for violation identification and documentation of traffic violations are the violator video camera 9 (captures the violating vehicle and driver), the speed detection device (which is obscured under the violator video camera 9 in this figure, the license plate video camera 10 which is focused on and captures the license plate image close-up, the control unit 11 for the video cameras 9 and 10 and the speed detection device (e.g., RADAR or laser LIDAR) under 9 (or alternatively co-mounted 28 a and 28 b with the rear-facing and front-facing fixed-aim video cameras), the operator's touchscreen or keyboard input device 12 and the rear operator's display 13 ; 12 , and 13 are shown to the left of 9 , 10 , and 11 , but can be flip-flopped to the right for the convenience and comfort of the operator; this also can accommodate right- and left-handedness.
The violating vehicle video camera 9 captures the full front of the violating vehicle and the driver in color digital imagery, providing clear identification of the make, model, and color of the target vehicle. Depending upon lighting conditions and windshield tinting, the camera also will capture the driver's face or silhouette, which will help identify and document the violating driver. If the violation involves speeding, the speed detection device below the camera 9 generates the target vehicle and MEP speed information, which is the partial basis for determination whether a violation has occurred. Alternatively (or in addition), the MEP speed data may be fed to the composite digital display and the integrating personal computer 17 from the MEP vehicle's certified calibrated digital speedometer.
The license plate video camera 10 is zoomed by the operator to fill the license plate window on the operator's display screen 13 with the license plate image and on the camera's own display panel.
In order to capture the license plate, vehicle, and driver images and to capture the target vehicle's relative speed (relative to MEP or alternatively to fixed objects such as trees and bridges), the operator aims the co-mounted video cameras 9 and 10 and the speed detection device by moving the control handle 11 arm horizontally and vertically. The camera 9 is mounted directly over the speed detection device to ensure that the two devices are aimed at the same vehicle in a common vertical plane. Camera 9 is mounted to the right of the license plate video camera 10 since the license plate will typically be to the left of the driver.
The operator uses the images from cameras 9 and 10 and 18 , and the operator's display 13 as well as the speed detection information to determine whether there is a speed violation or other violation and whether the desired images are being captured.
Simultaneously, the operator enters information on the touchscreen or keyboard input device 12 for immediate availability of digitized license plate information and the violation detected (e.g., speeding, reckless driving, aggressive driving, failure to stop for a red light, failure to stop for a stop sign, or other violations that particularly concern the jurisdiction).
Optionally, the detection device, cameras 9 and 10 , touchscreen input device 12 , and operator's display 13 may move laterally as a unit on horizontal bars 14 that support them. This allows the operator to get a better angle or to get closer to a head-on angle or simply to change positions in the course of a work period.
The speed detection device output (and certified calibrated speedometer data) and the images from cameras 9 and 10 are fed to the composite display 16 . Other information is fed to the composite display from the operator's touchscreen input device 12 , the global position system device 15 (continuous feed of coordinates of approximate location), and the MEP vehicle driver's touchscreen data input device described later in FIG. 12 .
The entire composite display 16 with elements, which will be described in detail in FIG. 9 , is continuously captured by digital video camera 18 . The video images are clearly and continuously identifiable as to date, time, location, operator, and driver, and with these markings are readily available for copying as evidence or viewing for moving violation citation processing where the violation is not established or confirmed simply by viewing a single digital composite image that shows a vehicle speed clearly over the speed limit.
A separate still digital image of the composite display 16 will be taken by a digital camera mounted just under the video camera 18 . The still image is output directly to its camera's image storage device or to a high-speed personal computer 19 for storage and later transmission or download for citation processing.
The citation processor uses each violation still image as the basis for a citation and will report on the disposition of each violation identification. License plate images are the primary source for identification of violating vehicle ownership, and the operator inputs (manual or voice) are first and foremost the positive indication of intent to cite. Citations are processed and addressed to the registrant(s) of record for the violating vehicle in speeding violations, provided the vehicle description in the registration data is consistent with the vehicle image. Otherwise, the violation likely will be referred to other authorities.
Non-speeding violations may not be able to be processed on the basis of a single frame digital image, depending upon the training and police authorization of the MEP operator. If the MEP operator does not have sufficient authority to generate the citation, then review of the videotape or CD from camera 18 provides the necessary additional information for an authorized person to issue the citation, if warranted. The date and time on the still image provide the necessary cross-reference for the reviewer to rapidly find and review the relevant sections of videotape or CD.
In order for the digital images to be credible proof of violation, the speed detection device will need to be checked for calibration at the beginning and end of each shift and as recommended by the manufacturer after the jurisdiction discusses the intended use with the manufacturer. The calibration activity itself may be included on the videotape as evidence that it occurred as required.
The speed detection device, video cameras 9 , 10 , and 18 , the GPS device 15 , and the composite display elements 16 , and the PC 1 17 and PC 2 19 all are readily available from numerous commercial sources. The video cameras must produce high-resolution digital images capable of communicating all imagery and alphanumeric detail sufficiently clearly for legal proceedings. An example of the digital video cameras could be the Panasonic PV-DV950, which provides adequate image resolution and the necessary electronic image stabilization capability. However, only the video camera 18 records its images on videotape or CD. All other digital video cameras in the invention output video to separate monitors, requiring the PV-DV950's docking station direct video output. All equipment must be capable of sustained, heavy use and is placed in readily accessible space so that it is easy to remove and replace any piece of equipment that is not performing correctly.
Additional digital video images are provided on a continuous basis from fixed cameras 23 , 21 , 22 , and 20 , respectively at 0 degrees, 90 degrees, 180 degrees, and 270 degrees (90 and 270 are optional). These additional images are direct output from the video cameras and provide a continuous context in, the composite display 16 for the violation images and facilitate continuity of imaging as a vehicle passes from the rearward view to the frontward view or from front view to the back. As indicated above, the speed detection devices may be fixed-aimed and co-mounted with video cameras 22 and 23 .
The power supply 24 for the computers, monitors, and other electrical equipment is located on the frame. However, in some climates and seasons, it may be necessary to have air conditioning and fans for the equipment and work area. In this case, generator and air conditioning equipment beyond the vehicle's capabilities may be placed on the roof of the vehicle.
The image and data transceiver 25 supports remotely activated transmission of license plate, date, time, and location data as well as selected violation images ready for processing. All these data are stored on the high-speed personal computer 19 for transmission on demand or for later download via landline or at a fixed facility. Every license plate entered by the operator is saved automatically to the personal computer 19 along with the respective date, time, GPS location, and MEP driver entered street-type—and highway name or number. These data are useful to law enforcement agencies and officers as well as to highway departments and planners.
FIG. 4 shows a view from above the system operator's equipment for detecting speed and capturing traffic violations. The operator observes traffic behavior either directly through the rear window or front windshield or virtually through the operator's display 13 and viewing screens of cameras 9 and 10 showing images of traffic to the rear or in front. When the operator determines that a violation is occurring, the operator aims the speed detector and vehicle and license plate cameras 9 and 10 at the targeted vehicle. If in the judgment of the operator a violation other than speeding is being or has been captured on the continuous digital video (display 16 and video camera 18 ), the operator will obtain the best still image considering distance and relative speed of the vehicle and MEP for later use in identifying the violation on tape for review and citation. The operator may ask MEP's driver to slow a bit to allow the violator to approach, permitting a better image of the license plate, vehicle, and driver.
For suspected speeding, the operator will aim the speed detector and two video cameras 9 and 10 at the targeted vehicle and acquire the target speed data and images for determination of whether a violation has occurred and, if so, for tracking of the vehicle until the desired images of the license plate and vehicle/driver are achieved, permitting a still digital image of the respective composite display 16 , using the still digital camera paired with the digital video camera 18 .
FIG. 5 shows the operator's view of the configuration of the violation identification and image capture elements. The violator vehicle (and driver) digital video camera 9 is set into a padded frame over the speed detector 28 , which also is set into a padded frame. To the left of the speed detector 28 is the license plate digital video camera 10 also set into a padded frame. The license plate video camera 10 is attached to the main assembly by a stiff rotation joint to permit adjustment of its orientation to a preferred elevation from which its elevation for license capture can be fine-tuned as will be discussed in relation to FIG. 8 . The viewing screens of both cameras 9 and 10 are opened facing the operator, facilitating system operation. In each instance, the padding is to reduce the jarring effects of bumps in the road on the sensitive equipment and the quality of the video and still digital images. All video cameras have image stabilization to further dampen the effects of roadbumps on images. The elevation hinge 29 permits adjustment of the vertical alignment and the horizontal pivot 30 permits horizontal aiming—together providing the necessary degrees of motion to facilitate the desired aiming of the detection and image capture system.
FIG. 6 shows a view of the left side of the movable, aimable, speed detector and video camera assembly mounted on its assembly support frame and carriage. The vehicle video camera 9 is above the partially obscured speed detector 28 with the violating vehicle license plate video camera 10 between the viewer and the speed detector. The license plate camera 10 is portrayed in parallel alignment with the speed detector. The aimable set of speed detection and imaging equipment is presented in its neutral position resting on its support, reflecting the action of the light spring to draw the system back to center alignment which facilitates unmanned, straight-back monitoring of traffic behavior when not otherwise aimed by the operator. The speed detection and license plate video camera control 26 will be discussed in detail in relation to FIG. 8 . The detection and camera assembly is mounted with a hinge 29 and pivot 30 to the assembly frame 34 , permitting aiming from side to side with adjustment of the elevation below the resting position. An adjustment wheel-nut permits the operator to set the resting elevation of the assembly. The assembly frame is supported by three bars 32 and 35 and a track under the assembly frame base 33 . The support bars 32 and 35 and the floor support track under the sliding assembly base 33 are fixed to the MEP frame referenced in FIGS. 14 and 15 .
Optionally, the assembly and frame described in FIG. 6 may be moved laterally by the system operator as previously described. In order to move the frame and assembly, the operator must disengage the locking pin and, when the assembly reaches the desired position, reengage the locking pin. FIG. 7 shows the optional foot-operated, lateral position-lock for the movable detection and violator identification equipment assembly. The position-lock sits atop the assembly base 33 , which rests on the floor support track 36 . A spring 38 pulls a pin down into the floor support track unless the pin is pulled up by the operator pressing on the top of the pedal 37 with a foot, which through lever action pulls the pin away from the track. The track 36 has perpendicular notches along the top surface, which permit the pin to set itself, preventing the assembly from sliding to one side or the other.
FIG. 8 shows the control for activation of speed detection and license plate video camera and composite still imaging. After the operator aims the detection and camera assembly, the license plate camera likely will need to be zoomed in or out from its last position to capture the license plate of the target vehicle in the full field of its respective display window on the operator's display 13 in FIGS. 3 , 4 , and later in FIG. 11 , and on the respective screen in the composite display 16 . Rotation of the handle in the vertical axis to zoom in (raising the wrist) or out (lowering the wrist) with the video camera focused on the license plate accomplishes this task. Pulling and holding the trigger activates the speed detection device (e.g., radar, laser). If a violation is detected and the camera images 9 and 10 are ready, then pressing the button 41 at the top of the handle takes a still digital image of the composite display 16 as documentation of the violation. Even if speeding is not charged but some other violation is, the operator may choose to include the speed measurement in the documentation for completeness and objectivity.
FIG. 9 shows the layout of the composite display ( 16 in FIG. 3 ) for continuous digital videotaping and still image capture. Across the top of the display, continuous images are displayed on separate 5″ screens from the video cameras 20 , 21 , 22 , and 23 identified in FIG. 3 . On the left half of the display and below the rear field digital video image from camera 22 , images and data pertaining to a rearward target are displayed. The largest image on a video screen (at least 13″) is from the target vehicle and driver video camera 9 in FIG. 3 . Below the image are 13 data elements: a MEP/target vehicle speed display connected to the speed detection unit, a GPS display of coordinates, a display of the target license plate video image, the MEP vehicle speed from the vehicle speedometer, the violator tracking time from the operator's computer, and a computer monitor displaying 6 data elements some of which are automated inputs and the rest of which are inputs from either the system operator or the MEP vehicle driver. The MEP speed and the target vehicle speed are measured and displayed by the speed detection device 28 in FIG. 5 or by the alternative fixed-aim speed detector co-located with the video cameras 22 and 23 . The posted speed limit is entered by the MEP vehicle driver as will be discussed with FIG. 12 . The target license plate is captured by zoomed video camera 10 . Separately and time permitting, the system operator enters the license plate through a touchscreen which will be discussed in relation to FIG. 10 . An alternative is the use of voice-recognition software so the MEP operator can speak the license plate state and characters for computerized insertion. Yet another alternative is to combine manual entry of a voice track pointer with continuously recorded voice track on the system videotape, which captures “live” driver and operator narratives in which the violator's license plate number is spoken. Since the system operator's entry of the license plate provides an immediate digitized identifier, a subsequent still image is identified by the license plate number as well as the date and time and location. If the vehicle is traveling too fast to permit touchscreen entry of the license plate, then the digitized license plate field will be blank and the date, time and location will be the only identifiers for the vehicle and image until a processor views the image, determines the license plate state and characters, and enters same to complete the data link in a separate database. The GPS location is generated by the GPS device 15 , which is part of the composite display 16 and is used in conjunction with the highway or street information entered by the MEP vehicle driver from the input device to be described in FIG. 12 . The violation detected or identified by the operator is entered by the system operator through the input device in FIG. 10 . Lastly, the names or identifiers of the system operator and the MEP van driver are displayed in the bottom space. The optional right-hand half of the composite monitor display covers the same information but for the forward-facing detection and imaging assembly.
FIG. 10 presents the system operator's touchscreen or keyboard data input device, which is divided into four clusters of input keys: state two-letter abbreviations, digits, letters, and pre-coded violation keys. The system operator uses the device to input digitized license plate data using the state abbreviations, digits and letters. The state information fills automatically into the two-character space at the left of the license plate entry location. The rest of the license plate (letters and digits) will fill from the right as the operator enters the information so that no empty space is left to the right of the data and so that the system can adapt to license plates that use anywhere from 1 character to 10 characters. The system operator also enters the violation detected using pre-coded keys for simple entry. The violation is spelled out so that part of the resulting still image can be printed and mailed along with the citation. An additional key in the lower right of the operator's touchscreen/keyboard starts, stops, and resets a tracking timer which allows the operator to document the elapsed time a violator was tracked before the operator actually determines that a violation has taken place and certification via still image is initiated. The timer value is included in the composite display 16 data (see FIG. 9 ).
FIG. 11 shows the information displayed on the system operator's screen display ( 13 in FIGS. 3 and 4 ). The display layout is the same in the forward and the rearward units. The operator uses this screen display together with the images from cameras 9 , 10 , and 18 to determine the sufficiency of the license plate and vehicle images and data prior to triggering the speed detection and still image. Triggering the still image is the certifying event that will cause a citation or warning to be generated and mailed.
FIG. 12 presents the MEP vehicle driver's touchscreen or keyboard data input device. The driver's input must be limited so as not to interfere with the job of driving and with the safety of the vehicle and others in the vicinity. Yet, there are some data which the driver is best situated to enter easily and safely. Pre-coding a number of keys at the beginning of the day or shift or run eliminates the risk of MEP driver distraction. The driver will enter the street or highway identification, the posted speed limit for each respective stretch of road as the vehicle moves along its route, and whether the MEP vehicle is in a work zone or not. As the street or speed limit or work zone status changes, so the driver will change the input to the system. To make the driver's input task safe and simple, anticipated roads to be traveled can be pre-coded as can dominant speed limits so that a single touch enters the desired multi-character entry. For instance, a single touch could cause entry of “I-66” or “George Washington Parkway” or “16th Street, NW” or “MD state route 5” or “7100 Fairfax County Parkway.” Likewise, a single touch could enter “55” mph. The work zone key is a toggle “yes” or “no”. The MEP driver inputs are networked to the system operator and the composite display 16 .
FIG. 13 shows the driver's screen display which together with the input screen (or keyboard) is placed in front of the dashboard to the right of the steering wheel. In this position, the driver can keep track of the active data in the system and the speed of the MEP vehicle in relation to the speed limit and the planned speed. MEP vehicle speed is fed to the personal computer 17 , the composite display 16 (see FIG. 9 ), and the driver's display screen from the MEP vehicle's certified calibrated digital speedometer.
FIG. 14 illustrates the frame base on which the equipment assembly and integrated operator work area are built and which is installed and removed as a unit through the rear of the vehicle. The base for the operator's seat is in the middle. Set-screws or bolts on each side of the frame help anchor the total assembly, which is fastened to the floor where passenger seats normally would be placed. The frame consists substantially of bars welded together with sawtooth grooves across each of the bars on the side facing up. The grooves make it possible for bars placed over the frame to grip the frame bars (locking teeth) and to be matched with and bolted or fastened to the seat anchors in the floor.
FIG. 15 shows the generic van-type vehicle with a cut-away view of the frame base in installed position without the additional crossbars bolted to the floor. The frame is sized to the type of vehicle that the jurisdiction wishes to use.
FIG. 16 shows the equipment and integrated work area installed in the back of a van-type vehicle. | A manned, mobile traffic enforcement platform with aimable violation detection and documentation devices, employing digital video and still images, incorporating contextual information as well as data input by the system operator and driver, with numerous commercial-off-the-shelf components and a physically integrated composite display. The mobile enforcement platform (MEP) is operated by trained system operators, typically sworn-officers, who apply pre-determined criteria, protocols, procedures and routines to generate conclusive, court-acceptable violation documentation. MEP supports detection, identification, and documentation of violations in any lane behind or in front of the moving MEP vehicle or from the roadside. MEP captures most types of moving violations, including aggressive driving, in readily retrievable documentation formatted for later mail citation and court use. MEP increases police and court productivity, reduces police officer paperwork and court time, increases enforcement credibility, reduces crash costs and fatalities, improves highway safety, and augments homeland security capabilities. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to vehicular brake locking mechanisms, and particularly to such brake locking mechanisms for impeding theft of the vehicle.
2. DESCRIPTION OF THE PRIOR ART
Brake locking mechanisms to deter or impede theft of vehicles such as automobiles, trucks, trailers and the like are well known. However, such mechanisms heretofore known have had one or more disadvantages. For example, in U.S. Pat. Nos. 3,482,666; 3,874,747; 4,007,815; and Re. 29,913; a brake locking mechanism is installed at each brake to prevent movement of an otherwise hydraulically or pneumatically operated brake rod mechanism. This involves installation of a brake locking device at each brake, generally modifying each existing brake to accommodate the locking mechanism, and installing an auxiliary control system to operate the brake locking mechanism.
Another type of brake locking mechanism involves positioning a valve in the brake power fluid line between the master cylinder and the brakes as seen in U.S. Pat. Nos. 4,040,675; 3,973,803; 3,653,730; 3,625,573; 3,617,100; and 3,515,442. With this mechanism, the brakes are locked in the applied position by pressurizing the brake fluid and then closing the valve in the brake fluid line to prevent release of the pressure. However, this type of mechanism has the disadvantage that installation in an existing brake system is complicated by the necessity of breaking the hydraulic fluid line. Further, it is generally a possibility in such systems that the valve in the brake line could close during operation of the vehicle, and thereby render the brakes inoperable while the vehicle is in motion.
It is an object of the present invention to provide a brake locking mechanism which does not require a separate installation at each brake or breaking any brake fluid lines for installation, and further which does not interfere with the normal operation of the brakes while the vehicle is in motion.
SUMMARY OF THE INVENTION
The present invention provides a brake locking mechanism for use with a vehicular brake system having one or more fluid operated brakes, a cylinder for pressurizing the brake fluid, and an actuator for reciprocating a piston in the cylinder in one direction to apply the brakes and in another direction to release the brakes. Briefly, the mechanism includes a housing adapted to securely fit between the actuator and the cylinder, means within the housing for reciprocating the piston responsively to the actuator, and means for releasably locking the reciprocating means with the piston in the brake-applying position.
In another aspect, the invention provides a brake locking mechanism for use in a vehicular braking system having a plurality of fluid operated brakes, a master cylinder with a reciprocatable piston moveable between a brake applying position in which the brake fluid is pressurized and a brake releasing position in which the brake fluid is depressurized, and an actuator for reciprocating the piston operable from within a driver's compartment of the vehicle. The mechanism comprises a housing adapted to fit between the actuator and the cylinder, a bore formed in the housing, a ratcheted rod slideable in the bore and operable to reciprocate the piston responsively to the actuator, and a pawl disposed in the housing for releasably engaging the ratchet to lock the rod in the brake-applying position, thereby rendering the rod nonresponsive to the actuator. The pawl may be released, for example, by a keyed switch or engaging mechanism mounted in the driver's compartment which can be operated only with the proper key.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of an embodiment of a vehicular brake system having a brake locking mechanism according to the present invention.
FIG. 2 is a side sectional view of an embodiment of a brake locking mechanism of the present invention installed between a master cylinder and an actuator therefor in the unlocked position.
FIG. 3 is a side sectional view of the brake locking mechanism of FIG. 2 in the locked position.
FIG. 4 is a cross-sectional view of the brake locking mechanism of FIG. 2 as seen along the lines 4-4.
FIG. 5 is a cross-sectional view of the brake locking mechanism of FIG. 3 as seen along the lines 5-5.
FIG. 6 is a side sectional view of an alternate embodiment of a brake locking mechanism of the present invention, shown in the locked position.
FIG. 7 is a side sectional view of the brake locking mechanism of FIG. 6, shown in the unlocked position.
FIG. 8 is a side sectional view of a remote locking device for operation of the brake locking mechanism of the invention, shown in the locked position.
FIG. 9 is a side sectional view of the locking device of FIG. 8, shown in the unlocked position.
FIG. 10 is an end view of the locking device of FIGS. 8 and 9 as seen along the lines 10-10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As seen in FIG. 1, a vehicular braking system S includes master cylinder A, brake fluid lines B, and brakes C. The master cylinder A is typically operated by means of a rod D which is responsive to foot pedal E. Rod D is typically installed to make the operation of the master cylinder A responsive thereto, directly in the case of a standard brake system, or with the aid of a power booster F in the case of power brakes. According to the present invention, a locking mechanism 10 is positioned between the actuator F and the master cylinder A. The locking mechanism 10 is remotely operable by a locking device 11 mounted, for example, on the dashboard of the vehicle passenger compartment.
As seen in FIGS. 2, 3, 6 and 7, the conventional master cylinder A has a bore 12 formed therein which receives a piston 14 having seal means 16,18 therebetween. The piston 14 is reciprocatable to compress and decompress the brake fluid for operating the brakes. The master cylinder A has an extended portion 20 which fits into a corresponding recess 22 formed in the typical power booster F in conventional brake systems when the locking mechanism 10 is not present. The power booster F typically has a housing 24, diaphragm 26, vacuum chamber 28, hydraulic push rod 30, seal 32, reaction disk 34 and valve operating rod assembly 36 (shown only in part) which is operatively connected with the foot pedal E. When the locking mechanism 10 is not employed, the end 38 of the push rod 36 engages the piston 14 in the centrally disposed recess 40 formed therein. Movement of the push rod 36 is thus responsive to the foot pedal E and reciprocates the piston 14 to operate the brakes.
According to the present invention, the locking mechanism 10 is disposed between the master cylinder A and the power booster F or other conventional apparatus for reciprocating the piston 14 as may be present. Referring to FIGS. 2-7, the locking mechanism 10 has a housing 50 with a first end 52 adapted to engage the conventional reciprocating apparatus and a second end 54 adapted to engage the master cylinder A. In the illustrated embodiment, the end 52 is an extended portion of dimension similar to the extended portion 20 of the master cylinder A which is thus receivable in the corresponding recess 22 of the power booster F. The second end 54 includes an enlarged bore dimensioned to correspond similarly to the recess 22 so that the extended portion 20 of the master cylinder A may be received therein.
A bore 56 is formed longitudinally through the housing 50 and has a ratcheted transfer rod 58 positioned slidably therein. The rod 58 has a first central longitudinal recess 59 formed therein for engagement by the end 38 of the push rod 36. At the opposite end of the rod 58, there is formed another central longitudinal recess 60 in which a transfer pin 62 is positioned and biased by spring 64. The transfer pin 62 extends from the recess 60 and has a head 65 in engagement with the piston 14 in the recess 40 formed therein.
The rod 58 is provided with ratchet teeth 66 along the longitudinal exterior surface thereof. A pawl member 68 is positioned in a recess 70 at the end 54 adjacent the bore 56 and rod 58 therein. The pawl member 68 may have any suitable shape, but is shown in the preferred shape of a semicircular annulus or washer. The pawl 68 is held in place by a retaining element 71 which is illustrated as a washer disposed between the extended portion 20 of the master cylinder A and the inside face 72 of the enlarged bore 54 formed in the housing 50. A transverse bore or port 74 is formed in the housing 50 to receive a pawl actuator 76 which is described in more detail hereinbelow.
The brake locking mechanism 10 is readily installed in most conventional vehicular brake systems by disconnecting the master cylinder A from the power booster F, or other brake actuating mechanism, placing the mechanism 10 therebetween and reattaching the master cylinder A to the power booster F with the mechanism 10 thereby secured interposed between the master cylinder A and the power booster F. Typically, the master cylinder A is secured to the power booster F by two bolts which are easily removed and replaced with longer bolts to accommodate the longitudinal dimension of the housing 50. As seen in FIGS. 4 and 5, the housing has a pair of opposed longitudinal flanges 78,80 on either side thereof for receiving the bolts 82,84. Alternatively, peripheral longitudinal bores could be formed in the housing 50 for this purpose. It is also desirable to insert a push rod return spring 86 in the power booster F to prevent disengagement of the push rod 30 from the reaction disk 34.
In normal operation of the brake system, the piston 14 is reciprocated responsively to the foot pedal E and push rod 36 by transfer of force from the end 38 of the push rod 36 through the rod 58 and spring-biased pin 62 to the piston 14. When it is desired to lock the brakes, the pawl 68 is pushed radially inward against the rod 58 by the pawl actuator 76. Then the brake pedal E is depressed by the vehicle operator which pushes the push rod 36 and rod 58 to reciprocate the piston 14 into the brake applying piston. The pawl 68 engages the teeth 66 preventing retraction of the rod 58, and the piston 14 is held securely in the brake applying position. If the brake fluid expands or contracts due to temperature changes thereof, the brakes remain applied because of the biasing of the pin 62 by the spring 64. In this manner, the vehicle cannot be driven without disengaging the pawl actuator 76 which may be controlled by a locked and/or hidden control mechanism. When the operator desires to disengage the brake lock 10, the pawl actuator 76 is disengaged from the pawl 68 and the pawl 68 is retracted so that the rod 58 may move freely in the bore 56 and the brakes operated normally. In some embodiments, the brake pedal E may have to be depressed following disengagement of the pawl actuator 76 in order to release the pawl 68 from the ratchet 66.
The pawl actuator 76 may be mechanically or electrically operated by a remote mechanism or switch which is desirably hidden and/or locked with a key or combination, for example, to deter or impede unauthorized use of the vehicle. In FIGS. 2-5 and 8-10, there is shown a keyed, mechanically operated embodiment of the pawl actuator 76. In this embodiment, a rod or cable 100 runs from the transverse bore 74 in the housing 50 to a remote location, such as, for example the dashboard or another convenient location of the vehicle operating compartment. The cable 100 is provided with a sleeve 102 connected to the housing 50 at the bore 74 by means of the nipple 104 in threaded engagement therewith. At the end of the cable 100, there is desirably provided a spring 106 for biasing the pawl 68, and a pin 108 disposed longitudinally in the spring 106 having a head 110 adjacent the pawl 68. The pin 108 thus prevents the spring 106 from being overcompressed. The spring 106 also facilitates engagement of the pawl 68 by allowing for some limited movement thereof as the pawl 68 rises over the teeth 66 during travel of the rod 58 during the locking thereof.
The remote end of the cable 100 and sleeve 102 is preferably connected to a lockable, keyed push button device or barrel lock 120 of a well known type as illustrated in FIGS. 8-10. The barrel lock 120 includes a housing 122 mounted on the dashboard of the vehicle (not shown) by means of screws or bolts, or the like (not shown). The sleeve 102 is attached at an end plate 124 having a port 126 for receiving a threaded nipple 128 securing the sleeve 102 thereto. The cable 100 extends through the nipple 128 and port 126 into an enlarged bore 130 formed in the housing 122 where it is securely attached to a cylinder 132 by means of, for example, a threaded connector 134 on bottom cylinder plate 135. The bottom cylinder plate 135 has a transverse dimension corresponding to the enlarged bore 130, while the cylinder 132 has a transverse dimension corresponding to the bore 136. The cylinder 132 is slideable in the enlarged bore 130 and the reduced bore portion 136, and is biased by spring 138. The cylinder 132 has a spring-biased catch member 140 which is extended from the cylinder 132 when the cylinder 132 is depressed into the bore 130,136 to engage a face 142, thereby preventing retraction of the cylinder 132 from the bore 130,136. The catch member 140 is retractable to the cylinder 132 by means of a key inserted into the cylinder 132 in a keyhole 144 formed therein.
In operation, the barrel lock 120 engages the pawl 68 by depression of the cylinder 132 by the vehicle operator. The cylinder 132 pushes the cable 100 to bias the pawl 68 with the spring 106 for locking of the rod 58 as described above. The cylinder 132 is locked in the depressed position by the extension of catch member 140 into engagement with the face 142. When it is desired to unlock the brakes and return them to normal operation, a key is inserted into the keyhole 144 of the cylinder 132 and turned to retract the catch member 140 into the cylinder 132. The spring 138 pushes the cylinder 132 to the top of the bore 136 with the bottom cylinder plate 135 in engagement with the face 142. This in turn retracts the cable 100 so that the biasing of the pawl 68 by the spring 106 is removed. The pawl 68 will then drop and disengage from the teeth 66 upon movement of rod 58 via the foot pedal E, returning the brake system to normal operation.
In an alternate embodiment illustrated in FIGS. 6 and 7, the pawl 68 is engaged and disengaged electronically. A solenoid 200 is positioned at the bore 74 by, for example, threaded engagement of a solenoid nipple 202 therewith. The solenoid 200 is provided with a core 204 slideable therein and having a tapered portion 206 extending into the bore 74 adjacent the pawl 68. The solenoid 200 is desirably housed in a transverse extension 208 of the housing 50 in order to inhibit tampering therewith by unauthorized persons.
The solenoid 200 is operated by means of a switch 210 connected to a power source 212 and the solenoid 200 by means of wires 214,216. The wires 214,216 are desirably sheathed in a tamper-resistant sleeve (not shown). The switch 210 may be mounted on the dashboard of the vehicle passenger compartment or tied directly or by relay switches to the vehicle ignition switch. The switch 210 may also be operated by a key or combination lock as desired.
The locking mechanism of the present invention can be used to deter unauthorized use of the vehicle and/or as an emergency or parking brake. The mechanism is readily installed since the hydraulic brake fluid lines do not need to be broken for this purpose.
The foregoing description of the invention is illustrative and explanatory thereof. Various changes in the materials, apparatus, and particular parts employed will occur to those skilled in the art. It is intended that all such variations within the scope and spirit of the appended claims be embraced thereby. | A brake locking mechanism of the anti-theft type for use with an automobile vehicular brake system having one or more fluid operated brakes, a master cylinder and an actuator for reciprocating a piston in the cylinder to apply and release the brakes. The locking mechanism has a housing adapted to fit between the master cylinder and the actuator, means such as a ratcheted rod within the housing for reciprocating the piston responsively to the actuator, and means such as a pawl operatively associated with the ratcheted rod for locking the reciprocating means with the piston in the brake applying position. The locking means is remotely controlled from a keyed or combination lockable control mechanism located in the driving compartment of the vehicle which may be mechanical or electronic. | 1 |
This invention was made with Government support under Contract No. DAAK21-83-C-0012 awarded by the Department of the Army.
BACKGROUND OF THE INVENTION
This invention pertains generally to fuzes for artillery projectiles, and particularly to an encoder for a fuze capable of providing a multiple of discrete timing settings in a single revolution of a setting collar.
As is known, it is often necessary to delay the arming of an artillery projectile after firing. In a changing battlefield, the capability to change the length of the delay quickly and easily may determine the outcome of the battle. It is desirable to provide a fuze for an artillery projectile with a multiple of discrete timing settings thereby providing greater flexibility while minimizing the number of components in the fuze. A problem arises in the operation of known fuzes because of inadvertent resetting of the fuze when handling the projectile for the purpose of gun loading. Also known fuzes are apt to reset due to the inertial effects upon the setter locks of the fuze during the influence of the dynamic forces of the gun.
SUMMARY OF THE INVENTION
With the foregoing background of this invention in mind, it is a primary object of this invention to provide, for an artillery projectile, a fuze with an encoder having a multiple of discrete timing settings in a single revolution of a setting collar.
Another object of this invention is to provide a fuze which is adapted to reduce the inertial effects upon the setter locks of a fuze during the influence of dynamic forces from a gun.
Still another object of this invention is to provide a fuze which is adapted to reduce the possibility of resetting the time delay of the fuze when handling the projectile for the purpose of gun loading.
A still further object of this invention is to provide a fuze with an arrangement of components resulting in simplified assembly procedures in production.
The foregoing and other objects of this invention are met generally by a contemplated fuze wherein an encoder comprising an encoder ring, having an inner surface with a predetermined mask pattern, is locked by a spring lock exerting pressure in a radially outward motion, thus enhanced when the fuze is exposed to the influence of dynamic forces from a gun. The spring lock cooperates with a lock pin such that a radially inward deflection of the lock pin deflects the spring lock so that the encoder ring with a reaction surface is unlocked and can be fully rotated by a setting collar acting through a detent spring on the reaction surface. If the encoder ring is locked, the detent spring is deflected over the reaction surface of the encoder ring when the setting collar is rotated, thereby preventing the encoder ring from being changed. A plurality of actuators, which determine a digital word that represents a length of time for a time delay in a digital timing circuit for the fuze, is actuated by the predetermined mask pattern. The digital word is changed by rotating the setting collar while the encoder ring is unlocked.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of this invention reference is now made to the following description of the accompanying drawings, wherein:
FIG. 1 is an isometric view, exploded and partially torn away, showing various elements of the encoder according to the invention;
FIG. 2 is a cross-sectional view, partially torn away, showing a lock pin cooperating with a spring lock and locking teeth;
FIG. 3 is a cross-sectional view showing a detent spring reacting with a setting collar and the encoder ring;
FIG. 4 is an isometric view, exploded, showing various elements of an encoder switch assembly;
FIG. 5 is a cross-sectional view of a single actuator interacting with a predetermined mask pattern in the encoder ring;
FIG. 6 is a cross-sectional diagram of a section of the encoder according to the second embodiment of the invention;
FIG. 7 is an isometric view of a section of an encoder according to the second embodiment of the invention;
FIG. 8 is an isometric view of a lock spring and a lock pin according to the second embodiment of the invention; and
FIG. 9 is a cross-sectional view showing the detent spring cooperating with a vernier encoder ring, a coarse encoder ring and the setting collar according to the second embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, a head 100 of an artillery projectile (not shown) with a portion broken away is shown with a fuze encoder 110 according to this invention. The artillery projectile (not shown) is either a non-spinning or spin stabized projectile shot from a gun. A fuze base 1 with interface thread 3 is used to attach head 100 to the artillery projectile (not shown) by screwing the head 100 to the artillery projectile. Fuze encoder 110 is shown to comprise lock pin 14' and lock pin 14 with associated components (not numbered). Since the associated components (not numbered) used with lock pin 14 are the same as the associated components (not shown) used with lock pin 14', only the associated components (not numbered) used with lock pin 14 are described in detail. Fuze encoder 110 includes fuze shelf 7, lock pin 14, annular groove 18, spring lock 29, encoder ring 21, encoder mask 22, locking teeth 28, window 8 detent spring 16 (FIG. 3), setting collar 9, reaction surface 35, flute 42 and encoding switch assembly 50.
The fuze shelf 7 is provided on the fuze base 1 to support encoder ring 21, window 8 and setting collar 9, which are mounted encircling cylindrical surface 23 of fuze base 1. The window 8, having a circumferential shape and an extended skirt 25, is secured to the fuze shelf 7 by any known means, such as by epoxying the extended skirt 25 to a mating groove 24 in the fuze shelf 7. A radial bore 17 extending through the fuze shelf 7 is provided to accommodate lock pin 14. The annular groove 18 is provided in the shelf 7 of sufficient depth to intersect the bore 17 and continues an equal distance radially from the bore 17. Inserted in the bore 17 is the lock pin 14 with an elastomeric seal such as a 0-ring (not shown) which, while maintaining a seal, allows motion of the lock pin 14 relative to the fuze shelf 7. In the local area of the lock pin 14 the outer contour of the fuze shelf 7 and the window 8 are relieved to permit manual deflection of the lock pin 14 radially inward, while the lock pin 14 is prevented from extending outward beyond the original contour of the fuze shelf 7. The spring lock 29 is inserted in the annular groove 18. A recess 31 in spring lock 29 engages a control groove (not shown) in lock pin 14 which is similar to control groove 32' shown in lock pin 14' . The spring lock 29 exerts radial force outward upon lock pin 14. Lock tangs 30a, 30b and 30c on the spring lock 29 engage locking teeth 28 on encoding ring 21.
The encoder ring 21 is shown having a varying vertical cross-section and includes two slots as typified by slot 33. The encoder mask 22 with a predetermined mask pattern 27 of lands and grooves is disposed on an inner surface of the encoding ring 21. The lands and grooves (not numbered) activate switches, such as actuator 509, (FIG. 4), forming a mechanical read only memory as described hereinafter. The predetermined mask pattern 27 is aligned with the locking teeth 28 which are facing inward on encoding ring 21. A predetermined scale 36 is disposed on the periphery of the encoder ring 21. Here the scale represents time in seconds but could also represent other parameters for the fuze encoder. Each element (not numbered) of the scale 36 has a corresponding element in the predetermined mask pattern 27 and is aligned with each corresponding element of mask pattern 27.
Referring now to FIG. 2, encoder ring 21 is placed over cylindrical surface 23 (FIG. 1) of base 1 such that the encoder ring 21 is supported by fuze shelf 7 (FIG. 1), and lock tangs 30a, 30b and 30c engage locking teeth 28. When lock pin 14 is depressed radially inward, the lock tangs 30a, 30b and 30c on spring lock 29 are disengaged from locking teeth 28, thereby permitting rotation of encoder ring 21.
Referring to FIG. 3, detent spring 16 is inserted into a space 37 between the encoder ring 21 and the setting collar 9. As shown in FIG. 1, the setting collar 9 has a cross-section loosely conforming internally to the encoder ring 21 and conforming externally to the aerodynamic profile of the head 100 (FIG. 1). Flutes as typified by flute 42 and flute 42a (FIG. 1), are provided using indented surfaces on the external surface of setting collar 9 to facilitate positive gripping of the setting collar 9 by a user (not shown). The setting collar 9 employs an upper collar seal (not shown) and a lower collar seal (not shown) such as an O-ring, both having elastomeric properties, at the upper and lower circular interfaces, respectively, to protect the components (not numbered) of the fuze encoder 110 from external environments.
Slots 33 and 33' are respectively provided in the encoder ring 21 to maintain the detent spring 16 and an opposing detent spring 16' in a fixed position in relation to the encoder ring 21. Spring ends 34a and 34b on detent spring 16 interact with reaction surface 35 which is a feature provided on the inner surface of the setting collar 9. In a similar manner, spring ends 34a' and 34b' on detent spring 16' interact with reaction surface 35 so that as setting collar 9 is rotated around fuze base 1, encoder ring 21 is rotated correspondingly. When encoder ring 21 is locked, thereby preventing the encoder ring 21 from rotating, spring ends 34a, 34b, 34a' and 34b' slip over reaction surface 35 which alleviates the force presented on encoder ring 21 when setting collar 9 is rotated around fuze base 1.
Referring again to FIG. 1, encoder switch assembly 50 includes a plurality (here 8) of wireform actuators 52. Encoder switch assembly 50 is shaped as shown loosely conforming to the cylindrical surface 23 of fuze base 1. The plurality of wireform actuators is connected to circuitry (not shown) which is to be described hereinafter. Encoder switch assembly 50 is mounted in a recess 8 in fuze base 1. The encoder switch assembly 50 is mounted so that each one of the plurality of wireform actuators 52 is aligned with a corresponding element (not numbered) of the predetermined mask pattern 27 providing a mechanical read only memory (not numbered). The encoder ring 21 and encoder switch assembly 50 provide a time delay section (not numbered) in the head 100 of the artillery projectile.
Referring now to FIG. 4, the encoder switch assembly 50 is shown to include a spring index plate 508, a flexprint assembly 510 and the plurality of actuators 52 as typified by actuator 509. Spring index plate 508, having a first and a second surface, is shaped with the first surface having a contour loosely matching the contour of cylindrical surface 23 (FIG. 1) of fuze base 1 (FIG. 2) and with the second surface having a chamber for accommodating the flexprint assembly 510, as described hereinafter. Additionally, spring index plate 508 has a plurality of slots 525 and grooves 526 and 527 for supporting the plurality of actuators 52. Actuator 509, having a center and a first end 536 and a second end 537 and typical of each one of the plurality of actuators 52, has a flange 530 at the center of the actuator 509. Next to one side of flange 530 on actuator 509 is a first contact 532 and next to an opposing side of flange 530 is a second contact 533 providing a pair. When encoder switch assembly 50 is assembled, flange 530 is set in slot 521 which is one of the plurality of slots 525. Additionally, the first end 536 of actuator 509 is mated with groove 522 which is one of the plurality of grooves 526 and the second end 537 of actuator 509 is mated with groove 523 which is is one of the plurality of grooves 527. Local deformation or any other known means in each of the plurality of grooves 526 and 527 lock each one of the plurality of actuators 52 in place.
Flexprint assembly 510 comprises a nonconducting material 512 having a surface shaped as shown, which fits in the chamber of spring index plate 508 and attached in any known means, such as by epoxying. Conductive circuitry 514, capable of conducting electric current, is disposed on the surface of the nonconducting material 512. The conductive circuitry 514 includes common contact surfaces 515 and 516 and a plurality of pairs 519 of contact pads as typified by contact pad 517 and contact pad 518. Between each one of the pairs 519 of contact pads is a hole, as typified by hole 513, extending through the nonconducting material 512 and capable of allowing a corresponding flange, as typified by flange 530, of one of the plurality of actuators 52 to pass through. Contact pad 517 and contact pad 518 are dimensioned such that when flange 530 is placed through hole 513, contact pad 517 is resting against contact 532 of actuator 509 and contact pad 518 is resting against contact 533 of actuator 509.
Common contact surfaces 515 and 516 are disposed on flexprint assembly 510 and dimensioned so that a first end, such as first end 536, of each one of the plurality of actuators 52 rests against the common contact surface 515 and a second end, such as second end 537, of each of the plurality of actuators 52 rests against the common contact surface 516. If common contact surfaces 515 and 516 are connected to ground, then by opening or closing a connection made by each one of the plurality of pairs 519 of contacts pads and the corresponding contacts of one of the plurality of actuators 52, a switch is created and a one or a zero can be represented for a bit in a digital word. As in each of the actuators 52, by having contact pads 517 and 518 making a connection, in parallel, to contacts 532 and 533, respectively, a connection is ensured since if either contact pad 517 or 518 loses connection with contact 532 or 533, respectively, the remaining contact pad and contact are still connected.
In assembly, flexprint assembly 510 is mounted in the chamber of spring index plate 508, and attached by any known means. Actuator 509 is secured to spring index plate 508 by placing flange 530 through hole 513 and slot 521, mounting first end 536 in groove 522 and mounting second end 537 in groove 523. Each of the remaining plurality of actuators 52 is secured to spring index plate 508 in a like manner, creating a plurality of switches for selecting a digital word.
Referring now to FIG. 5, actuator 509, typical of each of the plurality of wireform actuators 52 (FIG. 4), is shown with a contact 58 in the closed position, thereby closing a circuit (not shown). As the encoder ring 21 with code mask 22 is rotated around fuze base 1, the predetermined mask pattern 27 of lands and grooves will either push on actuator 509 thereby breaking contact 58, or not push on actuator 509, thereby closing contact 58, depending upon the position of code mask 22. Letting each of the plurality of wireform actuators 52 represent a bit in a digital word, it should be apparent to one of skill in the art that with eight actuators an 8 bit digital word can be provided. The predetermined mask pattern 27 of lands and grooves on encoder ring 21 selectively actuates the eight actuators (not shown) so that the predetermined mask pattern 27 of lands and grooves provides a mechanical read only memory map such that each element of the predetermined mask pattern 27 selects a corresponding digital word. It should be noted that centrifrugal spin force is in the same direction as the spring force which closes the contact 58 of actuator 509. Spin force thereby adds to the constant pressure, increasing the assurance of closure.
Referring again to FIG. 1, it should be apparent that locking teeth 28 determine the number of increments possible as encoder ring 21 makes one revolution. In the embodiment shown, there are eighty teeth so that eighty settings are possible. Although the encoder switch assembly 50 (FIG. 4) has a capacity of 256 settings, the number of settings is controlled by the number of locking teeth 28.
It will now be apparent to one of skill in the art that the inward deflection of the lock pin 14 displaces spring lock 29, thereby disengaging lock tangs 30a, 30b and 30c from locking teeth 28 on encoder ring 21. Rotation of the setting collar 9 causes coaxial rotation of the encoder ring 21 reacting through detent spring 16, which is possible because the locking teeth 28 are free from the lock tangs 30a, 30b and 30c. The setting collar 9 is rotated until the user (not shown), viewing through window 8 at an index 5, selects an appropriate element of the scale 36. The foregoing action selects the corresponding element of the mask pattern 27 which selectively actuates the mechanical read only memory (not numbered) for setting the time delay of the head 100. Release of the lock pin 14 will cause the lock tangs 30a, 30b, and 30c to engage the locking teeth 28 of the encoder ring 21 as the spring lock 29 is defected radially outward. Rotation of the setting collar 9, while the lock tangs 30a, 30b and 30c are engaged with locking teeth 28, will cause deflection of the spring ends 34a, 34b, 34a' and 34b' (FIG. 3) so that no reaction is allowed to transfer rotation to the encoder ring 21. The latter prevents a prior setting from being changed by an unintentional setting collar change.
Referring now to FIG. 6, a head 200 with a dual encoder 210 according to a second embodiment of this invention is illustrated to include elements as in the first embodiment including fuze base 1, fuze shelf 7, window 8, setting collar 9, lock pin 14, and detent spring 16 with all their attendant features and functions. In the geometric space occupied by the encoding ring 21 (FIG. 1) and code mask 22 (FIG. 1) in the first embodiment are a concentric pair of encoder rings: Coarse encoder ring 225 with a coarse code mask 226 and vernier encoder ring 227 with a vernier code mask 228.
The fuze shelf 7 is formed on the fuze base 1 to support coarse encoder ring 225 and window 8 which are mounted around cylindrical surface 23 of fuze base 1. Window 8 is secured to fuze shelf 7 as disclosed hereinbefore in the first embodiment. Vernier encoder ring 227 is supported by coarse encoder ring 225 and encircles coarse encoder ring 225 below detent spring 16 and encircles cylindrical surface 23 of fuze base 1 above the detent spring 16. Coarse encoder ring 225 is divided into a plurality of coarse settings (here 50 settings) as determined by the number of coarse locking teeth 236 (FIG. 7) on coarse encoder ring 225. Each one of the coarse locking teeth 236 (FIG. 7) has a corresponding coarse encoder setting 262 (FIG. 7) which is displayed in window 8. Coarse code mask 226, which is formed as part of coarse encoder ring 225, has a predetermined mask pattern (not shown) forming a mechanical read only memory map on the inner surface of coarse encoder ring 225 which activate actuators (not shown) protruding beyond cylindrical surface 23 of fuze base 1.
Vernier encoder ring 227 is divided into a plurality of vernier settings (here 100 settings) as determined by fine locking teeth 237 (FIG. 7) on vernier encoder ring 227. Each one of the fine locking teeth 237 (FIG. 7) has a corresponding vernier encoder setting 264 (FIG. 7) which is displayed in window 8. Vernier code mask 228 which is formed as part of vernier encoder ring 227 has a predetermined mask pattern (not shown) forming a mechanical read only memory map on the inner surface of the vernier encoder ring 227 which activates actuators (not shown) protruding beyond cylindrical surface 23 of fuze base 1.
Referring now to FIG. 8, spring lock 238 cooperates with lock pin 14 as spring lock 29 (FIG. 2) cooperated with lock pin 14 as described hereinbefore. In this second embodiment, spring lock 238 has a plurality of dual lock tangs as typified by dual lock tang 239. Dual lock tang 239 has a fine lock tang 202 and a coarse lock tang 204 as shown and operates as described hereinafter.
Referring again to FIG. 6, spring lock 238 is shown when the vernier encoder ring 227 and the coarse encoder ring 225 are locked. When the lock pin 14 is released, the spring lock 238 is exerting pressure in a radially outward position such that dual lock tang 239 engages coarse locking teeth 236 (FIG. 7) and fine locking teeth 237 (FIG. 7). In said position, coarse encoder ring 225 and fine encoder ring 227 are secured from moving by dual lock tang 239.
When it is desirable to change the settings of the dual encoder 210, lock pin 14 is depressed radially inwardly so that spring lock 238 moves inwardly which disengages the plurality of dual lock tangs, including dual lock tang 239, from coarse locking teeth 236 and fine locking teeth 237. The latter allows a user (not shown) to rotate setting collar 9 which causes, as described hereinafter, coarse encoder ring 225 to rotate until a desirable position is selected using index 205 (FIG. 7).
Upon selecting a desired position for coarse encoder ring 225, lock pin 14 is partially released so that the plurality of dual lock tangs including dual lock tang 239 on spring lock 238 engages coarse locking teeth 236 while fine locking teeth 237 remain disengaged. The latter allows a user (not shown) to rotate setting collar 9, which causes, as described hereinafter, vernier encoder ring 227 to rotate until a desirable position is selected using index 205 (FIG. 7). Upon selecting a desired position for vernier encoder ring 227, lock pin 14 is completely released as shown so that the plurality of dual lock tangs including dual lock tang 239 engage coarse locking teeth 236 (FIG. 7) and fine locking teeth 237 (FIG. 7).
Referring now to FIG. 9, detent spring 16, having spring ends 34a and 34b, is shown as used in the dual encoder 210. Slot 233 in vernier encoder ring 227 holds detent spring 16 in a fixed position relative to vernier encoder ring 227. When the coarse encoder ring 225 and the vernier encoder ring 227 are locked, spring ends 34a and 34b slip over reaction surface 35 of setting collar 9. When the coarse encoder ring 225 and the vernier encoder ring 227 are unlocked, detent spring 16 reacts with a reaction surface 240 of the coarse encoder ring 225 at spring point 41 of the detent spring 16 so that as the setting collar 9 is rotated, the coarse encoder ring 225 is rotated correspondingly. The vernier encoder ring 227 is also rotated by the latter. When the coarse encoder ring 225 is locked and the vernier encoder ring 227 is unlocked, spring point 41 of the detent spring 16 will slip over reaction surface 240 of the coarse encoder ring 225. Since the vernier encoder ring 227 is unlocked, the vernier encoder ring 227 is rotated as setting collar 9 is rotated until a desired position is selected at which time the vernier encoder ring 227 is locked. An inadvertent resetting of the fuze is prevented by the hereinabove described action.
Referring again to FIG. 6, it will now be apparent to one of skill in the art that the inward deflection of the lock pin 14 displaces spring lock 238, thereby disengaging the plurality of lock tangs (not shown) on spring lock 238 from the coarse locking teeth 236 (FIG. 7) and the vernier locking teeth 237 (FIG. 7). Rotation of the setting collar 9 causes the vernier encoder ring 227 and the coarse encoder ring 225, reacting through detent spring 16 (FIG. 9), to rotate. The setting collar 9 is rotated until the user (not shown), viewing through window 8 at index 205 (FIG. 7), selects a desired element of the coarse encoder setting 262. The foregoing action selected a corresponding element of the mask pattern (not shown) which actuated the plurality of actuators (not shown) which corresponds to the selected element of the coarse encoder setting 262 (FIG. 7). Partial release of the lock pin 14 will cause the plurality of lock tangs (not shown) to engage the coarse locking teeth 236 (FIG. 7) which locked the coarse encoder ring 225 while the vernier encoder ring 227 remains unlocked. The setting collar 9 is rotated further until the user (not shown), viewing through window 8 at index 205, selects a desired element of the vernier encoder setting 264. The foregoing action selected a corresponding element of the mask pattern (not shown) which actuated a plurality of actuators (not shown) which corresponded to the selected element of the vernier encoder setting 264. Releasing fully lock pin 14 caused the plurality of lock tangs (not shown) to engage the fine locking teeth 237 (FIG. 7) in addition to the coarse locking teeth 236 (FIG. 7), thereby locking the vernier encoder ring 227 in addition to the coarse encoder ring 225. Further rotation of the setting collar 9 will cause deflection of the spring ends 34a and 34b (FIG. 9) so that no reaction is allowed to transfer rotation to either the vernier encoder ring 227 or the coarse encoder ring 225.
Having described this invention, it will now be apparent to one of skill in the art that the number and disposition of the various locking teeth may be changed without affecting this invention. Further, the location and the number of detent springs could be changed to achieve different pressure. Also the type and number of actuators used to read the predetermined mask pattern could be changed. The invention could be used in all types of fuzes including proximity fuzes wherein delayed activation of the fuze is required. It is felt, therefore, that this invention should not be restricted to its disclosed embodiment, but rather should be limited only by the spirit and scope of the appended claims. | A time delay mechanism force fuze wherein the mechanism comprising an encoder ring, having an inner surface with a predetermined mask pattern of lands and grooves, is locked by a spring lock exerting pressure in a radially outward motion, thus enhanced when the fuze is exposed to the influence of dynamic forces from a gun, is shown. The spring lock cooperates with a lock pin such that a radially inward deflection of the lock pin deflects the spring lock so that the encoder ring with a reaction surface is unlocked and can be fully rotated by a setting collar acting through a detent spring on the reaction surface. If the encoder ring is locked, the detent spring is deflected over the reaction surface of the encoder ring when the setting collar is rotated, thereby preventing the encoder ring from being changed. A plurality of actuators, which determines a digital word that represents a length of time for a time delay in a digital timing circuit for the fuze, is actuated by the predetermined mask pattern. The digital word is changed by rotating the setting collar while the encoder ring is unlocked. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Patent Provisional Application No. 61/190,963, filed 3 Sep. 2008, hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to the field of multichannel audio. More particularly, the invention relates to a method for the provision of audio channels suitable for application to loudspeakers located above conventional front loudspeakers. The invention also relates to apparatus for performing the method and a computer program for performing the method.
SUMMARY OF THE INVENTION
[0003] In accordance with aspects of the invention, a method of enhancing the reproduction of multiple audio channels, the channels including channels intended for playback to the front of a listening area and channels intended for playback to the sides and/or rear of the listening area, comprises extracting out-of-phase sound information from a pair of the channels intended for playback to the sides or rear sides of the listening area, and applying the out-of-phase sound information to one or more loudspeakers located above loudspeakers playing back channels intended for playback to the front of the listening area.
[0004] The extracting may extract two sets of out-of-phase information and the applying may apply the first set of out-of-phase information to one or more left vertical height loudspeakers located above one or more left loudspeakers playing back a channel or channels intended for playback to the left front of the listening area and may apply the second set of out-of-phase information to one or more right vertical height loudspeakers located above one or more right loudspeakers playing back a channel or channels intended for playback to the right front of the listening area. According to a first alternative, the extracting may extract a single-channel monophonic audio signal comprising out-of-phase components in the pair of channels and divide the monophonic audio signal into two signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers. According to a second alternative, extracting may extract two audio signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers, each of which vertical height signals comprises out-of-phase components in the pair of channels, the left vertical height signal being weighted to the left side and/or left rear side channel in the pair of channels and the right vertical height signal being weighted to the right side and/or right rear side channel in the pair of channels.
[0005] The signals applied to the left vertical height and right vertical height loudspeakers preferably are in phase with each other in order to minimize out-of-phase signal cancellation at particular positions in the listening area.
[0006] According to the first of three alternatives, there is one pair of channels intended for playback to the sides and/or rear sides of the listening area, a left surround channel and a right surround channel. According to the second of the three alternatives, there is one pair of channels intended for playback to the sides and/or rear sides of the listening area, a left rear surround channel and a right rear surround channel. According to the third of the three alternatives, there are two pairs of channels intended for playback to the sides and/or rear sides of the listening area, a pair of side surround channels and a pair of rear surround channels, and wherein the pair of side surround channels are the left surround and right surround channels and the pair of rear surround channels are the left rear surround and right rear surround channels.
[0007] The extracting may extract the out-of-phase sound information using a passive matrix. The pair of channels from which the out-of-phase sound information is extracted may be designated Ls and Rs and the extracted out-of-phase sound information may be designated Lvh and Rvh, such that the relationships among Lvh, Rvh, Ls and Rs may be characterized by
[0000] Lvh =[(0.871* Ls )−(0.49* Rs )], and
[0000] Rvh =[(−0.49* Ls )+(0.871* Rs )].
[0000] Alternatively, the extracting may extract the out-of-phase sound information using an active matrix.
[0008] The multiple audio channels may be derived from a pair of audio source signals. The pair of audio signals may be a stereophonic pair of audio signals into which directional information is encoded. Alternatively, the multiple audio channels may be derived from more than two audio source signals comprising independent signals representing respective channels intended for playback to the front of the listening area and to the sides and/or rear of the listening area. A pair of independent signals representing respective channels intended for playback to the sides and/or rear of the listening area may be encoded with out-of-phase vertical height information.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a schematic plan view of an environment showing idealized loudspeaker locations for reproducing left (L), center (C), and right (R) audio channels intended for playback to the front of a listening area and left surround (Ls) and right surround (Rs) audio channels intended for playback to the sides of a listening area.
[0010] FIG. 2 is a schematic plan view of an environment showing idealized loudspeaker locations for reproducing left (L), center (C), and right (R) audio channels intended for playback to the front of a listening area and left surround (Ls). right surround (Rs), left rear surround (Lrs) and right rear surround (Rrs) audio channels intended for playback to the sides and rear sides of a listening area.
[0011] FIG. 3 shows the FIG. 1 example to which vertical height loudspeaker locations in accordance with aspects of the present invention have been added.
[0012] FIG. 4 shows the FIG. 3 example in a small room environment.
[0013] FIG. 5 shows the FIG. 1 example to which vertical height loudspeaker locations in accordance with aspects of the present invention have been added.
[0014] FIG. 6 shows the FIG. 5 example in a small room environment.
[0015] None of FIGS. 1-6 is to scale.
[0016] FIGS. 7-10 show examples of various ways according to aspects of the present invention in which signals for applying to loudspeakers at the Lvh and Rvh loudspeaker locations may be obtained.
DESCRIPTION OF THE INVENTION
[0017] FIG. 1 is a schematic plan view of an environment showing idealized loudspeaker locations for reproducing left (L), center (C), and right (R) audio channels intended for playback to the front of a listening area and left surround (Ls) and right surround (Rs) audio channels intended for playback to the sides of a listening area. Such arrangements typically also include an “LFE” (low frequency effects) loudspeaker (such as a subwoofer) and are often referred to as “5.1” channel playback arrangements (five main channels plus the LFE channel). For simplicity in presentation, no further reference will be made to the LFE channel, it not being necessary to the exposition or understanding of the invention.
[0018] A notional listening area 2 having a center 4 is shown among the five idealized loudspeaker locations. Setting the center loudspeaker location at 0 degrees with respect to the listening area center, the other loudspeaker locations may have a range of relative angular locations as shown—the right loudspeaker location from 22 to 30 degrees (the left being the mirror image location range) and the right surround loudspeaker location from 90 to 110 degrees (the left surround being the mirror image location range).
[0019] FIG. 2 is a schematic plan view of an environment showing idealized loudspeaker locations for reproducing left (L), center (C), and right (R) audio channels intended for playback to the front of a listening area and left surround (Ls), right surround (Rs), left rear surround (Lrs) and right rear surround (Rrs) audio channels intended for playback to the sides and rear sides of a listening area. Such arrangements typically are often referred to as “7.1” channel playback arrangements (seven main channels plus an LFE channel).
[0020] A notional listening area 6 having a center 8 is shown among the seven idealized loudspeaker locations. Setting the center loudspeaker location at 0 degrees with respect to the listening area center, the other loudspeaker locations may have a range of relative angular locations as shown—the right loudspeaker location from 22 to 30 degrees (the left being the mirror image location range), the right surround loudspeaker location from 90 to 110 degrees (the left surround being the mirror image location range), and the right rear surround loudspeaker location (the left rear surround being the mirror image location range).
[0021] FIG. 3 shows the FIG. 1 example to which vertical height loudspeaker locations in accordance with aspects of the present invention have been added. A right vertical height (Rvh) loudspeaker location is shown in dashed lines (to indicate that it is above the right (R) loudspeaker location) within an angle range of 22 to 45 degrees with respect to the listening area center 4 . A left vertical height (Lvh) loudspeaker location is shown in dashed lines (to indicate that it is above the left (L) loudspeaker location) within a mirror image of the angle range of 22 to 45 degrees with respect to the listening area center 4 .
[0022] FIG. 4 shows the FIG. 3 example in a small room environment. A sofa 10 is located in the listening area 2 . Loudspeakers are located at the L, LFE, C, R, Lvh, Rvh, Ls and Rs loudspeaker locations. Equipment associated with the multiple audio channels are shown schematically at 12 . A video screen 13 is located above the center loudspeaker location.
[0023] It will be noted that the Lvh and Rvh loudspeaker locations are above the loudspeaker locations of the front audio channels. For example, it has been found that suitable Lvh and Rvh loudspeaker locations are at least one meter above the L and R loudspeaker locations and as high as possible. Also, although it has been found that the Lvh and Rvh loudspeaker locations may be at an angle wider than the L and R loudspeaker locations (up to 45 degrees rather than 30 degrees, for example), the Lvh and Rvh loudspeaker locations preferably are substantially directly above the L and R loudspeaker locations. It will also be noted that the Lvh and Rvh loudspeaker locations are above the Ls and Rs loudspeaker locations.
[0024] FIG. 5 shows the FIG. 1 example to which vertical height loudspeaker locations in accordance with aspects of the present invention have been added. A right vertical height (Rvh) loudspeaker location is shown in dashed lines (to indicate that it is above the right (R) loudspeaker location) within an angle range of 22 to 45 degrees with respect to the listening area center 4 . A left vertical height (Lvh) loudspeaker location is shown in dashed lines (to indicate that it is above the left (L) loudspeaker location) within a mirror image of the angle range of 22 to 45 degrees with respect to the listening area center 8 .
[0025] FIG. 6 shows the FIG. 5 example in a small room environment. A sofa 10 is located in the listening area 2 . Loudspeakers are located at the L, LFE, C, R, Lvh, Rvh, Ls, Rs, Rrs and Lrs loudspeaker locations. Equipment associated with the multiple audio channels are shown schematically at 12 . A video screen 13 is located above the center loudspeaker location.
[0026] It will be noted that the Lvh and Rvh loudspeaker locations are above the loudspeaker locations of the front audio channels. For example, it has been found that suitable Lvh and Rvh loudspeaker locations are at least one meter above the L and R loudspeaker locations and as high as possible. Also, although it has been found that the Lvh and Rvh loudspeaker locations may be at an angle wider than the L and R loudspeaker locations (up to 45 degrees rather than 30 degrees, for example), the Lvh and Rvh loudspeaker locations preferably are substantially directly above the L and R loudspeaker locations. It will also be noted that the Lvh and Rvh loudspeaker locations are above the Ls, Rs, Lrs and Rrs loudspeaker locations.
[0027] FIGS. 7-10 show examples of various ways according to aspects of the present invention in which signals for applying to loudspeakers at the Lvh and Rvh loudspeaker locations may be obtained.
[0028] Referring first to FIG. 7 , five audio channels (L, C, R, Ls and Rs) for applying to respective loudspeakers at the five loudspeaker locations common to the examples of FIGS. 1 , 3 and 4 are shown. Out-of-phase sound information in the pair of channels intended for playback from the loudspeaker locations (Ls, Rs) at the sides of the listening area is extracted by an extractor or extracting process (“Extract Out-of-Phase”) 16 to provide signals for application to loudspeakers at the Lvh and Rvh loudspeaker locations ( FIGS. 3 and 4 ). Device or process 16 may be, for example, a passive or active matrix. A suitable passive matrix may be characterized as
[0000] Lvh =[(0.871* Ls )−(0.49* Rs )], and
[0000] Rvh =[(−0.49* Ls )+(0.871* Rs )].
[0000] The quiescent matrix condition of a suitable active matrix may also be characterized in the same manner.
[0029] Thus, the extracting device or process 16 extracts two audio signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers. Each of the vertical height signals comprise out-of-phase components in Ls and Rs channels, the left vertical height signal being weighted to the left side and/or left rear side channel in the pair of channels and the right vertical height signal being weighted to the right side and/or right rear side channel in the pair of channels by virtue of the matrix coefficients (0.871 and 0.49, in the example). Preferably, the vertical height signals are in-phase with respect to one another.
[0030] In the example of FIG. 8 , seven audio channels (L, C, R, Ls, Rs, Lrs and Rrs) for applying to respective loudspeakers at the seven loudspeaker locations common to the examples of FIGS. 2 , 5 and 6 are shown. Out-of-phase sound information in the pair of channels intended for playback from the loudspeaker locations (Ls, Rs) at the sides of the listening area is extracted by an extractor or extracting process (“Extract Out-of-Phase”) 16 to provide signals for application to loudspeakers at the Lvh and Rvh loudspeaker locations ( FIGS. 5 and 6 ). Device or process 16 may be, for example, a passive or active matrix. A suitable passive matrix may be characterized as
[0000] Lvh =[(0.871* Lrs )−(0.49* Rrs )], and
[0000] Rvh =[(−0.49* Lrs )+(0.871* Rrs )].
[0000] The quiescent matrix condition of a suitable active matrix may also be characterized in the same manner.
[0031] Thus, the extracting device or process 16 extracts two audio signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers. Each of the vertical height signals comprise out-of-phase components in Ls and Rs channels, the left vertical height signal being weighted to the left side and/or left rear side channel in the pair of channels and the right vertical height signal being weighted to the right side and/or right rear side channel in the pair of channels by virtue of the matrix coefficients (0.871 and 0.49, in the example). Preferably, the vertical height signals are in-phase with respect to one another.
[0032] Although it has been found suitable to extract the left vertical height signal and right vertical height signal from the Ls and Rs channel pair, the vertical height signals may also be extracted from the Lrs and Rrs channel pair.
[0033] In the example of FIG. 9 , five audio channels (L, C, R, Ls and Rs) for applying to respective loudspeakers at the five loudspeaker locations common to the examples of FIGS. 1 , 3 and 4 are shown. Out-of-phase sound information in the pair of channels intended for playback from the loudspeaker locations (Ls, Rs) at the sides of the listening area is extracted by an extractor or extracting process (“Extract Out-of-Phase”) 18 and a signal splitter or signal splitting process (“Split Signal”) 20 to provide signals for application to loudspeakers at the Lvh and Rvh loudspeaker locations ( FIGS. 3 and 4 ). In this example, the extracting device or process derives a single monophonic signal rather than two stereophonic-like signals as in the examples of FIGS. 7 and 8 . Device or process 18 may be, for example, a passive or active matrix. A suitable passive matrix may be characterized as
[0000] Lvh=Rvh =( Ls−Rs ).
[0000] The quiescent matrix condition of a suitable active matrix may also be characterized in the same manner. The signal splitting device or process 20 may be considered to be part of the extracting device or process 18 .
[0034] The single monophonic signal may be split into two copies of the same signal. Alternatively, some type of pseudo-stereo derivation may be applied to the monophonic signal.
[0035] Thus, the extracting device or process 18 extracts two audio signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers. Each of the vertical height signals comprise out-of-phase components in Ls and Rs channels. Preferably, the vertical height signals are in-phase with respect to one another.
[0036] In the example of FIG. 10 , seven audio channels (L, C, R, Ls, Rs, Lrs and Rrs) for applying to respective loudspeakers at the seven loudspeaker locations common to the examples of FIGS. 2 , 5 and 6 are shown. Out-of-phase sound information in the pair of channels intended for playback from the loudspeaker locations (Ls, Rs) at the sides of the listening area is extracted by an extractor or extracting process (“Extract Out-of-Phase”) 18 and a signal splitter or signal splitting process (“Split Signal”) 20 to provide signals for application to loudspeakers at the Lvh and Rvh loudspeaker locations ( FIGS. 3 and 4 ). In this example, the extracting device or process derives a single monophonic signal rather than two stereophonic-like signals as in the examples of FIGS. 7 and 8 . Device or process 18 may be, for example, a passive or active matrix. A suitable passive matrix may be characterized as
[0000] Lvh=Rvh =( Lrs−Rrs ).
[0000] The quiescent matrix condition of a suitable active matrix may also be characterized in the same manner. The signal splitting device or process 20 may be considered to be part of the extracting device or process 18 .
[0037] The single monophonic signal may be split into two copies of the same signal. Alternatively, some type of pseudo-stereo derivation may be applied to the monophonic signal.
[0038] Thus, the extracting device or process 18 extracts two audio signals, a left vertical height signal and a right vertical height signal, for coupling, respectively, to the left vertical height and right vertical height loudspeakers. Each of the vertical height signals comprise out-of-phase components in Ls and Rs channels. Preferably, the vertical height signals are in-phase with respect to one another.
[0039] Although it has been found suitable to extract the left vertical height signal and right vertical height signal from the Ls and Rs channel pair, the vertical height signals may also be extracted from the Lrs and Rrs channel pair.
[0040] In the various exemplary embodiments of FIGS. 3-10 , the multiple audio channels (L, C, R, Ls, Rs, Lvh, Rvh; L, C, R, Ls, Rs, Lrs, Rrs, Lvh, Rvh) may be audio channels derived from a pair of audio source signals. Such pair of audio signals may be a stereophonic pair of audio signals into which directional information is encoded. A pair of independent signals representing respective channels intended for playback to the sides and/or rear of the listening area may be encoded with out-of-phase vertical height information. In the absence of such encoding, which may be difficult to implement, the vertical height signals obtained may be considered to be pseudo-height signals. It is an aspect of the present invention that, in view of their manner of derivation, such pseudo-height signals are unlikely to include sounds that are non-sensical or out-of-place when reproduced by loudspeakers in the Lvh and Rvh positions. Such pseudo-height signals will comprise mainly ambient or diffuse sounds present in the side or rear side channels.
[0041] Alternatively, the multiple audio channels may be derived from more than two audio source signals comprising independent (or discrete) signals representing respective channels intended for playback to the front of the listening area and to the sides and/or rear of the listening area. A pair of independent signals representing respective channels intended for playback to the sides and/or rear of the listening area may be encoded with out-of-phase vertical height information. In that case, sounds may be explicitly located for playback by loudspeakers at the Lvh and Rvh loudspeaker locations.
[0042] For simplicity the various figures do not show relative time delays and gain adjustments as may be necessary in implementing a practical sound reproduction arrangement. The manner of implementing such time delays and gain adjustments are well known in the art and do not form a part of the present invention.
[0043] It will be understood that the arrangements of FIGS. 1-6 for reproducing multiple audio channels are examples of environments for aspects of the present invention. For example, the angular locations of the loudspeaker locations in the FIG. 1 and FIG. 2 examples are not critical to the invention. Also, it should also be understood that more than one loudspeaker may be placed at or in proximity to a loudspeaker location.
Implementation
[0044] The invention may be implemented in hardware or software, or a combination of both (e.g., programmable logic arrays). Unless otherwise specified, the algorithms included as part of the invention are not inherently related to any particular computer or other apparatus. In particular, various general-purpose machines may be used with programs written in accordance with the teachings herein, or it may be more convenient to construct more specialized apparatus (e.g., integrated circuits) to perform the required method steps. Thus, the invention may be implemented in one or more computer programs executing on one or more programmable computer systems each comprising at least one processor, at least one data storage system (including volatile and non-volatile memory and/or storage elements), at least one input device or port, and at least one output device or port. Program code is applied to input data to perform the functions described herein and generate output information. The output information is applied to one or more output devices, in known fashion.
[0045] Each such program may be implemented in any desired computer language (including machine, assembly, or high level procedural, logical, or object oriented programming languages) to communicate with a computer system. In any case, the language may be a compiled or interpreted language.
[0046] Each such computer program is preferably stored on or downloaded to a storage media or device (e.g., solid state memory or media, or magnetic or optical media) readable by a general or special purpose programmable computer, for configuring and operating the computer when the storage media or device is read by the computer system to perform the procedures described herein. The inventive system may also be considered to be implemented as a computer-readable storage medium, configured with a computer program, where the storage medium so configured causes a computer system to operate in a specific and predefined manner to perform the functions described herein.
[0047] A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, some of the steps described herein may be order independent, and thus can be performed in an order different from that described. | This invention relates to the field of multichannel audio. More particularly, the invention relates to a method for the provision of audio channels suitable for application to loudspeakers located above conventional front loudspeakers. | 7 |
FIELD OF THE INVENTION
The present invention relates to a control circuit for a laser printer using a laser diode.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,612,555 and particularly FIG. 7 thereof discloses a control circuit for a laser beam scanner apparatus. The laser printer described therein has a switching amplifier for controlling a laser diode. A variable current source is used as a common emitter resistor for the two switching transistors and a second current source is used to adjust the base current through the laser diode. A photodiode is also provided which measures the emitted amount of light. The energization current through the laser diode is determined on the basis of this measurement of the emitted amount of light.
One characteristic of a laser diode is that when a current is supplied to it, a small period of time elapses before the laser diode actually emits light. This switch-on or turn-on delay time is particularly troublesome when the laser diode is used in a high speed or high resolution laser printer. With a switch-on delay time of about 6 nsec and a writing frequency of about 10 MHz, the switch-on point of the laser lies approximately 6 μm later than expected. A broadening of the image due to this inherent time delay is visually disturbing to the eye with respect to fonts with a resolution, for example, of 20 image dots per mm.
This troublesome characteristic of an inherent turn-on delay time has not been overcome in the area of a laser diode in a laser printer. For example the Transaction of the IECE of Japan, Vol. E65, No. 10 (October 1982) at pp. 584-85 deals with the duty cycle of a diode laser in an optical disk system, not a laser printer. Similarly the Conference Proceedings of the Third European Conference On Optical Communication (Sept. 14-16, 1977) NTC-Fachberichte Band 59 at pp. 208-10 relates to optical communication systems, wherein the main requirement is that the turn-on delay be as short as possible so that the light pulses fall within the appropriate time slot. Other image recording devices are described in U.S. Pat. Nos. 4,387,983 and 4,594,596.
It would be desirable, therefore, to provide a control circuit for a laser printer using a laser diode wherein the inherent time delay as well as other disadvantages are obviated.
SUMMARY OF THE INVENTION
The present invention provides a correction circuit which is used in a control circuit for a laser printer having a switching amplifier for supplying current to a laser diode, the latter being modulated by means of an image signal. The correction circuit performs the function of lengthening the image signal by a correction time which substantially corresponds to the time period between when current is first supplied to the laser diode and when the laser diode emits (i.e., the turn-on delay time). As a result of this correction, the line written by the laser printer corresponds exactly to the image information supplied, there is no broadening or distortion of the image and the base current adjustment to the switching amplifier can be effected less critically.
Other details, objects and advantages of the present invention will become more readily apparent from the following description of a presently preferred embodiment thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings, a preferred embodiment of the present invention is illustrated, by way of example only, wherein:
FIG. 1 is a block diagram of a control circuit using the present invention;
FIG. 2 is a circuit diagram of a laser switching amplifier used in the control circuit of FIG. 1;
FIG. 3 is a circuit diagram of a correction circuit used in the control circuit of FIG. 1;
FIG. 4 is a timing diagram showing the shape and relative positions of the signals which occurs in the correction circuit of FIG. 3;
FIG. 5 is a circuit diagram of a protective circuit used in the control circuit of FIG. 1;
FIG. 6 is a circuit diagram of a voltage-to-current converter used in the control circuit of FIG. 1;
FIG. 7 is a circuit diagram of a light intensity-to-voltage converter used in the control circuit of FIG. 1;
FIG. 8 is a circuit diagram of a sample-and-hold circuit used in the control circuit of FIG. 1;
FIG. 9 is a circuit diagram of a differential amplifier used in the control circuit of FIG. 1; and
FIG. 10 is a circuit diagram of a regulating circuit used in the control circuit of FIG. 1;
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a block diagram of a control circuit which utilizes the present invention. Typically, a control circuit of this kind is used in a laser printer to control a laser diode which is modulated by means of an image or video signal. The modulated laser beam is deflected linewise over a photo-sensitive medium by means of a polygonal mirror. The laser diode is driven by a laser switching amplifier 11. Preferably, the laser diode is disposed in an envelope which also contains a photodiode which delivers a feedback signal related to the amount of light emitted by the laser diode. The feedback signal is converted into a voltage by a light intensity-to-voltage converter 12. This feedback voltage is fed to a sample-and-hold means 13. After an image line has been written, a sampling is fed via a line 19 to the sample-and-hold means 13. The feedback voltage which was present at the time of sampling is retained until the next sampling signal. The sampled feedback voltage is fed to a differential amplifier 17 and is compared with a reference signal fed via line 20. This reference signal represents the required light output of the laser diode. In the event of an inequality of the two signals a differential signal is generated and is fed to a regulating circuit 16. Regulating circuit 16 delivers a d.c. voltage which is fed to a voltage-to-current converter 15. The current generated therein acts as a switching current for the laser diode. If the laser diode output is too low, the current will increase via circuits 12, 13, 17, 16 and 15 so that the light output of the laser diode increases.
The regulating system described above corrects the light output on each image line while the response time of the regulating circuit is equivalent to a number of image lines. The image signal is first fed via line 18 to a correction circuit 10 before being fed to the rest of the control circuit. As will be described hereinafter, the correction circuit 10 compensates for the turn-on delay of the laser diode. The corrected image signal is fed as a modulation signal to the laser switching amplifier 11. The image signal is also fed from the correction circuit 10 to a protective circuit 14, with the output of the latter being connected to the regulating circuit 16.
FIG. 2 shows a circuit diagram for a typical laser switching amplifier used in the control circuit of FIG. 1. The main portion of this circuit is formed by a differential amplifier having a common current source 32 in the emitter leads of transistors 30 and 31. The right-hand chain of the differential amplifier is formed by transistor 31, resistors 45 and 46, and laser diode 51. The left-hand chain of the differential amplifier is formed by transistor 30, resistors 42 and 43, capacitor 44, and diodes 47 and 48. The base of transistor 31 is at a fixed potential due to a voltage divider formed by resistors 38 and 39. Preferably, the voltage divider is connected to a reference voltage source 53 while the base is connected to a capacitor 40 in order to ensure a stable potential on the base of transistor 31. The collector lead of transistor 31 contains a collector resistor 46 connected in series with a protective diode 49 which is connected in the cut-off direction to the reference voltage 53. The base of the input transistor 30 is also at a fixed potential due to a voltage divider formed by resistors 35 and 36. The modulation signal is fed to the base of transistor 30 via resistor 37.
If the modulation signal on line 67 is higher than the voltage on the base of transistor 31, transistor 30 will be turned on (i.e. it will conduct) and transistor 31 will be cut off. The current through transistor 30 is determined by the current source 32. In this configuration, current flowing through the laser diode 51 and resistor 45 will have a value which is determined only by the reference voltage 53 and resistor 45. The current flowing through the laser diode will not be determined by current source 32.
If the modulation signal on line 67 causes the base voltage of transistor 30 to fall below the base voltage of transistor 31, transistor 30 will be cut off and transistor 31 will be turned on (i.e. conduct). The current which flows through the laser diode 51 is now determined by the current source 32 since the value of resistor 45 is much larger than the value of the collector resistor 46. Diodes 33 and 34 decouple the base-emitter capacitances of the transistors 30 and 31 to prevent current oscillations.
To obtain ideal switching characteristics for the laser switching amplifier 11, the circuit of FIG. 2 is made symmetrical. This ensures that both the leading and trailing flanks of the current pulse through the laser diode 51 are substantially identical for a symmetrical input pulse on line 67 of 10 MHz. Diodes 47 and 48 and capacitor 44 create the same load for transistor 30 as the laser diode 51 does for transistor 31. Similarly, resistor 43 is equal to resistor 45 in order to give a dynamic load in the left-hand chain identical to the dynamic load in the right-hand chain. This also ensures that there is always a voltage drop across the load even when the current through the current source 32 is absent or at times when transistor 30 and transistor 31 operate in the switching zone. The symmetrical filter formed by resistors 42, 46 and capacitor 41 reduces the current overshoot to a negligible value.
When the laser diode 51 is on, the photodiode 52 which is disposed in a housing 50 with the laser diode 51 will deliver a photocurrent to the light intensity-to-voltage converter 12 which represents the amount of light emitted by the laser diode. In this LI to V converter 12, an example of which is shown in detail in FIG. 7, the photodiode current is fed to the inverting input of an amplifier 120 which together with resistor 123 converts this current into a feedback voltage. Amplifier 121, the gain of which can be set by means of a potentiometer 122 and a resistor 124, gives an output signal on line 125 whose value at the maximum light output of laser diode 51 is equivalent to a predetermined voltage.
The output signal on line 125 is fed to a sample-and-hold circuit 130 such as the one shown in FIG. 8. After each written line, a sampling pulse is fed to the sample-and-hold circuit 130 via a line 19 and a voltage divider formed by the resistors 131 and 132. When a sampling pulse is received, the instantaneous value of the feedback voltage on line 125 is made available on line 133.
The sampled feedback voltage is fed to the inverting input of a differential amplifier 140 such as the one shown in FIG. 9 via a resistor 143. In addition, a reference voltage is fed to the inverting input of the amplifier 140 via line 20 and a voltage divider formed by resistors 146 and 144. The value of the reference voltage, preferably, is related to the required current through the laser diode. The difference between the two voltages is amplified by differential amplifier 140 by an amount related to resistor 145. Zener diode 147 prevents the output voltage on line 148 from being excessive which could happen if an excessive reference voltage was used on line 20. This also prevents the current through the laser diode from exceeding a maximum value. The differential amplifier 140 is set to a fixed base line voltage by a voltage divider formed by the resistors 141 and 142 and reference voltage 53.
The differential voltage on line 148 is fed to a regulating circuit 16 such as the one shown in FIG. 10. This regulating circuit is constructed as an integrator around operational amplifier 150, resistor 152 and capacitor 151. The speed of regulation of the integrator is determined by resistors 152, 154 and capacitor 151. The integrated signal is flattened by a filter formed by resistor 153 and capacitor 156. The positive input of the operational amplifier 150 is connected to a reference voltage 53 via a resistor 155 and also to a protective circuit 14 via line 101.
The output signal of regulating circuit 16 is fed via line 116 to a voltage-to-current converter 15 such as the one shown in FIG. 6. V to I converter 15 regulates the current through the laser diode 51 in such manner as to give a constant light output. A variable current source is formed by transistor 110, resistor 119 and two operational amplifiers 111 and 115. Capacitor 113 serves to stabilize the circuit. The range of regulation of the current source is such that even at the end of the life of the laser diode there is still sufficient current available to provide the maximum light output from the laser diode.
The image signal is fed through correction circuit 10 (as shown in FIG. 3) and then over line 69 to a protective circuit 14 such as the one shown in FIG. 5. There, the image signal is fed to the inverting input of operational amplifier 90, which is constructed as a comparator circuit, where it is compared with a d.c. voltage on the noninverting input of the operational amplifier 90. This d.c. voltage is adjusted by means of resistors 92 and 93. If no image signal is supplied (i.e. when the laser printer and laser diode are off), capacitor 102 will be slowly charged up via resistor 94. If this voltage, which is fed via resistor 95 to the noninverting input of a second operational amplifier 91, is higher than the voltage on the inverting input, the output of this second operational amplifier goes high and transistor 100 will conduct. Since the collector of transistor 100 is connected via line 101 to the noninverting input of operational amplifier 150 (see FIG. 10), the voltage at this point will decrease and the current source will be switched off. This switching-off time occupies approximately two image line times.
When current is first fed to the laser diode 51, it takes about 6 nsec before the laser diode emits or delivers light. However, when the current is switched off, the light output decreases to zero immediately without delay. In order to correct for this anomaly, correction circuit 10, such as the one shown in FIG. 3, is added to the control circuit as shown in FIG. 1. A symmetrical image signal (see the first line of FIG. 4) is fed to a NAND gate 60 via line 18. The output of this signal on line 68 is inverted and delayed for a time period 80 with respect to the original image signal. This time period 80 is approximately 3 nsec and is due to the gating delay of NAND gate 60. This signal is fed through two more NAND gates 61 and 62 and then via line 72 to an input of a third NAND gate 63. The signals on lines 71 and 72 are thus always delayed for an additional gating time period 80 with respect to their respective input signal. The signal on line 68 is fed to the other input of NAND gate 63. The leading flank of the resulting signal on line 73 is thus delayed for twice the time period 80 (i.e., 6 nsec) and the trailing flank is delayed for four times time period 80 (i.e., 12 nsec) with respect to the original image signal. Since a "low" signal is required for the laser diode to emit light, the signal on line 73 is inverted again by means of NAND gate 64 and the resulting corrected image signal or modulation signal becomes available on line 67.
The time period 81 is thus lengthened by 2×3 nsec=6 nsec, with respect to the corresponding time period 83 of the original image signal. When measured from the switching-off time, the current through the laser diode 51 is switched on 6 nsec earlier than when measured from the switching-off time of the original image signal. Thus, the light delivery starts at exactly the right time. The off time 82 is correspondingly shortened by 6 nsec.
For the correction described above to work properly, it is important that the leading and trailing flanks of the image signal by symmetrical with respect to one another. This can be achieved by gating the image signal with the laser printer clock signal. In this way any image pulse distortion caused by supply lines which stray capacities is completely eliminated.
The present invention is not limited to the preferred embodiment described above. For example, the correction can also be achieved by allowing the trailing flank of the (inverted) image signal always to go high again 6 nsec later by means of a timing circuit. The correction can also be performeed dynamically. For example, the number of pulses delivered by a high frequency (HF) clock signal generator can be counted by an up-down counter in the time period elapsing between the image signal going high and the laser diode 51 going on (determined via the photodiode 52 or another externally disposed diode). When the image signal goes low the counter is switched over to a down-counter and the energizing signal remains high until the counter has counter down to the zero position. The counter is synchronized with the HF clock pulses.
While a presently preferred embodiment of practicing the invention has been shown and described with particularity in connection with the accompanying drawings, the invention may otherwise be embodied within the scope of the following claims. | A control circuit for a laser printer is described which utilizes a laser switching amplifier for supplying current to a laser diode, the latter being modulated by means of image signals. The control circuit has a correction circuit which compensates for the turn-on delay time of the laser diode. Preferably, the correction circuit lengthens the incoming image signal which controls the laser diode by a correction time which substantially corresponds to the time that elapses between when current is supplied to the laser diode and when the laser diode delivers its light, thereby eliminating distortion of the final image. | 7 |
BACKGROUND OF THE INVENTION
Bimetallic thermal strips comprised of two metals having dissimilar thermal expansion rates are well known and are used in various temperature actuated devices such as thermostats and circuit breakers. The principle by which such bimetallic strips operate depends upon the dissimilar rates of thermal expansion of the two materials. The strip bends toward the material having the lower rate of thermal expansion when the strip is heated. Alternatively, the strip bends toward the material having the higher rate of the expansion when the strip is cooled.
Similarly, the principle of magnetostriction relates to the expansion which a magnetostrictive material undergoes when subjected to a magnetic field. Bimetallic magnetostrictive strips operate on a principle similar to bimetallic thermal strips. Bimetallic magnetostrictive strips have been used heretofore and are shown in U.S. Pat. No. 2,475,148 issued on July 5, 1949 to F. Massa for TRANSDUCER MEANS, U.S. Pat. No. 2,764,647 issued on July 25, 1956 to W. G. Leslie et al for a MAGNETOSTRICTIVE RELAY, and in U.S. Pat. No. 3,216,131 issued on Nov. 9, 1965 to J. Singerman for a MAGNETOSTRICTION TEACHING DEVICE. The construction and operation of magnetostrictive strips is further shown and explained in these patents. However, the utility of a magnetostrictive strip as a closure device has not heretofore been recognized.
SUMMARY OF THE INVENTION
In accordance with the invention a magnetostrictive closure member comprises a housing having an opening adapted to receive closure means and closure means adapted to close the opening in the housing. The closure member further comprises a bimetallic magnetostrictive strip which operates the closure means. One end of the magnetostrictive strip is attached to the closure means and the other end of the magnetostrictive strip is attached to the housing.
In some embodiments of the present invention, the magnetostrictive strip may also comprise the closure means.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a front view of a novelty candy container in the form of a "flying saucer" which uses a magnetostrictive closure member in accordance with a first embodiment of the present invention;
FIG. 2 is a front view of the candy container of FIG. 1 with the closure member in its open position;
FIG. 3 is a side view of the candy container of FIG. 2;
FIG. 4 is a partially cut away sectional view of a second embodiment of the present invention as used in a remotely controlled valve; and
FIG. 5 a front view of the embodiment of FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring generally to FIg. 1, a container 10 in the form of a "flying saucer" is shown. The container 10 may be made of any suitable material, such as a plastic or a metal, and it includes a magnetostrictive closure member or door 12 made of a strip of two materials having dissimilar magnetostrictive characteristics. The container 10 may be used as a novelty device to hold candy or similar articles. However, it should be recognized that the magnetostrictive door 12 of the present invention should not be limited as a curiosity device.
Referring generally to FIg. 2, a side view of the container 10 is shown. The magnetostrictive door 12 is comprised of two metals 14, 16 having different magnetostrictive characteristics. A magnet 18, which may be either a permanent magnet or an electromagnet, is shown in close proximity to the magnetostrictive door 12. The magnetic field produced by the magnet 18 acts upon the metals 14, 16 such that the material 16 on the inside portion of the door 12 expands relative to the material 14 on the outside portion of the door 12. The relative expansion of the inner material 16 with respect to the outer material 14 causes the door 12 to open by bending outward. The opening of the door 12 is not dependent upon the presence of a hinge of any sort, but only upon the relative difference in the expansion rates of the magnetostrictive materials 14, 16 in the presence of a magnetic field.
Referring generally to FIG. 3 a front view of the container 10 with the door 12 in its open position is shown. When the door 12 is bent upward by a field from the magnet 18 the interior of the container 10 is exposed. Articles within the container 10 such as pieces of candy 20 are exposed.
Removal of the magnet 18 from proximity with the door 12 allows the materials 14, 16 to return to their site prior to magnetostriction. In the embodiment of FIGS. 1-3, the door 12 will close.
Referring generally to FIGS. 4 and 5, a magnetostrictive valve 20 for remotely controlling fluid flow is shown enclosed in a portion of a sealed pipe 22. The valve 20 includes a bimetallic magnetostrictive closure member 24 comprised of two materials 26, 28 having different magnetostrictive expansion rates. The valve 20 is further comprised of a housing portion 30 having an opening 31 and connected to the inside wall 32 of the pipe 22. In a pipe 22 having a circular cross-section, the housing 30 comprises an annular ring extending around and sealed to the interior wall 32 of the pipe 22. A ring seal 33 is also located on the plate 28 to ensure against leakage through the valve 20. The housing 30 of the valve 20 is preferrably mounted at an angle to the direction of fluid flow (shown by an arrow in FIG. 4).
Mounted outside of the pipe 22 and on either side of the valve or closure member 24 are a pair of electromagnets 34, 36. The electromagnets 34, 36 provide a magnetic field when energized by a voltage supply 38. A switch 40 is used to interrupt the current flow through the electromagnets 34, 36 to remove the magnetic field from between the electromagnets 34, 36.
In operation, the valve 20 is normally biased to a closed position and sealed by the ring 32 whereby no fluid flow takes place through the closure member 24. The closure member 24 is opened by closing the switch 40 to establish a magnetic field between the electromagnets 34, 36. The magnetostrictive material 28 closest to the closure member 24 has a higher coefficient of magnetostrictive expansion than the magnetostrictive material 26 away from the closure member 24. A magnetic field between the electromagnets 34, 36 causes the magnetostrictive materials to bend to the broken line position indicated in FIG. 4, thus moving the closure member 24 away from the housing 30. Since the closure member 24 is now substantially parallel to the flow of fluid, it provides minimal obstruction to fluid flow. Thus, the fluid flow within the pipe 22 can be remotely controlled from outside the pipe 22. The magnetostrictive valve 20 is especially useful in applications where the controlled fluid is of a toxic or corrosive nature. | A bimetallic closure member comprised of two materials having dissimilar magnetostrictive characteristics does not require a hinge, when subjected to a magnetic field, or alternatively, when removed from a magnetic field, the materials contract or expand at different rates causing the member to bend thereby opening or closing the closure member. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to reversible addition-fragmentation chain transfer reagents (RAFT reagents). More particularly, the present invention relates to organometallic RAFT reagents.
2. Description of the Related Art
Recently, with increased maturity of polymer technologies, polymer applications are involved in not only traditional plastics and synthetic resins industries but also high technology industries such as electronics, optoelectronics, communications and biotechnologies. Some relative polymer materials with specific properties are critical for the related industries. For example, photo resistant reagents for preparation of nano-type devices and nano-polymer hybrid materials for dramatically enhancing mechanical properties are all much sought after.
The properties of polymer materials are dependent on configuration. For example, polymerization degrees, molecular weight distribution and components thereof behave in relation to the performance of the polymer materials. The traditional active cation and anion polymerization methods can be used to control the polymerization degree of some monomers and narrow distribution of molecular weight, however, they are limited in their ability to precisely modify the configuration of polymer products. As well, the variety of monomers applied to the above polymerization methods is limited, and strict reaction conditions thereof also restrict use in related industries.
Free radical polymerization is a recently developed technique for controlled polymerization and is widely used in present industry. Nearly 50% of polymer materials such as styrenes, acrylates, methyl methacrylates (MMA) or acrylonitrile (AN) are polymerized in such way. In addition, reaction conditions of free radical polymerization are also milder compared to those of active cation and anion polymerization due to processing under organic solvents. After removal of oxygen gas and other stabilizers, the free radical polymerization can proceed in water.
Since traditional free radical polymerization methods are unable to control polymerization degrees of polymer products, wider molecular weight distribution of the polymer products is observed and the polydispersity index (defined as the ratio of the weight average molecular weight to number average molecular weight, Mw/Mn) is generally more than 2.
Accordingly, it is necessary to develop a novel polymerization method, in which polymerization degree of polymer products is controllable, in order to provide polymer materials with desired configuration and narrow molecular weight distributions and further explore application of polymer materials.
In 1998, CSIRO disclosed an active free radical polymerization method called reversible addition-fragmentation chain transfer process (RAFT process) to prepare polymer products with narrow molecular weight distribution and further control the polymer chain length. The so-called RAFT process is a combination of general procedures for traditional free radical polymerizations with the addition of a fixed amount of reversible addition-fragmentation chain transfer reagent (RAFT reagent). In general, RAFT process controls most free radical polymerizations for alkene monomers.
However, it is very inefficient to polymerize some monomers, such as acrylate, through RAFT process, since such monomers produce polymerization only under very dilute solution conditions to provide polymer products with narrow molecular weight distribution. Since the above problem causes longer reaction time and incomplete reaction of polymerization, it is neither economical nor convenient.
Furthermore, demands and significance of polymer materials having terminal organometallic functional groups are steadily on the increase due to application thereof to dispersants, hybrid materials, optoelectrical materials and nanotechnologies. However, polymer materials having terminal organometallic functional groups are unable to be prepared through conventional RAFT reagents. Therefore, it is necessary to develop a novel RAFT reagent for preparing polymer materials having terminal organometallic functional groups with controllable polymerization degree.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide organometallic RAFT reagents used in free radical polymerization providing precisely modification of the molecular weight of polymer products and narrowing of the distribution of molecular weight. Compared with conventional polymerizations, processes of free radical polymerization employing the organometallic RAFT reagents according to the present invention do not require processing in highly dilute solution, making them suitable for use with any kind of monomer. In addition, the RAFT reagents can be used not only in the preparation of organic polymer materials but also of polymer materials having terminal organometallic functional groups.
Another object of the present invention is to provide free radical polymerization processes employing organometallic RAFT reagents in order to efficiently polymerize free radical polymerizable monomers to produce polymer materials with low polydispersity index.
Still another object of the present invention is to provide polymer materials with low polydispersity index. Due to the specific properties, such as low polydispersity index, controllable molecular weight, and terminal organometallic functional groups, of the polymer materials, the application fields of the polymer materials in the present invention are vast.
To achieve these objects, the organometallic RAFT reagent according to the present invention comprises thiocarbonylthio metallic complexes with the structures represented by formula (I):
or Formula (II):
Accordingly, n is 2˜5, and L can be the same or different ligand which remains bound to M under polymerization conditions and is monodentate ligand, bidentate ligands, or multi-dentate ligands, such as carbon monoxide, cyanides, halide, phosphorus-containing ligands, nitrogen-containing ligands, sulfur-containing ligands, or oxygen-containing ligands.
T can be the same or different and is P, C, O N or C.
M can be the same or different and is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, N, Pd, Pt or Sc, preferably Ti, Zr, Cr, Mo, W, Fe, Ru, Os, Ni, Pd, Pt, Rh, or Ir, most preferably Cr, Mo, or W.
R 1 and R 2 can be the same or different and is H, saturated or unsaturated alkyl group, cycloalkyl group, heterocycloalkyl group, polycyclic alkyl group, aryl group, heteroaryl group, or alkylaryl group, with the saturated or unsaturated alkyl group straight or branched and having 1 to 20 carbon atoms.
R 3 can be alkyl group, aryl group, alkylaryl group, aminoalkyl group, alkylamino group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, polycyclic alkyl group, —R″CN or —R″COOH, with R″ a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and, preferably, R 3 —CH 2 Ph or —CH 2 CN.
R 4 can be alkylene group, arylene group or alkylarylene group, such as methylene group, ethylene group, or propylene group.
To achieve another object of the present invention, the present invention also provides a free radical polymerization process employing organometallic RAFT reagents. The process provides at least one free radically polymerizable monomer to react with at least one initiator and at least one organometallic RAFT reagent to undergo polymerization to produce polymers having terminal organometallic functional groups with low polydispersity index, with the at least one organometallic RAFT reagent comprising thiocarbonylthio metallic complexes with structures shown by formula (I) or formula (II).
Moreover, the free radical polymerization process employing organometallic RAFT reagents further comprise, after completing the preparation of polymers having terminal organometallic functional groups, subjecting the obtained polymers to elimination to remove the terminal organometallic functional group thereof, providing the corresponding organic polymers.
The present invention additionally provides polymers with low polydispersity index processed with at least one free radically polymerizable monomer, at least one initiator and at least one organometallic RAFT reagent via polymerization, wherein the at least one RAFT reagent comprises the thiocarbonylthio metallic complexes with the structures represented by formula (I) or formula (II).
According to the polymers of the present invention, the polydispersity index thereof is 1.4 or less. Preferably, the polydispersity index thereof is 1.3 or less in some preferred embodiments.
The present invention also provides another polymer with low polydispersity index, the reaction product of the following steps.
First, at least one free radically polymerizable monomer is reacted with at least one initiator and at least one organometallic RAFT reagent via polymerization to prepare polymers having terminal organometallic functional groups, wherein the at least one organometallic RAFT reagent comprises the thiocarbonylthio metallic complexes with the structures represented by formula (I) or formula (II).
Next, the obtained polymers are subjected to elimination to provide the corresponding organic polymers with polydispersity index of 1.4 or less through the removal of the terminal organometallic functional group thereof.
In order to understand the above and other objects, characteristics and advantages, the preferred embodiments and comparative embodiments of the present invention are now detailed described with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention can be more fully understood by reading the subsequent detailed description in conjunction with the examples and references made to the accompanying drawings, wherein:
FIG. 1 is a graph plotting molecular weight and polydispersity index against conversion of polymers as disclosed in Example 6˜8.
FIG. 2 is a graph plotting molecular weight and polydispersity index against conversion of polymers as disclosed in Example 9˜11.
DETAILED DESCRIPTION OF THE INVENTION
In order to further understand the present invention, the suitable reactants for the polymerizations according to the present invention are described in the following.
According to the present invention, the at least one initiator employed is an agent, such as peroxide or azo initiator, which generates, upon activation, free radical species through decomposition, and can be 2,2′-azobis(2-cyano-2-butane), dimethyl 2,2′-azobis(methyl isobutyrate), 4,4′-azobis(4-cyanopentanoic acid), 4,4′-azobis(4-cyanopentan-1-ol), 1,1′-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2-cyanopropane, 2,2′-azobis[2-methyl-(N)-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2′-azobis[2-methyl-N-hydroxyethyl)]propionamide, 2,2′-azobis(N,N′-dimethyleneisobutyramidine)dihydrochloride, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramine), 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(isobutyramide)dihydrate, 2,2′-azobis(2,2,4-trimethylpentane), 2,2′-azobis(2-methylpropane), dilauroyl peroxide, tertiary amyl peroxides, tertiary amyl peroxydicarbonates, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, t-butylperoxy isobutyrate, t-amyl peroxypivalate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, potassium peroxydisulfate, ammonium peroxydisulfate, di-tert butyl peroxide, di-t-butyl hyponitrite, dicumyl hyponitrite or combinations thereof.
According to the present invention, the at least one free radically polymerizable monomer can be acrylate, styrene or derivatives thereof. “Derivative” herein means a monomer having substituent functional groups, such as, but not limited to, fluorine atom, halogen atom, alkyl group, alkoxy group, phenyl group, phenoxy group, heterocyclic group, cyano group, halogen atom, trifluoromethyl group, silyl group, and the like.
In the present invention, the acrylate and derivatives thereof serving as reactive monomers can be acrylic acid, methyl acrylate, dimethylamino ethyl acrylate, diethylamino ethyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, hexyl acrylate, methacrylic acid alkyl ester, (1,6-hexanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, neopentylglycol adipate di(meth)acrylate), neopentylglycol di(meth)acrylate hydroxypivalate, dicyclopentadienyl di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylol propane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(acryloxyethyl) isocyanurate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hex(meth)acrylate or derivatives substituted optionally by at least one fluorine atom, alkyl, or alkyloxy group of the above.
According to another aspect of the present invention, the acrylate and derivatives thereof can be acrylate is monomers according to formula (III) or formula (IV).
Formula (III) is
and Formula (IV) is
Accordingly, R 5 can be hydrogen atom, fluorine atom, halogen atom, cyano group, saturated or unsaturated alkyl group, amino group, cycloalkyl group, heterocycloalkyl group, polycyclic alkyl group, aryl group, heteroaryl group, alkylaryl group, or arylalkyl group, wherein the saturated or unsaturated alkyl group can be straight or branched and has 1 to 20 carbon atoms.
R 6 and R 7 can be the same or different and is hydrogen atom, saturated or unsaturated alkyl group, cycloalkyl group, heterocycloalkyl group, polycyclic alkyl group, adamantyl group, aryl group, heteroaryl group, or alkylaryl group, wherein the saturated or unsaturated alkyl group can be straight or branched and has 1 to 20 carbon atoms.
In addition, at least one hydrogen atom bonded to the carbon atom of the acrylate monomers according to formula (III) or formula (IV) can be substituted optionally by fluorine atom, halogen atom, cyano group, alkyl group, alkoxy group, heterocycloalkyl group, aryl group, alkylaryl group, or heteroaryl group.
In the present invention, the styrene and derivatives thereof serving as reactive monomers can be styrene monomers according to formula (V).
Formula (V) is
Accordingly, R 8 can be hydrogen atom, fluorine atom, halogen atom, cyano group, saturated or unsaturated alkyl group, amino group, cycloalkyl group, heterocycloalkyl group, polycyclic alkyl group, aryl group, heteroaryl group, alkylaryl group, or arylalkyl group, wherein the saturated or unsaturated alkyl group can be straight or branched and has 1 to 20 carbon atoms.
In addition, at least one hydrogen atom bonded to the carbon atom of the styrene monomers according to formula (V) can be substituted optionally by fluorine atom, halogen atom, cyano group, alkyl group, alkoxy group, heterocycloalkyl group, aryl group, alkylaryl group, or heteroaryl group.
The following embodiments are intended to clarify the invention more fully without limiting the scope of the claims, since numerous modifications and variations will be apparent to those skilled in this art.
Preparation of Organometallic Raft Reagents
EXAMPLE 1
Organometallic RAFT reagents (1):
In a nitrogen atmosphere, 0.65 g (1 mmol) of [W(CO) 5 P(C 6 H 5 ) 2 C(═S)S]K, and 30 ml of dichloromethane were added to a round-bottom flask at room temperature to provide a maroon solution. Next, 2 ml of iodomethyl cyanide was added to the round-bottom flask, providing a red solution. After mixing completely for 60 minutes, the solvent was removed by vacuum evaporation, and the resulting mixture subjected to extraction with toluene, filtered, and condensed, providing W(CO) 5 P(C 6 H 5 ) 2 C(═S)SCH 2 CN, a thiocarbonylthio metallic complex according to the present invention. The reaction according to Example 1 is shown below.
L=CO, M=W, T=P, R 1 ═R 2 =phenyl, R 3 ═CH 2 CN, X=K, n=5.
The analysis data:
1 H NMR (CDCl 3 , ppm): δ 4.09 (s, 2H, CH2), 7.13 (m, 6H, Ph), 7.81 (m, 4H, Ph).
31 P NMR (CDCl 3 , ppm): δ 63.4 (Jw−p=251.99 Hz).
EXAMPLE 2
Organometallic RAFT reagents (2):
In a nitrogen atmosphere, 0.74 g (1 mmol) of [W(CO) 5 P(C 6 H 5 ) 2 C(═S)S]Et 4 N, and 30 ml of dichloromethane were added to a round-bottom flask at room temperature to provide a maroon solution. Next, 2 ml (2 mmol) of α-benzyl bromide was added to the round-bottom flask. After mixing completely for 60 minutes, the solvent was removed by vacuum evaporation, and the resulting mixture subjected to extraction with toluene 20 ml, filtered, and condensed, providing W(CO) 5 P(C 6 H 5 ) 2 C(═S)SCH 2 C 6 H 5 , a thiocarbonylthio metallic complex according to the present invention. The reaction according to Example 2 is shown below.
L=CO, M=W, T=P, R 1 ═R 2 =phenyl, R 3 =benzyl, X=Et 4 N, n=5.
The analysis data:
1H NMR (CDCl3, ppm): δ 4.51 s (s, 2H, CH2), 7.28 m (m, 5H, Be), 7.47 m (m, 6H, Ph), 7.64 m (m, 4H, Ph).
31P NMR (CDCl3, ppm): δ 59.8 (Jw−p=251.99 Hz).
EXAMPLE 3
Organometallic RAFT reagents (3):
In a nitrogen atmosphere, 0.74 g (1 mmol) of [W(CO) 5 P(C 6 H 5 ) 2 C(═S)S]K, and 30 ml of dichloromethane were added to a round-bottom flask at room temperature to provide a maroon solution. Next, 0.03 ml (1 mmol) of methylene iodide was added to the round-bottom flask. After mixing completely for 80 minutes, the solvent removed by vacuum evaporation, and the resulting mixture was subjected to extraction with toluene 20 ml, filtered, and condensed, providing [W(CO) 5 P(C 6 H 5 ) 2 C(═S)SCH 2 S(═S)C(C 6 H 5 ) 2 PW(CO) 5 ], a thiocarbonylthio metallic complex according to the present invention. The reaction according to Example 3 is shown below.
L=CO, M=W, T=P, R 1 ═R 2 =phenyl, R 4 ═—CH—, X=K, n=5.
The analysis data:
1 H NMR (CDCl 3 , ppm): δ 5.01 (s, 2H, CH2), 7.40–7.66 (m, 10H, Ph).
31 P NMR (CDCl 3 , ppm): δ 59.55 (Jw−p=250.96 Hz).
EXAMPLE 4
Organometallic RAFT reagents (4):
Example 4 was performed as Example 3 except for substitution of 0.032 ml of ethylene iodide for 0.03 ml of methylene iodide. After filtering and condensing, the residue was subjected to purification, providing [W(CO) 5 P(C 6 H 5 ) 2 C(═S)SC 2 H 4 S(═S)C(C 6 H 5 ) 2 PW(CO) 5 ]. The analysis data:
1 H NMR (CDCl 3 , ppm): δ 4.08 (s, 4H, CH2), 7.45–7.78 (m, 10H, Ph).
31 P NMR (CDCl 3 , ppm): δ 61.27 (Jw−p=254.05 Hz).
EXAMPLE 5
Organometallic RAFT reagents (5):
Example 5 was performed as Example 3 except for substitution of 0.033 ml of propylene iodide for 0.03 ml of methylene iodide. After filtering and condensing, the residue was subjected to purification, providing [W(CO) 5 P(C 6 H 5 ) 2 C(═S)SC 2 H 4 S(═S)C(C 6 H 5 ) 2 PW(CO) 5 ]. The analysis data:
1 H NMR (CDCl 3 , ppm): δ 1.97 (m, 2H, SCH 2 CH2), 3.34 (s, 4H, SCH2), 7.50–7.66 (m, 10H, Ph).
31 P NMR (CDCl 3 , ppm): δ 59.64 (Jw−p=250.13 Hz).
Free Radical Polymerization Employing Organometallic Raft Reagents
EXAMPLE 6
m≧2
5.4 mg (0.027 mmol) AIBN, as an initiator, and Organometallic RAFT reagents (1) (0.0649 mmol) were put into a polymerization bottle, bottle gas was displaced with nitrogen and 1.25 ml dehydrated toluene and isobutyl acrylate (25.6 mmol), as monomers were added. The above mixture was degassed with four freeze-pump-thaw cycles in the closed system to remove oxygen, the system was heated to 60° C. and reacted 6 hours. After reaction and cooling, the solvent was removed by vacuum evaporation and dimethylformamide was added. By precipitation with water, a polymer product in a 80% yield was obtained, with average molecular weight of 76705 by gel permeation chromatography (GPC) analysis, with polydispersity index (PDI) of 1.26.
The reaction according to Example 3 is shown below.
L=CO, M=W, n=5, T=P, R 1 ═R 2 =phenyl, R 3 ═CH 2 CN, R 5 =H, R 6 =—C(CH3)3, m≧2.
EXAMPLES 7˜8
Examples 7 and 8 were performed as Example 6 except that reaction times were reduced to 3 hours and 1 hour, respectively. The properties of polymer products thereof are shown in Table 1.
The exact relationship between molecular weight, polydispersity index, and conversion of polymers as disclosed in Example 6˜8 is shown in FIG. 1 .
COMPARATIVE EXAMPLE 1
Comparative Example 1 was performed as Example 6 except with an absence of organometallic RAFT reagent and the reduced reaction time of 3 hours. The properties of polymer product thereof are shown in Table 1.
TABLE 1
Molar rate of
monomers to
weight
organometallic
average
RAFT
Reaction
conversion
molecular
reagent (1)
time
(%)
weight (Mw)
PDI (Mw/Mn)
Example 6
600
6
80.5
76705
1.26
Example 7
600
3
75.4
64416
1.21
Example 8
600
1
44.1
43894
1.19
Comparative
3
96.2
185859
1.42
example 1
EXAMPLE 9
m≧2
5.5 mg (0.028 mmol) AIBN, as an initiator, and Organometallic RAFT reagents (1) (0.048 mmol) were put into a polymerization bottle, the bottle gas was displaced with nitrogen and 1.25 ml dehydrated toluene and styrene (28.0 mmol), as monomers were added. The above mixture was degassed with five freeze-pump-thaw cycles in the closed system to remove oxygen, the system was heated to 60° C. and reacted for 25 hours. After reaction and cooling, the solvent was removed by vacuum evaporation and dimethylformamide was added. By precipitation with water, a polymer product, as a pink solid in a 32% yield, was obtained with average molecular weight of 35391 by gel permeation chromatography (GPC) analysis, with PDI of 1.33.
The reaction according to Example 9 is shown below.
L=CO, M=W, n=5, T=P, R 1 ═R 2 =phenyl, R 3 ═CH 2 CN, , m≧2.
EXAMPLES 10˜11
Examples 10 and 11 were performed as Example 9 except that reaction times were reduced to 20 hours and 15 hour respectively. The properties of polymer products thereof are shown in Table 2.
The exact relationship between molecular weight, polydispersity index, and conversion of polymers as disclosed in Example 9˜11 is shown in FIG. 2 .
COMPARATIVE EXAMPLE 2
Comparative Example 2 was performed as Example 9 except an absence of organometallic RAFT reagent and the reduced reaction time for 15 hours. The properties of polymer product thereof are shown in Table 2.
TABLE 2
Molar rate of
monomers to
weight
organometallic
average
RAFT
Reaction
conversion
molecular
reagent (1)
time
(%)
weight(Mw)
PDI (Mw/Mn)
Example 9
600
25
32
35391
1.33
Example
600
20
29
33258
1.35
10
Example
600
15
25.7
29843
1.33
11
Comparative
15
38
134558
1.51
example 2
The polymerizations as described in Comparative Examples 1 and 2 were performed without the existence of organometallic RAFT reagents. Referring to Table 1 and 2, the molecule weight of polymer products, compared to Examples 6˜11, are widely increased and uncontrollable, and the PDI is increased. Moreover, the polymers obtained by Comparative Examples 1 and 2 do not have terminal organometallic functional groups in the polymer chain thereof.
Synthesis of Organic Polymers Through Organometallic Raft Reagaents
EXAMPLE 12
m≧2
1 g of Polymer (1), having terminal organometallic functional groups, as disclosed in Example 6, and 20 ml of acetonitrile were added to a round-bottom flask with low polydispersity index. After mixing completely, the resulting mixture was heated and reacted 15 hours with stirring. By precipitation with methanol, filtration, and condensation, an organic polymer product was obtained. The reaction according to Example 12 is shown below.
m≧2
Accordingly, the organometallic RAFT reagents according to the present invention can be employed in free radical polymerization to produce polymers having terminal organometallic functional groups with low polydispersity index. Moreover, the polymers further subjected to perform demetallization giving pure organic polymers.
Furthermore, free radical polymerizable monomers, such as acrylate or styrene, can be efficiently polymerized in relatively concentrated solution by the organometallic RAFT reagents.
While the invention has been described by way of example and in terms of the preferred examples, it is to be understood that the invention is not limited to the disclosed examples. To the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements. | Organometallic reversible addition-fragmentation chain transfer reagents (RAFT reagents), processes of free radical polymerization employing the same and polymers with low polydispersity index obtained thereby. The process includes polymerizing at least one monomer with at least one initiator and at least one organometallic RAFT reagent to obtain polymers having terminal organometallic functional groups with low polydispersity index. In addition, the terminal organometallic functional group may be removed by subjecting the obtained polymer to elimination to provide the corresponding organic polymers. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims the priority of PCT Application No. PCT/CH2007/000120, filed on Mar. 5, 2007, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The invention is based on a double trim tab for watercraft, in which lifting movement of an interceptor occurs by an actuation cylinder.
BACKGROUND OF THE INVENTION
Trim tabs are used to improve the glide angle of watercraft, which by changes in the direction of flow shift the corresponding uplift zones in order to facilitate more favorable weight distribution and or to start the vehicle gliding faster, as described in U.S. Pat. No. 3,628,487 or U.S. 2004/0014376 A1.
Recently other systems have also been marketed, such as submersible flow interceptors, described in Patent TW499382B or also U.S. Pat. No. 6,006,689.
SUMMARY OF THE INVENTION
The invention is designed to achieve effective trimming with the greatest possible uplift and lowest resistance values both at slow and high speeds with a trim tab for watercraft of the kind mentioned at the start. The trim tab is at the same time to be simplified by kinematics, which make it possible to accomplish the various objectives with only one hydraulic cylinder and reduce or eliminate course deviations as a result of the trimming.
Flow interceptors prove their worth at slower speeds, since they rapidly produce uplift and generate little resistance. At higher speeds conventional trim tabs have an advantage, since these, as an effective extension of the watercraft length, are more efficient at trimming while at the same time generating less resistance than the flow interceptor version.
However, trim tabs create an undesirable side effect, when they are not raised or lowered in parallel, of diverting the course of the watercraft as a result of uplift and resistance differences between the starboard and port sides, a circumstance which is actually used as an aid to steering in various applications in large jet-propelled watercraft. However for trimming conventional craft, this side effect is extremely inconvenient, since it forces the operator to make a steering correction every time the trim tabs—whether flow interceptor or tab—are activated in order to keep the craft on a given course.
The double tab, which on the one hand is in form of a flow interceptor and in the first phase also acts as one, and which on the other hand acts as a standard tab in the event of a greater performance requirement, with both tabs being operated by a single actuator. The double tab thus creates the desired trim at an economical price and by means of the built-in course correction device, the watercraft continues on the course chosen in the event of trim alteration without significant counter-steering measures being required.
The double trim tab does not require any special alloys and can be manufactured from corresponding corrosion-proof metal or plastic or from a combination of both materials.
With this invention, this is achieved by the characteristics of the first claim, which optimize the trim of a watercraft by means of two tabs or at least one tab that possesses a course correction device.
The basic objective of the invention is to achieve the greatest possible efficiency in the trimming of a watercraft as far as possible over the entire trim area by means of a double trim tab and at the same time to integrate corresponding automatic course correction guidance.
Further advantageous characteristics of the invention arise from the subclaims.
BRIEF DESCRIPTION OF THE DRAWINGS
Design examples of the invention are explained in more detail below on the basis of drawings. Identical elements in the various figures are provided with identical reference marks.
FIG. 1 is a side elevation of a double trim tab with the most important elements for the trim function
FIG. 2 is a side elevation of a double trim tab with the activated flow interceptor
FIG. 3 is a side elevation of a double trim tab with the activated flow interceptor and activated bottom tab
FIG. 4 is a side elevation of a double trim tab with the activated flow interceptor with flow interceptor suspended and lowering of flow interceptor indicated
FIG. 5 is a plan view of a double trim tab with the most important elements for the trim function and integrated course correction element
FIG. 5 a is a plan view of a shortened flow interceptor with integrated course correction element
FIG. 6 is a plan view of a trim tab with separate course correction fins
FIG. 7 is a side elevation of a tab with course correction fin and sketch of lowering into water flow
FIG. 8 is a rear elevation of a flow interceptor end with cut-outs for course correction fins
FIG. 9 is a functional diagram of electronic course correction using a steering actuator with steering wheel feedback neutralization
Only components that are directly required for understanding the invention are shown.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a side elevation of double trim tab A in the starting position, consisting of flow interceptor 1 and bottom tab 2 and which are hinge-mounted via hinge 3 a . Actuator cylinder 4 is attached to flow interceptor 1 , hinge-mounted by bearing 4 a , 4 b , with actuation cylinder 4 being supported on transom 5 .
Return spring 6 is located on bottom tab 2 to guarantee that bottom tab 2 is located at limit stop 6 a when not in use, thereby facilitating a defined alignment to water flow. In addition, bottom tab 2 is connected via flexible connecting device 7 with flow interceptor 1 so that even in the event of spring force losses bottom tab 2 can be completely raised by means of actuation cylinder 4 and the water flow, represented by arrows, can flow away unhindered behind the watercraft.
Actuation cylinder 4 can also be supported directly on stern 8 of a watercraft. Actuation cylinder 4 can be an electric drive or a fluid cylinder. If actuation cylinder 4 is a fluid cylinder, it can be equipped with a mechanical lock not shown, so that in the event of a leak or pressure loss the trim does not drift off.
Return spring 6 can be a longitudinal compression or tension spring or a torsion spring or similar.
FIG. 2 shows a side elevation of double trim tab A with the activated flow interceptor 1 . By activation of actuation cylinder 4 via switch 12 or via electronic position sensor 13 , flow interceptor 1 is lowered and as a result flow interceptor end 1 a as well and develops flow resistance as well as uplift components, shown by arrow L. Bottom tab 2 does not move, on the one hand due to the upward pressure of the water flow and on the other due to return spring 6 and limit stop 6 a . The flexible connecting element 7 bends or folds accordingly as a result of the lowering of flow interceptor 1 .
FIG. 3 shows a side elevation of double trim tab A with the activated flow interceptor 1 and activated bottom tab 2 . By activating actuation cylinder 4 which presses flow interceptor 1 on bottom tab 2 , bottom tab 2 is pressed downwards against spring 6 by the continued extension of actuation cylinder 4 until actuation cylinder 4 has been fully extended.
As a result, the uplift increases further—represented by arrow L—and the trimming of the watercraft is also increased.
FIG. 4 shows a side elevation of another version of the double trim tab A described in FIG. 1-3 , consisting of front flow interceptor 9 and bottom tab 2 , mounted via hinges 3 a , 3 b . Hinge-mounted actuation cylinder 4 is attached to front flow interceptor 9 by bearings 4 a , 4 b , just as in double trim tab A presented in FIG. 1-3 .
The broken line represents the lowering of front flow interceptor 9 , which in this case activates the flow interceptor end 1 a before bottom tab 2 , namely directly at stern 8 of the watercraft and as a result bottom tab 2 acts in an ancillary manner.
FIG. 5 shows a plan view of double trim tab A with flow interceptor 1 with course correction device 10 , bottom tab 2 , both hinge-mounted by means of hinge 3 a and actuation cylinder 4 , which is supported via hinge mount 4 a on transom 5 and is attached to flow interceptor 1 by hinge mount 4 b . The return spring 6 is attached at one end to transom 5 and at the opposite end to bottom tab 2 through an opening (not shown) in flow interceptor 1 .
As a result of non-parallel lowering of one of both flow interceptors 1 , e.g. in the event of lateral inclination of a watercraft, uplift is not only generated at the desired position, but also leads to turning, that is to a course deviation of the watercraft, due to differing resistance values. To counteract this effect, flow interceptor end 1 a is brought into a favorable form by means of course correction device 10 so that the water flow can also flow laterally along the inclined flow interceptor end 1 a . The inclination can be linear or bow-shaped. This deflection flow stream generates a transverse force Q as counter-reaction—represented by the arrow Q—which counteracts the watercraft course drift and hence maintains the pre-selected course of the watercraft more accurately, meaning that less or even no counter-steering is required.
FIG. 5 a shows a plan view of flow interceptor 1 , which has turning elements or can be lowered in a linear fashion via a guidance device, with the flow interceptor end 1 a and the course correction device 10 , which generates the uplift and simultaneously also deflects the water flow sideways and thus generates transverse force Q—represented by arrow Q. The form of the course correction device 10 can be straight or arched.
FIG. 6 shows a plan view of bottom tab 2 with integrated course correction fins 11 , which can also be hinge-mounted. Depending on the watercraft type, an optimized default setting can be chosen, so that the steering correction in the case of trim activation remains as small as possible.
FIG. 7 shows a side elevation of bottom tab 2 with the integrated course correction fin 11 , which when actuation cylinder is retracted hardly touches the waterline W. The broken lines represent a lowering of bottom tab 2 and the simultaneous submersion of course correction fin 11 in the water flow.
FIG. 8 shows a rear elevation of flow interceptor end 1 a and the integrated course correction fins 11 , which are fixed or hinge-mounted.
FIG. 9 shows a functional diagram of an electronic course correction system, which in this case suppresses steering wheel feedback. Actuation of switch 12 or signal generation by electronic position sensor 13 to activate double trim tab A in the event of non-parallel operation of double trim tab A immediately results in a course drift of the watercraft, which is corrected by course correction device 10 or course correction fin 11 and or by electronic steering device 14 . This effect is a result of the circumstance that upon activation of switch 12 or signal generation of position sensor 13 , steering device 14 measures the actual course of the watercraft via the electronic compass 15 , saves the value and only thereafter is double trim tab A activated and in the event of deviation from course, gives the order to actuator 16 of the watercraft rudder or Z-drive or outboard motor, to carry out a corresponding steering movement, to maintain the previously saved course value. Electronic compass 15 can be a magnetic field probe- or a GPS device or similar.
It is vital that in the event of a change in rudder position or of the Z-drive steering angle or outboard motor steering angle by means of actuator 16 , the steering wheel 17 is not moved on account of uncoupling device 18 , so that the helmsman himself does not counterproductively counter-steer against the automatic steering movement in the event of an automatic course correction.
In the case of electric steering, uncoupling device 18 will not relay the corresponding steering signal to the steering wheel, in the case of a hydraulic system the uncoupling device 18 is uncoupled by means of a valve or a mechanical clutch or similar.
Steering device 14 accepts a certain drift window, i.e. a corresponding course deviation tolerance to avoid having to reset actuator 16 constantly. On the other hand, steering device 14 also permits a tolerance in the steering wheel movement. However, if steering wheel 17 is turned beyond a particular angle, which is recorded by rotation angle sensor 19 on steering wheel 17 , the course correction is cancelled and actuator 16 is automatically set in the standard position relationship between steering wheel 17 and rudder position or Z-drive or outboard motor.
The application of the invention is naturally not just limited to the design examples shown and described.
REFERENCE MARK LIST
1 Flow interceptor
1 a Flow interceptor end
2 Bottom tab
3 a , 3 b Hinge
4 Actuation cylinder
4 a , 4 b Bearing
5 Transom
6 Return spring
6 a Limit stop
7 Connecting device
8 Stern
9 Front flow interceptor
10 Course correction device
11 Course correction fin
12 Switch
13 Position sensor
14 Steering device
15 Electronic compasses
16 Actuator
17 Steering wheel
18 Uncoupling device
19 Rotation angle sensor
A Double trim tab
L Uplift force
Q Transverse force | The invention involves a double trim tab for watercraft in which connection the flow interceptor ( 1 ) is activated by an actuation cylinder ( 4 ) and the flow interceptor ( 1 ) activates the bottom tab ( 2 ). One of the tabs may have a course correction device ( 10 ) or a course correction fin ( 11 ). In addition, an electronic steering device ( 14 ) can likewise carry out a course correction in the event of a trim change in which connection the steering wheel ( 17 ) is kept neutral by means of an uncoupling device ( 18 ). | 1 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of Korean Patent Application No. 10-2015-0026231, filed Feb. 25, 2015, which is hereby incorporated by reference in its entirety into this application.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention generally relates to a firmware watermarking method, firmware based on the method, and an apparatus for performing firmware watermarking, and more particularly to a firmware watermarking method, firmware based on the method, and an apparatus for performing firmware watermarking, which can provide a basis for legally preparing for the forgery/modification of firmware in the Internet of Things (IoT) and embedded devices by embedding a watermark for of original firmware at the time of manufacture to ensure preparedness in the event of firmware forgery/modification.
[0004] 2. Description of the Related Art
[0005] Firmware, which is core software for operating hardware devices, such as embedded devices, is disposed in Nonvolatile Memory (NVM) 100 , as shown in FIG. 1 .
[0006] Firmware 10 includes a bootloader (or bootstrap) area including a magic signature, a boot code address, an integrity check value, a checksum (CRC-32), etc., a firmware metadata area including manufacturing information such as the manufacturer, device ID, and firmware version, and a firmware core area including information such as a boot code and a kernel.
[0007] Requirements for firmware security have increased recently in the IoT field, as well as in existing embedded device fields.
[0008] However, it is difficult to be prepared for firmware modification attacks using only the existing firmware security method.
[0009] Since the firmware 10 may be attacked someday due to the problem of key management even if the firmware 10 is encrypted, firmware cannot be completely safe from modification attacks.
[0010] As preceding technologies related to the present invention, there are disclosed Korean Patent Application Publication No. 2007-0017455 (entitled “Secure Protection Method for Access to Protected Resources in a Processor”), Korean Patent Application Publication No. 2011-0066707 (entitled “Method for Implementing Key Sharing and Update Mechanism Utilizing Watermark”), and Korean Patent Application Publication No. 2014-0070203 (entitled “Apparatus for Integrity Verification of Firmware of Embedded System and Method thereof”).
SUMMARY OF THE INVENTION
[0011] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a firmware watermarking method, firmware based on the method, and an apparatus for performing firmware watermarking, which can provide a basis for legally preparing for firmware modification attacks by embedding a watermark for original firmware in nonvolatile memory at the time of manufacturing embedded devices.
[0012] In accordance with an aspect of the present invention to accomplish the above object, there is provided a firmware watermarking method, the method being performed by an apparatus for performing the firmware watermarking method, the method including generating an original watermark for firmware; and embedding the generated original watermark in the firmware.
[0013] The firmware watermarking method may further include, as certain firmware is loaded, determining whether the firmware has been modified.
[0014] Determining whether the firmware has been modified may be performed by comparing a firmware watermark present in the firmware with the original watermark.
[0015] When the firmware watermark present in the firmware does not match the original watermark, it may be determined that currently loaded firmware has been modified.
[0016] Generating the original watermark for the firmware may include extracting significant information from the firmware and generating a firmware signature based on the extracted significant information and a secret key; and generating the original watermark based on the generated firmware signature and the secret key.
[0017] Generating the original watermark based on the generated firmware signature and the secret key may include generating the original watermark by performing XOR encryption on the generated firmware signature and the secret key.
[0018] The secret key may be managed by a firmware manufacturer.
[0019] The firmware watermarking method may further include storing the generated original watermark in a firmware database.
[0020] The firmware database may store secret keys and original watermarks for respective embedded device IDs.
[0021] In accordance with another aspect of the present invention to accomplish the above object, there is provided firmware, including an original watermark generated based on a firmware signature and a secret key, wherein the firmware signature is generated based on significant information, present in certain firmware, and the secret key.
[0022] The original watermark may be generated by performing XOR encryption on the firmware signature and the secret key.
[0023] In accordance with a further aspect of the present invention to accomplish the above object, there is provided an apparatus, including a key generation unit for generating secret keys; a firmware database for storing the secret keys from the key generation unit and storing original watermarks generated for respective firmware components; and a management unit for controlling generation of each original watermark, storing the generated original watermark in the firmware database, embedding the generated original watermark in corresponding firmware, and controlling a comparison between a firmware watermark of currently loaded firmware and the original watermark.
[0024] The management unit may be configured to compare the firmware watermark of the currently loaded firmware with the original watermark, and determine that the currently loaded firmware has not been forged/modified if the watermarks match each other.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0026] FIG. 1 is a configuration diagram of existing firmware;
[0027] FIG. 2 is a configuration diagram of firmware according to the present invention;
[0028] FIG. 3 is a flowchart showing a firmware watermarking method according to an embodiment of the present invention;
[0029] FIG. 4 is a flowchart showing a firmware watermarking method according to another embodiment of the present invention;
[0030] FIG. 5 is a configuration diagram showing an apparatus for performing a firmware watermarking method according to the present invention; and
[0031] FIG. 6 is a diagram showing a computer system in which an embodiment of the present invention is implemented.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] The present invention may be variously changed and may have various embodiments, and specific embodiments will be described in detail below with reference to the attached drawings.
[0033] However, it should be understood that those embodiments are not intended to limit the present invention to specific disclosure forms and they include all changes, equivalents or modifications included in the spirit and scope of the present invention.
[0034] The terms used in the present specification are merely used to describe specific embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless a description to the contrary is specifically pointed out in context. In the present specification, it should be understood that the terms such as “include” or “have” are merely intended to indicate that features, numbers, steps, operations, components, parts, or combinations thereof are present, and are not intended to exclude a possibility that one or more other features, numbers, steps, operations, components, parts, or combinations thereof will be present or added.
[0035] Unless differently defined, all terms used here including technical or scientific terms have the same meanings as the terms generally understood by those skilled in the art to which the present invention pertains. The terms identical to those defined in generally used dictionaries should be interpreted as having meanings identical to contextual meanings of the related art, and are not interpreted as being ideal or excessively formal meanings unless they are definitely defined in the present specification.
[0036] Embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, the same reference numerals are used to designate the same or similar elements throughout the drawings and repeated descriptions of the same components will be omitted.
[0037] The present invention may be used by the owner of an embedded device and firmware at the level of a digital forensics service.
[0038] The present invention is based on logic for responding to firmware modification attacks from the standpoint of digital forensics in response to firmware modification attacks. That is, when firmware is maliciously forged/modified by firmware modification attacks, the present invention may utilize such logic as legal response data. In other words, the present invention may be understood to be a security device which prevents device manufacturers from assuming legal responsibility for the occurrence of attacks even if it is difficult to defend against attacks.
[0039] FIG. 2 is a configuration diagram of firmware according to the present invention. Firmware 20 according to the present invention is located in a nonvolatile memory (NVM) area 200 , and includes a bootloader area, a firmware metadata area, and a firmware core area, in the same manner as existing firmware.
[0040] The difference in structure between the firmware 20 and existing firmware is that the firmware 20 according to the present invention additionally includes an Exclusive OR (XOR) encryption-based firmware watermark (W).
[0041] FIG. 3 is a flowchart showing a firmware watermarking method according to an embodiment of the present invention.
[0042] First, for firmware watermarking, original firmware is prepared at step S 10 .
[0043] Then, a secret key K for the prepared original firmware is generated at step S 12 , and the generated secret key K is stored in a firmware database (DB) 30 . Here, the secret key K is configured to be managed by a device and firmware manufacturer (the agent of legal right and distribution). For example, the firmware DB 30 may store secret keys K for respective embedded device IDs corresponding to original firmware components.
[0044] Then, significant information (message: M) (e.g. manufacturer information, embedded device IDs, integrity information (including hash values), etc.) is extracted from the prepared original firmware, and a firmware signature (S) is generated based on the extracted significant information M and the secret key K at step S 14 . Here, the significant information M may be regarded as identity information. In the present invention, the firmware signature S may be generated based on, for example, a keyed-hash message authentication code (HMAC). This may be represented by the following Equation (1):
[0000]
S
=
HMAC
(
M
)
=
H
(
K
H
(
K
M
)
)
(
1
)
[0045] The meaning of Equation (1) is “Hash(key∥Hash (key∥message))”. Further, as the hash function, Message Digest 5 (MD5), SHA-1, or SHA-256 may be used.
[0046] Thereafter, firmware watermark W is generated based on the generated firmware signature S and the secret key K at step S 16 . Here, in the present invention, the firmware watermark W may be generated based on XOR encryption. This may be represented by the following Equation (2):
[0000] W=S (XOR) K (2)
[0000] where
W: firmware watermark S: firmware signature K: secret key
[0050] Then, the generated firmware watermark W is embedded in the firmware 20 (watermarked firmware) at step S 18 .
[0051] In this way, the firmware watermark W may be embedded in the firmware 20 .
[0052] Thereafter, when firmware having any firmware watermark W is loaded by a third party at step S 20 , significant information M is extracted from the currently loaded firmware, and the firmware signature S of the currently loaded firmware may be determined based on the extracted significant information M and the secret key K stored in the firmware DB 30 at step S 22 . Further, since “S=W(XOR)K” is satisfied, the firmware watermark W of the currently loaded firmware may be determined.
[0053] In FIG. 3 , step S 12 may be understood to be performed by the key generation unit 40 of FIG. 5 , which will be described later, and steps S 14 to S 18 and step S 22 may be understood to be performed by the management unit 44 of FIG. 5 , which will be described later.
[0054] FIG. 4 is a flowchart showing a firmware watermarking method according to another embodiment of the present invention. The process of FIG. 4 is almost identical to that of FIG. 3 .
[0055] First, original firmware is prepared for firmware watermarking at step S 30 .
[0056] Then, a secret key K for the prepared original firmware is generated at step S 32 , and the secret key K is stored in a firmware DB 32 .
[0057] Thereafter, significant (identity) information M is extracted from the prepared original firmware, and a firmware signature S is generated based on the extracted significant information M and the secret key K at step S 34 . For example, the firmware signature S may be generated based on, for example, HMAC (keyed hash). This may be represented by the above-described Equation (1).
[0058] Thereafter, a firmware watermark W is generated based on the generated firmware signature S and the secret key K at step S 36 . Here, the firmware watermark W may be generated based on XOR encryption. This may be represented by the above-described Equation (2).
[0059] Further, the generated firmware watermark W is set as original watermark W org for the corresponding original firmware, and is stored in the firmware DB 32 at step S 38 , and the original watermark W org is embedded in the original firmware (watermarked firmware) at step S 40 . For example, the firmware DB 32 may store secret keys K and original watermarks W org for respective embedded device IDs corresponding to the original firmware components.
[0060] In the above-described embodiments of the present invention, the secret key K is used twice to generate the firmware watermark W. However, the secret key (K or K S ), which is used to generate a firmware signature S depending on the requirements of the developer and the user, and the secret key (K or K W ), which is used to generate a final firmware watermark W, may be differently set.
[0061] When this process is performed, the firmware W (i.e. original watermark W org ) may be embedded in the original firmware 20 . Meanwhile, in order to extract the firmware watermark W embedded in the original firmware 20 , the conversion operation in the above-described procedure of embedding the firmware watermark W may be performed in reverse.
[0062] Next, when firmware having any firmware watermark W is loaded by a third party at step S 42 , significant information M is extracted from the currently loaded firmware, and the firmware signature S of the currently loaded firmware may be determined based on the extracted significant information M and the secret key K stored in the firmware DB 32 at step S 44 . Further, since “S=W(XOR)K” is satisfied, the firmware watermark W of the currently loaded firmware may be determined.
[0063] Thereafter, the original watermark W org of the corresponding firmware stored in the firmware DB 32 is loaded, and then it is verified whether the firmware watermark W of the currently loaded firmware matches the loaded original watermark W org by comparing the watermarks with each other at step S 46 .
[0064] If the watermarks match each other, it is determined that the currently loaded firmware has not been forged/modified, whereas if the watermarks do not match each other, it is determined that the currently loaded firmware has been forged/modified.
[0065] That is, even if a third party damages (modifies) the integrity information of the firmware, it is difficult to know which type of watermark is present in the corresponding firmware. Therefore, if the watermark of the currently loaded firmware is compared with a previously stored original watermark, the forgery/modification of the firmware may be determined. Further, even if a third party randomly generates a watermark and embeds it in firmware, when the generated watermark does not match the original watermark, it may be determined that such a modification has been made due to a malicious attack by the third party, and thus a device manufacturer need not assume legal responsibility. Of course, if a third party modifies the remaining information present in the firmware without taking into consideration the watermark, the watermark will not be present in the firmware, so that it may be easily determined that such a modification has been made due to the malicious attack by the third party, thus preventing the device manufacturer from assuming responsibility for such an attack.
[0066] In FIG. 4 , it may be understood that step S 32 is performed by the key generation unit 40 of FIG. 5 , which will be described later, and steps S 34 to S 40 and S 44 to S 46 are performed by the management unit 44 of FIG. 5 , which will be described later.
[0067] FIG. 5 is a configuration diagram showing an apparatus for performing a firmware watermarking method according to the present invention.
[0068] The apparatus for performing the firmware watermarking method according to the present invention includes a key generation unit 40 , a firmware DB 42 , and a management unit 44 .
[0069] The key generation unit 40 may generate secret keys K for respective embedded devices.
[0070] The firmware DB 42 stores the secret keys K from the key generation unit 40 . Further, the firmware DB 42 stores original watermarks W org for respective original firmware components. In other words, the firmware DB 42 may store secret keys K and original watermarks W org for respective embedded device IDs corresponding to the original firmware components.
[0071] The management unit 44 controls the generation of the original watermark W org of the corresponding original firmware, stores the generated original watermark W org in the firmware DB 42 while embedding (recording) the original watermark in the original firmware, and controls the comparison between the firmware watermark W of currently loaded firmware and the original watermark W org .
[0072] The management unit 44 compares the firmware watermark W of the currently loaded firmware with the loaded original watermark W org , and if the watermarks match each other, determines that the currently loaded firmware has not been forged/modified, whereas if the watermarks do not match each other, determines that the currently loaded firmware has been forged/modified.
[0073] Meanwhile, the embodiment of the present invention may be implemented in a computer system. As shown in FIG. 6 , a computer system 120 includes one or more processors 121 , memory 123 , a user interface input device 126 , a user interface output device 127 , and storage 128 , which communicate with each other through a bus 122 . The computer system 120 may further include one or more network interfaces 129 connected to a network 130 . Each processor 121 may be a Central Processing Unit (CPU) or a semiconductor device for executing processing instructions stored in the memory 123 or the storage 128 . Each of the memory 123 and the storage 128 may be any of various types of volatile or nonvolatile storage media. For example, the memory 123 may include Read Only Memory (ROM) 124 or Random Access Memory (RAM) 125 .
[0074] Further, when the computer system 120 is implemented in a small-sized computing device in preparation for the IoT age, if an Ethernet cable is connected to the computing device, the computing device may function as a wireless sharer, so that a mobile device may be coupled in a wireless manner to a gateway to perform encryption/decryption functions. Therefore, the computer system 120 may further include a wireless communication chip (WiFi chip) 131 .
[0075] Therefore, the embodiment of the present invention may be implemented as a non-temporary computer-readable storage medium in which a computer-implemented method or computer-executable instructions are recorded. When the computer-readable instructions are executed by a processor, the instructions may perform the method according to at least one aspect of the present invention.
[0076] In accordance with the present invention having the above configuration, a watermark for original firmware is embedded at the time of manufacture in preparation for firmware forgery/modification of IoT and embedded devices, thus enabling pre-emptive defense and post-attack legal response to firmware modification attacks, and enabling integrity to be verified in real time/non-real time in relation to whether firmware has been modified.
[0077] That is, when a problem occurs in a device or a system due to cyber or physical attacks, the present invention may be used not only in the legal response related to the field of digital forensics, but also in the real-time/non-real-time verification of firmware integrity.
[0078] As described above, optimal embodiments of the present invention have been disclosed in the drawings and the specification. Although specific terms have been used in the present specification, these are merely intended to describe the present invention and are not intended to limit the meanings thereof or the scope of the present invention described in the accompanying claims. Therefore, those skilled in the art will appreciate that various modifications and other equivalent embodiments are possible from the embodiments. Therefore, the technical scope of the present invention should be defined by the technical spirit of the claims. | Disclosed herein are a firmware watermarking method, firmware based on the method, and an apparatus for performing firmware watermarking, which can provide a basis for legally preparing for firmware modification attacks by embedding a watermark for original firmware in nonvolatile memory at the time of manufacturing embedded devices. The presented method is a firmware watermarking method performed by an apparatus for performing the firmware watermarking method, the method including generating an original watermark for firmware, and embedding the generated original watermark in the firmware. | 6 |
FIELD OF THE INVENTION
This invention relates to a device for setting of stitching conditions in an electronic control sewing machine which forms stitched patterns.
BACKGROUND OF THE INVENTION
In such a sewing machine which controls amounts of needle amplitude and amounts of fabric feed per each of operations of a key, it is not preferable to finely divide changing amounts of controls with respect to a unit operation in order to obtain a determined control through a lesser number of operations. However, on the other hand, fine controls are required as the controlling functions. In the conventional electronic control sewing machine, these two requirements have not been satisfied.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a device to designate quantitatively the amount of the needle amplitude and the amount of the fabric feed by a keyboard. Functions of the keyboard are switched to designation of the needle amplitude amount and to designation of the fabric feed amount by means of a switch designating key. The keyboard is operated, for example, twice so that the needle amplitude amount or the fabric feed amount are designated by two-digit numbers, respectively.
The present invention will be explained with reference to the attached drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a front panel of a sewing machine, showing an embodiment of the invention; and
FIG. 2 is a control block diagram.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be explained in reference to an embodiment shown in the attached drawing. A front panel 1 is provided on a front face of a sewing machine (not shown). A keyboard 2 is used for selecting patterns, and controlling a needle amplitude amount, a fabric feed amount and a basic line of a straight stitching, and it designates them by twice pushing or, for the control of the basic line by once pushing keys with a pattern number. A switch designating key 3 is for switching functions of the keyboard 2 each time of its operations, and is for lighting a lamp 4 of a pattern selection, a lamp 5 of an amplitude setting, a lamp 6 of a feed setting and a lamp 7 of a basic line of a straight stitching.
Each of indicators 8, 9, 10 of seven LED segments corresponds to each of the lamps 4, 5, 6. With respect to items lighted by said lamps, the numbers thereof designated by the keyboard 2 are indicated. While the lamp 7 is lighted, the basic line indicating lamps 11, 12, 13 respectively correspond to a designation key 14 of a specific number 0, a designation key 15 of a specific number 1 and a designation key 16 of a specific number 2. When those keys are pushed, the lamps are lighted to designate a left (L), a middle (M) and a right (R) with respect to the basic line of the straight stitching.
FIG. 2 is a control block diagram. The keyboard 2 shows representatively one of the ten keys or switches, and an output line is made L level by operation of each of them.
A switching device 17 successively switches, per each of operations of the switch designating key 3, the number designated by the keyboard 2 to a pattern number memory device 18, an encoder 19 for controlling the needle amplitude, an encoder 20 for controlling the fabric feed or a latch 21 for controlling the basic line of the straight stitching.
A counter 22 counts number of actuations of the switch designating key 3, and a decoder 23 decodes the counted values per each of the actuations and outputs H level signals from terminals (a) (b) (c) (d) thereof. The output from the terminal (a) of the decoder 23 gives designation of the numerical value by the keyboard 2 to the pattern number memory device 18, and lights the lamp 4. Similarly, the output from the terminal (b) works the encoder 19 and the lamp 5, and the output from the terminal (c) works the encoder 20 and the lamp 6, and the output from the terminal (d) works the latch 21.
The pattern number memory device 18 designates a data reading-out initial address of the pattern data memory device 24 in accordance with operation of the keyboard 2, and outputs from an auto data memory device 25 auto data BA and FA concerning the amplitude and the feed common to each stitch of said pattern.
The auto data BA and FA control the stitching data from the pattern data memory device 24 in the pattern data computing device 26, and make auto setting values of coefficients for computing the size (mm) of the pattern, while the encoders 19, 20 encode the designation of the numerical values of the keyboard 2 to give them to AND-OR circuits 27, 28.
The encoders 19, 20 receive respectively auto data BA and FA from an auto data memory device 25. The auto data BA of the encoder 19 and the designated data by the keyboard 2 are switched each other by a flip-flop 29. The auto data FA of the encoder 20 and the designated data by the keyboard 2 are switched each other by a flip-flop 30.
The flip-flops 29, 30 are set by supplying a control power source, or are set by receiving L level signal at set terminals (S) via AND circuit 31 when a pattern number memory device 18 receives an operation signal of the keyboard 2. At this time, outputs of AND-OR circuits 27, 28 are made auto data BA and FA respectively by the outputs Q, and when the terminal (b) of the decoder 23 is H level, the flip-flop 29 receives H level signal at a reset terminal (R) and is reset, or when the terminal (c) is H level, the flip-flop 30 is similarly reset, and at this time the outputs of AND-OR circuits 27, 28 are switched to values of the encoders 19, 20.
When the pattern is selected, the latch 32 receives a signal L 1 of AND circuit 31, and the pattern number memory device 18 issues an output and it latches the pattern number and causes the decoder 33 to show it on the indicator 8.
When the terminal (b) of the decoder 23 is H level and the keyboard 2 is operated, the latch 34 receives a latch signal via AND circuit 35 and then latches the output signal in accordance with the designation of the keyboard 2 of AND-OR circuit 27, and causes the decoder 36 to show it on the indicator 9.
When the terminal (c) of the decoder 23 is H level and the keyboard 2 is operated, the latch 37 receives the latch signal via AND circuit 38, and then latches the output signal in accordance with the designation of the keyboard 2 of AND-OR circuit 28 and causes the decoder 39 to show it on the indicator 10.
When a selected pattern is a straight stitch, the terminal (d) of the decoder 23 is H level and when any one of the specific keys 14, 15, 16 is operated the latch receives the latch signal and it latches the data designated then by the keys 14, 15, 16, and lights the basic line indicating lamps 11, 12, 13 in accordance with said designation.
When the pattern number memory device 18 designates the straight stitch, AND circuits 41, 42, 43 are operative and give the designated data then by the keys 14, 15, 16 to the latch 21.
The pattern data counting device 26 receives the signal BA' TA' or Sb of the latch 34, 37 or 21, and counts controlled values of the selected patterns and gives them to the pattern forming device 44.
A reference will next be made to actuation of the above mentioned structure.
When the control power source is supplied, the terminal (a) of the decoder 23 is made H level and an initial resetting is made in such a way that the number 0 is designated by the keyboard 2, so that the straight stitch is selected and the number of the straight stitch is shown in the indicator 8.
The flip-flops 29, 30 are set, and under this condition, the control signals BA', FA' to be input into the pattern data count device 26 are made auto data BA, FA respectively, and the signal BA' sets the central basic line. At this time, the signal Sb is not input.
When the switch designating key 3 is pushed three times in order to designate the left basic line (L) of the straight stitch, the lamp 7 is lighted. When the key 14 of the keyboard 2 is operated under this condition, the latch 21 latches the signal of the left basic line, and the lamp 11 is lighted and the pattern forming device 44 forms the straight stitch of the left basic line.
For selecting another pattern, the switch designating key 3 is pushed once, then the terminal (a) of the decoder 23 is made H level and the pattern selecting lamp 4 is lighted. Under this condition, the keyboard 2 is operated to designate the pattern number of two figures, then this pattern is selected. The control signals BA', FA' to be input into the pattern data count device 26 are made auto data BA, FA. Thus, the numbers set by the signals BA, FA are shown in the indicators 9, 10.
For enlarging or reducing the pattern in size in the amplitude direction, the switch designating key 3 is pushed, then the terminal (b) of the decoder 23 is made H level and the amplitude setting lamp 5 is lighted. The flip-flop 29 is reset, and under this condition, the keyboard 2 is operated to designate a size of the pattern in the needle amplitude direction with a two-digit number, and this number is indicated in the indicator 9 so that a required size is designated. Similarly, if the enlargement or reduction is required in the fabric feed direction, the switch designating key 3 is pushed, then the terminal (c) of the decoder 23 is made H level, and the flip-flop 30 is reset. Under this condition, the keyboard 2 is operated to designate the size of the pattern in the fabric feed direction, so that this figure is indicated in the indicator 10 and the size in the fabric feed direction is designated.
As mentioned above, depending upon the present invention, the size of the pattern may be controlled rapidly and finely by an easy operation. Since the keyboard 2 may be used in common with respect to the different functions, the space for the operating part in the panel may be reduced relatively. | A stitch condition setting device for an electronically controlled sewing machine that forms stitch patterns and has a reciprocating needle, a fabric feed and an electronic memory to store stitch control signals, the stitch condition setting device having an apparatus for separately designating a change in a needle amplitude amount and a fabric feed amount in accordance with a selected stitch pattern, an apparatus for switching the designating apparatus between designating the change in needle amplitude amount and designating the change in fabric feed amount; and an apparatus responsive to the designating apparatus and the switching apparatus for changing the needle amplitude amount and the fabric feed amount in accordance with the selected stitch pattern. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a device and assembly for cable bolt systems. In particular, the present invention relates to cable bolt apparatus which can be used to both mix associated cable resin and to tension the cable bolt assembly against a bearing plate.
[0003] 2. Background and Related Art
[0004] Steel bolts and cable bolts are commonly used in underground mines to stabilize geologic layers adjacent mine openings. For example, cable bolt assemblies are used to secure the geologic layers of the roof of a mine tunnel or drift to prevent roof strata from falling and causing obstructions or injury to persons or equipment in the tunnel.
[0005] Rigid members such as steel rods or rebar have long been used in anchoring systems in construction applications and as rock bolts in mining applications. For example, threaded rebar manufactured and sold by DYWIDAG under the brand name Threadbar has been used for rock bolts for years. Anchoring such rods or rebar at one end or at both ends allows the rod to bear a tension load. Steel rods have been particularly useful in anchoring applications because threads can be formed on the outer surface of the rods to receive desired bolts with corresponding threads or to receive other fastening devices such as a Frazer-Jones D9 expansion shell assembly. Rigid steel rods are, however, not always ideal because they are manufactured in finite, fixed lengths and long rods are often difficult to work with in confined spaces such as construction and mining sites. Rigid rods can also be subject to shearing stresses if, for example, there is ground movement adjacent the rod in a mining application.
[0006] Steel cables comprising multiple strands of steel have also been used as anchoring systems. Unlike rigid, steel rods, cables provide some flexibility along their length. That is, a cable can bent around an object or deflect when subject to ground movement adjacent the cable. In some instances, steel cable is easier to use in confined spaces. Historically, anchoring a cable at one or both ends is more difficult because the cable does not bear threads to receive bolts. A number of cable anchoring methods have been used. One example is a multistrand anchorage device which separates strands of the cable and anchors each strand individually or in groups such as the DYWIDAG Multistrand Posttensioning System. Another example comprises positioning a thread-bearing sleeve along the length of the cable at the desired locations to receive a desired bolt or Frazer-Jones D9 expansion shell assembly.
[0007] Another example includes unraveling the cable and sliding a ring over and down along the center or king wire of the cable to a desired location and then rewinding the cable. In this way, a bulge or ‘bird cage’ is formed in the cable due to a spreading of the wires in the area of the ring. The bulge or spreading of the wires permits resin used with the cable to permeate into the cable to enhance anchorage of the cable upon the setting of the resin. If mechanical anchorage is also desired, an additional thread-bearing or thread-like-bearing apparatus must still be added if a desired bolt or Frazer-Jones D9 expansion shell assembly is to be used.
[0008] A number of devices rely upon a thread-bearing sleeve being disposed about the cable or other threaded systems to tension a cable. The sleeve is positioned relative to the cable or other threaded systems which are used to tension the cable including:
[0009] (1) placing a threaded tube and clamping it on the cable;
[0010] (2) threading the cable itself;
[0011] (3) placing and securing the cable inside a threaded bar such as a DYWIDAG threadbar® with a hole in it; and
[0012] (4) using a threaded insert which is placed over the king wire and then threaded inside a Frazer-Jones D9 expansion shell assembly.
[0013] A number of cable and other bolt assemblies are known, including those taught by U.S. Pat. Nos. 2,667,037, 3,077,809, 4,509,889, 4,954,017, 4,984,937, 5,015,125, 5,026,517, 5,215,411, 5,230,589, 5,259,703, 5,375,946, 5,378,087, 5,441,372, 5,458,442, 5,525,013 and others.
[0014] These techniques include drilling a long hole into the earthen geology which is to be stabilized. A requisite amount of multi-component epoxy resin is placed in the hole at the desired location. The steel cable is also placed in the hole. A machine is used to spin the cable thereby mixing the multi-component epoxy to cause the chemical reaction between the multi-components. The epoxy sets and anchors the cable in the hole.
[0015] Known techniques for mixing multi-component epoxy include mechanical devices designed to spin the cable at a relatively low torque to mix the epoxy components followed by tensioning the cable using increased torque after the cable is cemented in place. The mechanical devices include known and available domed nuts, crimped bolts, perpendicular roll pins, shear pins, weld beads, and keys ways which permit spinning a nut or other structure on a threaded sleeve at a low torque without compromising or defeating the ability of the domed nuts, crimped bolts, perpendicular roll pins, shear pins, weld beads, and keys ways to at least temporarily fix the relative position of the nut and threaded sleeve affixed to the cable. In this way, the spinning of the cable mixes the epoxy resin components. After the cable is cemented in place, a higher torque is then applied, typically in the same direction as to low torque, to tension the cable which use of higher torque does compromise or defeat the ability of the domed nuts, crimped bolts, perpendicular roll pins, shear pins, weld beads, and keys ways to fix the relative position of the nut and threaded sleeve.
[0016] Accordingly, it would be an improvement in the art to augment or even replace current techniques with simpler devices and devices with permit the use of power tools which apply torque in opposing directions.
SUMMARY OF THE INVENTION
[0017] The present invention relates to an integral wedge barrel and threaded sleeve which can be used for both spinning to mix epoxy resin and used to tension a cable bolt.
[0018] The present invention contemplates a unitary or integral wedge barrel and threaded sleeve with a rotatable nut about the threaded sleeve. The threaded sleeve is disposed in an aperture of a bearing plate. A cable is disposed through the threaded sleeve and through the wedge barrel. The cable is fixed in place relative to the wedge barrel by common barrel wedges. When assembled the cable is fixed relative to the wedge barrel. The threaded sleeve is fixed relative to the barrel because the threaded sleeve and wedge barrel are either manufactured as one integral unit or are joined together in a fixed relationship by means of welding or some other common joining practice.
In use, the device permits reliable mixing of epoxy resin components by rotating the nut until it abuts the wedge barrel whereupon the cable will spin in the direction the nut is being turned. This turning or spinning action can be used to mix the epoxy resins. After the epoxy resin is set and the cable cemented in place, the nut can be turned or spun in the opposite direction causing the nut to move away from the wedge barrel and move toward the opposing bearing plate against which the nut can be forced by applying high torque to the nut whereby the cable is put under tension.
[0021] While the methods and processes of the present invention have proven to be particularly useful in the area of cable bolt tensioning, those skilled in the art can appreciate that the methods and processes can be used in a variety of different applications and in a variety of different areas of manufacture to yield an equivalent device.
[0022] These and other features and advantages of the present invention will be set forth or will become more fully apparent in the description that follows and in the appended claims. The features and advantages may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. Furthermore, the features and advantages of the invention may be learned by the practice of the invention or will be obvious from the description, as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] In order that the manner in which the above recited and other features and advantages of the present invention are obtained, a more particular description of the invention will be rendered by reference to specific embodiments thereof, which are illustrated in the appended drawings. Understanding that the drawings depict only typical embodiments of the present invention and are not, therefore, to be considered as limiting the scope of the invention, the present invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
[0024] FIG. 1 illustrates a perspective view of one embodiment of the device and system that provides a suitable structure and function for the present invention;
[0025] FIG. 2 illustrates a cross-sectional view of an embodiment of the present invention;
[0026] FIG. 3 illustrates a cross-sectional view of an embodiment of the present invention;
[0027] FIG. 4 illustrates use of the present invention with a breakaway view of a cable cemented into a geological formation.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention relates to a device for use in anchoring and tensioning cables or cable bolts to stabilize walls or ceilings in earthen bodies such a mines or other underground openings. In particular, the present invention is directed to a integral device which both facilitates mixing the epoxy resins used to anchor the cable bolt in the earthen body and tensioning the cable bolt after it is anchored in place. The present invention contemplate an integral wedge barrel used to capture a cable bolt and a threaded sleeve about the cable bolt.
[0029] FIG. 1 and the corresponding discussion are intended to provide a general description of one embodiment of the present invention. One skilled in the art will appreciate that the invention may be practiced by one or more embodiments in a variety of configurations. Mixing and tensioning assembly 10 is shown in perspective view. Assembly 10 comprises cable or cable bolt 20 , an integral body 30 of a wedge barrel and threaded sleeve disposed about cable bolt 20 , nut 40 disposed along integral body 30 and bearing plate 50 . Cable bolt 20 , nut 40 and bearing plate 50 are all commonly known, used and available cable bolt components.
[0030] Device or integral body 30 comprises a wedge barrel end 32 defining sloped interior surface 34 to receive a plurality of wedges 36 . Integral body 30 further comprises a threaded sleeve portion 38 . While the preferred embodiment contemplates integral body 30 being a continual unitary member, a person of skill in the art would recognize that other embodiments would contemplate an interface between a wedge barrel and a threaded sleeve achieved via a weld between a wedge barrel and a threaded sleeve, via a recessed barrel with a mating surface corresponding to a mating end of a threaded sleeve, via screwing the threaded sleeve into the wedge barrel, or via prongs on one end of the threaded sleeve engaging apertures in the wedge barrel, all to fix the interrelationship between the wedge barrel and the threaded sleeve. The result in all embodiments being a interdependent wedge barrel and threaded sleeve which when either part is acted upon by a force the same or substantially similar force is also transmitted to the other part of the integral body 30 .
[0031] Cable bolt 20 is disposed within integral body 30 . As is commonly known in the art, wedges 36 disposed between cable bolt 20 and wedge barrel 32 act by friction and/or other forces to fix cable bolt 20 within integral body 30 such that force along bolt 20 is transmitted to integral member 30 and vice versa.
[0032] Nut 40 is disposed along a length of body 30 between wedge barrel portion 32 and bearing plate 50 . Nut 40 can be turned in both directions. As shown in FIG. 2 , when nut 40 is turned until it abuts wedge barrel 32 then upon abutting wedge barrel portion 32 further turning of nut 40 will cause both body 30 and bolt 20 to turn or spin in the same direction. This spinning can be used to spin cable bolt 20 to mix epoxy resins as discussed below.
[0033] As shown in FIG. 3 , nut 40 can also be turned in the opposite direction until it abuts bearing plate 50 , or one or more optional washers 60 constructed of metal and/or HDEP, Teflon, nylon, or similar material to reduce friction. Bearing plate 50 defines a plate aperture 52 to permit plate 50 to move independent of body 30 . Similarly, optional washer 60 defines a washer aperture 62 to permit washer 60 to move independent of body 30 . Upon abutting plate 50 or washer 60 , continued turning or spinning of nut 40 in the same direction puts a force upon plate 50 thereby putting cable bolt 20 in tension as plate 50 is forced against a geologic formation such as rock, dirt or mineral. It will be appreciated that threaded sleeve portion 38 is of a sufficient length to permit tensioning and, as needed, retensioning of cable bolt 20 . Threaded sleeve portion 38 may be about twelve inches or longer or shorter depending the geologic conditions of use.
[0034] The present invention permits universal use of assembly 10 . For example, when sleeve threads are right-handed threads as is typical in coal mines, tools are used that are able to turn nut 40 in either direction as depicted in FIGS. 2 and 3 .
[0035] When sleeve threads are left-handed threads as is typical in hard rock mines, jack-legs are typical tools used to turn nuts 40 but are able to turn nut 40 in only one direction to force nuts 40 against bearing plates 50 . When tools such as unidirection jack-legs are used, the present invention further comprises means for providing a temporary, fixed interface between nut 40 and threaded sleeve portion 38 . The temporary, fixed interface between nut 40 and threaded sleeve portion 39 can be accomplished by known techniques previously discussed including but not limited to known frictional interfaces, weld beads, roll pins, keyway with keys, buggered threads, domed nuts, or crimped sleeves. As a result, turning of nut 40 also turns sleeve portion 38 which turns cable 20 . This commonly known unidirection turning of nut 40 can be used to both mix epoxy resins at a lower torque and then at higher torque to overcome, break or shear the temporary, fixed interface to place bolt 20 under tension.
[0036] An optional sleeve cover, not shown, extends along the length of threaded portion 39 from nut 40 through plate aperture 52 towards the end of portion 38 to protect the threads of portion 38 from being damaged or compromised prior to use. The sleeve cover is disposed about threaded portion 38 and can comprise plastic, soft metal, rubber, cardboard or any other suitable material capable of protecting the threads of sleeve portion 38 from damage prior to use.
[0037] As depicted in FIG. 4 , the subject wall, roof, or floor of a geologic structure 70 is drilled to create drill hole 72 . Epoxy resin components are placed in hole 72 at the desired location. Assembly 10 , preassembled and comprising cable 20 , body 30 , nut 40 and bearing plate 50 is placed such that cable 20 is inserted into hole 72 to a depth so a portion of cable 20 is inserted through or adjacent the epoxy resin components in hole 72 . Nut 40 is turned in the desired direction causing cable 20 to spin in hole 72 to mix the epoxy components to create a epoxy resin or cement 80 which acts to anchor cable 20 in hole 72 . After the resin or cement is set and cable 20 is anchored in hole 72 , nut 40 is again turned in the desired direction to force nut 40 against bearing plate 50 , or washer 60 . This pushes plate 50 against wall 70 putting cable 20 under tension. The appropriate tension is placed upon cable 20 help stabilize wall 70 . A plurality of assemblies 10 are used over an area to prevent geologic structures 70 from caving in and causing injury to persons or equipment.
[0038] While the Figures only depict a single cable comprising a plurality of wound or twisted wires, the present invention also contemplates assembly 10 being capable or receiving and securing a number of cables 20 as illustrated in U.S. Pat. No. 5,525,013.
[0039] Thus, as discussed herein, the embodiments of the present invention embrace an assembly 10 comprising a device which can be turned to facilitate both mixing resin or cement to anchor cable 20 and to put cable 20 under the desired tension to secure the adjacent surface.
[0040] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope. | The present invention is directed to a device and assembly for the anchoring and tensioning of cable bolts used in earthen formations to stabilize the earthen structures to prevent or minimize the caving in or sluffing-off of the earthen structure. The new invention presents an integral wedge barrel and threaded sleeve which can be turned to facilitate both the mixture of cementing resins and the physical tensioning of an anchored cable. | 4 |
This application is a continuation-in-part of U.S. Ser. No. 213,415 filed Jun. 30, 1988 now abandoned.
FIELD OF THE INVENTION
This application relates to color photographic materials. In a particular aspect, it relates to color photographic materials with a particular combination of development inhibitor releasing compound and cyan dye-forming coupler.
BACKGROUND OF THE INVENTION
Photographic couplers which release a development inhibitor in a controlled manner are described in U.S. Pat. Nos. 4,248,962 and 4,409,323, inter alia. These couplers comprise a coupler moiety which has a timing group joined in its coupling position. A development inhibitor is attached to the timing group and is released from it after the bond between the timing group and the coupler is cleaved as a result of reaction between the coupler and oxidized color developing agent. Mechanisms by which such release of the development inhibitor from the timing group can occur include an intermolecular nucleophilic displacement reaction, an electron transfer reaction, and a hydrolysis reaction. Development inhibitors also can be released, as a function of development, from timing groups which are released from compounds which are not couplers such as the hydrazides of U.S. Pat. No. 4,684,604 and the hydroquinones of European Patent Application No. 0,167,168.
One of the advantageous effects obtained as a result of release of a development inhibitor, either directly from a coupler or other carrier moiety, or through a timing group as described above, is an improvement in photographic performance, such as an improvement in the sharpness of the image formed.
Also known are cyan dye-forming image couplers that contain a ureido group in the 2-position.
Lau, U.S. Pat. No. 4,333,999 issued Jun. 8, 1982, describes cyan dye-forming couplers containing p-cyanophenylureido substituents in the 2-position of the coupler. These couplers are described as yielding dyes having desirable hues and good stability properties.
U.S. Pat. Nos. 4,777,616 and 4,849,328 describe couplers which improve upon those described in the '999 patent by modifying the 5-position substituent. The '999, '616, and '328 patents suggest the use of the cyan couplers therein described in combination with DIR couplers, but do not specifically suggest that they be used with couplers of the type described in the '962 or '323 patents.
U.S. Pat. Nos. 4,434,225 and 4,609,619 describe phenolic cyan dye-forming couplers containing a ureido group in the 2-position. Use of one of these couplers with a DIR coupler is mentioned in these patents. However, they do not describe any particular combination of phenolic coupler and DIR coupler nor the particular advantage deriving from the selection of the present invention.
It would be desirable to provide color photographic materials which have improved performance.
SUMMARY OF THE INVENTION
We have found that unexpected improvements in photographic performance, such as sharpness, speed and granularity, can be obtained with a photographic element comprising a support bearing a silver halide emulsion layer having associated therewith a DIR compound having the structure I: ##STR3## wherein:
CAR is a carrier moiety,
TIME is a timing group and
INH is a development inhibitor moiety; together with a cyan dye-forming coupler having the structure II: ##STR4## wherein:
m is 0 or 1;
n is 0, 1 or 2;
Y is halogen, or sulfonyl;
Q is --O-- or --NH--;
R 1 is an unsubstituted or a substituted, straight or branched chain alkyl group having from 1 to about 20 carbon atoms, an unsubstituted or a substituted cycloalkyl group having from 3 to about 8 carbon atoms in the ring, an alkylcarbonyl or an alkoxycarbonyl group having from 1 to about 20 carbon atoms in the alkyl or the alkoxy moiety;
R 2 is as defined for R 1 or is hydrogen;
R 3 is an unsubstituted or a substituted alkyl group having from 1 to about 24 carbon atoms, an unsubstituted or a substituted cycloalkyl group having from 3 to about 8 carbon atoms in the ring, an unsubstituted or a substituted aryl group having from 6 to about 24 carbon atoms, or an unsubstituted or a substituted heterocyclic group having from 3 to about 8 atoms in the heterocyclic ring, wherein the hetero ring atoms can be nitrogen, oxygen, or sulfur;
when R 3 is a primary alkyl group, R 1 contains at least 2 carbon atoms;
Z is hydrogen or a coupling-off group; and the --CN substituent on the phenyl ureido group is para or meta to the ureido group.
DETAILED DESCRIPTION OF THE INVENTION
When the R 1 and R 2 groups are substituted, such substituents include hydroxy, halogen, or alkoxy having from 1 to about 8 carbon atoms.
When the R 3 group is substituted, such substituents include alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido and sulfamoyl groups wherein the alkyl and aryl substituents, and the alkyl and aryl moieties of the alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, arylcarbonyl, acyl, acyloxy, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido and sulfamoyl substituents can contain, respectively, from 1 to about 10 carbon atoms and from 6 to about 30 carbon atoms and can be further substituted with such substituents.
Coupling off groups defined by Z are well known to those skilled in the art.
Representative classes of coupling-off groups include alkoxy, aryloxy, heteroyloxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamido, phosphonyloxy and arylazo. These coupling-off groups are described in the art, for example, in U.S. Pat. Nos. 2,455,169; 3,227,551; 3,432,521; 3,476,563; 3,617,291; 3,880,661; 4,052,212; 4,134,766; 4,753,871; 4,775,616; 4,849,328; and 4,923,791; and in U.K. Patents and published application Nos. 1,466,728; 1,531,927; 1,533,039; 2,006,755A and 2,017,704A.
Examples of suitable coupling-off groups which can be represented by Z are: ##STR5## Especially preferred Z groups are hydrogen and ##STR6## where R 4 is an alkyl or an alkoxy group having from 1 to about 10 carbon atoms.
While improvements in sharpness are obtained when couplers of Structure II, above, are used in combination with DIR compounds of Structure I above, especially advantageous effects are obtained with the following preferred couplers of Structure II:
In a preferred embodiment the cyano group is in the para position with respect to the ureido group and n is 0.
In a particular preferred embodiment, n is 0, the cyano group is para to the ureido group, R 1 is alkyl of 1 to about 20 carbon atoms and R 2 is hydrogen or alkyl of 1 to about 4 carbon atoms.
In an especially preferred embodiment, n is 0, the cyano group is para to the ureido group, R 1 is alkyl of 1 to about 14 carbon atoms, R 2 is hydrogen and R 3 is alkyl of 2 to about 24 carbon atoms.
The DIR compounds which satisfy Structure I are known in the art and are described in such patents as U.S. Pat. Nos. 4,248,962; 4,409,323; 4,684,604; 4,737,451; U.K. Patent Application No. 2,099,167; and EP Published Applications Nos. 167,168 and 255,085, as well as in U.S. Pat. Nos. 4,546,073; 4,564,587; 4,618,571; 4,698,297; and OLS No. 3,307,506. Other useful DIR compounds are described in DeSelms and Kapecki U.S. Pat. No. 4,782,012 issued Nov. 1, 1988; Szajewski, Poslusny and Slusarek U.S. patent application Ser. No. 334,261, filed Apr. 6, 1989, which is a continuation-in-part of Ser. No. 209,741, filed Jun. 21, 1988; Begley, Carmody and Buchanan U.S. Pat. Nos. 4,847,185 issued Jul. 11, 1989 and 4,857,440 issued Aug. 15, 1989; and Begley et al. U.S. patent application Nos. 483,600; 483,601; and 483,602 filed Feb. 22, 1990.
The carrier moiety, represented by CAR, can be any moiety which, as a result of reaction with oxidized color developing agent, will release the timing group. Preferably the carrier is a coupler, but it can be another group, such a hydrazide, a hydrazine or a hydroquinone. Coupler moieties can form a colored or colorless, diffusible or nondiffusible, reaction product with oxidized color developing agent. Preferred are cyan dye-forming coupler moieties.
When the carrier is a coupler moiety, the DIR compounds are DIR couplers represented by the structure ##STR7## where COUP is a coupler moiety.
Particularly preferred are couplers where COUP is a naphtholic cyan dye-forming coupler moiety represented by the following generalized structure: ##STR8## where:
the unsatisfied bond represents the point of attachment of the timing group, and
BALL is a ballast group such as aryl and alkyl, especially alkoxyaryl and aryloxyalkyl.
Also useful are compounds where COUP is a yellow dye forming coupler moiety having one of the structures ##STR9## where
the unsatisfied bond is the point of attachment to the timing group,
BALL is a ballast group such as alkoxycarbonyl, alkoxy, alkylsulfonamido and alkylsulfamyl,
X is as defined below, and
Y' is alkyl such as methyl and t-butyl, and aryl such as phenyl and alkoxy phenyl.
Preferred timing groups, represented by TIME, for use in these couplers are described in the aforementioned '962 and '323 patents and European Patent Application No. 0255085.
Particularly preferred are those timing groups which have the structures: ##STR10## where:
p is 1 to 4;
q is 0 or 1;
A is --O-- or ##STR11##
R 5 is hydrogen, alkyl of 1-20 carbon atoms or aryl of 6 to 20 carbon atoms; and
X is hydrogen and one or more substituents independently selected from hydroxy, cyano, fluoro, chloro, bromo, iodo, nitro, alkyl, alkoxy, aryl, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carbonamido, and sulfonamido.
Especially preferred are those timing groups having the structure: ##STR12## wherein
X is as defined above;
Q' is --N═ or ##STR13## and
W is a group characterized by a σ m value greater than 0.0 (σ m is determined as described in Hansch and Leo, Journal of Medicinal Chemistry, 16, 1207, 1973). Typical W groups are --NO 2 , --NHSO 2 CH 3 , --NHSO 2 C 16 H 33 , --NHCOCH 3 , --NHCOC 11 H 23 , --Cl, --Br, --OCH 3 , --OCH 2 CH 2 OCH 3 , etc.
The development inhibitor which is eventually released from the DIR coupler can be any of the development inhibitors known in the art, such as mercaptotetrazoles, selinotetrazoles, mercaptobenzothiazoles, selinobenzothiazoles, mercaptobenzoxazoles, selinobenzoxazoles, mercaptobenzimidazoles, selinobenzimidazoles, benzotriazoles, tetrazoles, triazoles, thiadiazoles, and benzodiazoles. Preferred are mercaptotetrazole inhibitors, benzotriazole inhibitors, and oxadiazole inhibitors. Particularly preferred are those inhibitors which are substituted with groups that cause them to be deactivated when they diffuse into processing solution. Such inhibitors are described in U.S. Pat. No. 4,477,563, U.K. Patent Application No. 2,099,167 and U.S. Pat. No. 4,782,012. Other useful inhibitors are described in Japanese Published Patent Application Nos. 60-233650, 60-225156, 60-182438 and European Published Patent Application Nos. 0167168, 0101621, 0192199, 0157146.
Examples of preferred couplers which satisfy structures I and II, respectively, are shown in Tables I and II below:
TABLE I__________________________________________________________________________Specific DIR couplers that are useful in the invention have thestructures: ##STR14##__________________________________________________________________________ ##STR15## I-1 ##STR16## I-2 ##STR17## I-3 ##STR18## I-4 ##STR19## I-5 ##STR20## I-6 ##STR21## I-7 ##STR22## I-8 ##STR23## I-9 ##STR24## I-10 ##STR25## I-11 ##STR26## I-12 ##STR27## I-13 ##STR28## I-14 ##STR29## ##STR30## I-15 ##STR31## I-16 ##STR32## I-17 ##STR33## I-18 ##STR34## I-19 ##STR35## I-20 ##STR36## I-21 ##STR37## I-22 ##STR38## I-23 ##STR39## I-24 ##STR40## I-25__________________________________________________________________________
TABLE II__________________________________________________________________________ Specific Image coupler that are useful in the invention have thestructures__________________________________________________________________________ ##STR41## R.sub.1 R.sub.2 R.sub.3 Q m Z CN__________________________________________________________________________II-1 C.sub.2 H.sub.5 H C.sub.16 H.sub.33 -n 0 OC.sub.6 H.sub.4OCH.sub.3 paraII-2 C.sub.2 H.sub.5 H " " H "II-3 C.sub.3 H.sub.7 -i H " " H "II-4 " H " " OC.sub.6 H.sub.4 OCH.sub.3 1 "II-5 C.sub.2 H.sub.5 H " " " metaII-6 C.sub.3 H.sub.7 -i H " O 1 " paraII-7 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CO.sub.2 C.sub.3 H.sub.7 C.sub.16 H.sub.33 -n O 1 H paraII-8 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR42## NH 1 OC.sub.6 H.sub.4 OCH.sub.3 1 paraII-9 C.sub.14 H.sub.29 H CH.sub.3 O 1 " paraII-10 C.sub.10 H.sub.21 H ##STR43## NH 1 " metaII-11 C.sub.4 H.sub.9 -n H C.sub.6 H.sub.11 -cyclo NH 1 H metaII-12 C.sub.2 H.sub.5 H ##STR44## O 1 OC.sub.6 H.sub.4 OCH.sub.3 . paraII-13 C.sub.4 H.sub.9 -t H C.sub.16 H.sub.33 -n O 1 " paraII-14 C.sub.2 H.sub.5 H ##STR45## NH 1 " paraII-15 C.sub.3 H.sub.7 -i H ##STR46## O 1 OC.sub.6 H.sub.4 OCH.sub.3 metaII-16 C.sub.3 H.sub.7 -i H C.sub.14 H.sub.29 -n -- 0 H paraII-17 C.sub.3 H.sub.7 -i H C.sub.14 H.sub.29 -n -- 0 OC.sub.6 H.sub.4C.sub.4 H.sub.9 -s para__________________________________________________________________________ ##STR47## R.sub.1 R.sub.2 R.sub.3 Q m Z Y CN__________________________________________________________________________II-18 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR48## 0 ##STR49## Cl meta paraII-19 iPr H C.sub.16 H.sub.33 -n NH 1 H SO.sub.2C.sub.3 H.sub.7 -n meta paraII-20 C.sub.5 H.sub.9 -cyclo H ##STR50## O 1 ##STR51## ##STR52## paraII-21n-Bun-Bu C.sub.12 H.sub.25 -n 0 ##STR53## Cl para meta__________________________________________________________________________
The compounds and couplers used in this invention are, in general, known compounds and can be prepared by techniques known in the art. Compounds, described in the copending application referred to above on page 7 are novel and can be prepared by the procedures described in that application, the disclosures of which are incorporated herein.
The coupler combinations of this invention can be incorporated in silver halide emulsions and the emulsions can be coated on a support to form a photographic element. Alternatively, one or both of the couplers can be incorporated in the same or different photographic elements adjacent the silver halide emulsion where, during development, the coupler will be in reactive association with development products such as oxidized color developing agent.
The photographic elements can be either single color or multicolor elements. In a multicolor element, the cyan dye-forming coupler is usually associated with a red-sensitive emulsion, although it could be associated with an unsensitized emulsion or an emulsion sensitized to a different region of the spectrum. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta image forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The dry layer thickness of individual emulsion layer units can be on the order of 0.5 to 6μ thick on a dry basis. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. The element typically will have a total thickness (excluding the support) of from 5 to 30μ.
In the following discussion of suitable materials for use in the elements of this invention, reference will be made to Research Disclosure, December 1978, Item 17643, published by Kenneth Mason Publications, Ltd., The Old Harbourmaster's, 8 North Street, Emsworth, Hampshire P010 7DD, ENGLAND, the disclosures of which are incorporated herein by reference. This publication will be identified hereafter by the term "Research Disclosure."
The silver halide emulsions employed in the elements of this invention can be comprised of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions can include silver halide grains of any conventional shape or size. Specifically, the emulsions can include coarse, medium or fine silver halide grains. High aspect ratio tabular grain emulsions are specifically contemplated, such as those disclosed by Wilgus et al U.S. Pat. Nos. 4,434,226, Daubendiek et al 4,414,310, Wey 4,399,215, Solberg et al 4,433,048, Mignot 4,386,156, Evans et al 4,504,570, Maskasky 4,400,463, Wey et al 4,414,306, Maskasky 4,435,501 and 4,643,966 and Daubendiek et al 4,672,027 and 4,693,964. Also specifically contemplated are those silver bromoiodide grains with a higher molar proportion of iodide in the core of the grain than in the periphery of the grain, such as those described in GB No. 1,027,146; JA No. 54/48,521; U.S. Pat. Nos. 4,379,837; 4,444,877; 4,665,012; 4,686,178; 4,565,778; 4,728,602; 4,668,614; 4,636,461; EP No. 264,954. The silver halide emulsions can be either monodisperse or polydisperse as precipitated. The grain size distribution of the emulsions can be controlled by silver halide grain separation techniques or by blending silver halide emulsions of differing grain sizes.
Sensitizing compounds, such as compounds of copper, thallium, lead, bismuth, cadmium and Group VIII noble metals, can be present during precipitation of the silver halide emulsion.
The emulsions can be surface-sensitive emulsions, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or internal latent image-forming emulsions, i.e., emulsions that form latent images predominantly in the interior of the silver halide grains. The emulsions can be negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
The silver halide emulsions can be surface sensitized. Noble metal (e.g., gold), middle chalcogen (e.g., sulfur, selenium, or tellurium), and reduction sensitizers, employed individually or in combination, are specifically contemplated. Typical chemical sensitizers are listed in Research Disclosure, Item 17643, cited above, Section III.
The silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines. Illustrative spectral sensitizing dyes are disclosed in Research Disclosure, Item 17643, cited above, Section IV.
Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Item 17643, Section IX and the publications cited therein.
In addition to the couplers described herein the elements of this invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These additional couplers can be incorporated as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
The coupler combinations of this invention can be used with bleach accelerator releasing couplers as described in European Patent Application No. 0,193,389 A and U.S. Pat. No. 4,912,024.
The coupler combinations of this invention can be used with colored masking couplers as described in U.S. Pat. No. 4,883,746.
The photographic elements of this invention can contain brighteners (Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section VI), antistain agents and image dye stabilizers (Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (Research Disclosure Section VIII), hardeners (Research Disclosure Section XI), plasticizers and lubricants (Research Disclosure Section XII), antistatic agents (Research Disclosure Section XIII), matting agents (Research Disclosure Section XVI) and development modifiers (Research Disclosure Section XXI).
The photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
Preferred color developing agents are p-phenylene diamines. Especially preferred are 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
With negative working silver halide this processing step leads to a negative image. To obtain a positive (or reversal) image, this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable. Alternatively, a direct positive emulsion can be employed to obtain a positive image.
Development is followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver and silver halide, washing and drying.
The following examples further illustrate this invention. In these examples, comparative couplers having the following structures were employed: ##STR54##
The structures of couplers of the invention are shown in Tables I and II above.
EXAMPLES 1-5
Photographic elements were prepared with the following layers, in the order indicated, on a cellulose acetate film support:
Layer 1
Red sensitized AgBrI emulsion (having an average grain diameter of 0.52 μm, 6.4 mole % I) (1.61 g Ag/m 2 , 2.69 g gel/m 2 ), cyan image coupler (see Table III) and cyan DIR coupler (see Table III). Equimolar quantities of image couplers were used in the elements and the DIR couplers were used in amounts that would give essentially the same density and gamma in each of the elements after exposure and processing.
Layer 2
Overcoat layer of gelatin (1.08 g/m 2 ) and Hardener bisvinylsulfonylmethane coated at 1.75% by weight of total gelatin.
The dried coatings were exposed (1/15 sec.) to daylight through a graduated density step wedge and processed at 37.8° C., as follows:
______________________________________color developer 3.25 min.bleach (Fe-EDTA) 4 min.wash 3 min.fix 4 min.wash 3 min.______________________________________
color developer composition:
______________________________________4-amino-3-methyl-N-ethyl-beta- 3.35 g/lhydroxyethylanaline sulfateK.sub.2 SO.sub.3 2.0 g/lK.sub.2 CO.sub.3 30.0 g/lKBr 1.25 g/lKI 0.0006 g/ladjusted to pH = 10.0______________________________________
Sharpness was evaluated by calculating AMT acutance values for a 35 mm system, as described in J. SMPTE, 82, 1009 (1973). Larger values of AMT indicate a sharper image is obtained. The results are reported in Table III.
TABLE III______________________________________ Image DIR Coupler Coupler 35 Sys.Example (g/m.sup.2) (g/m.sup.2) AMT.______________________________________1 C-1(0.85) I-1(0.043) 92.42 II-2(0.88) I-1(0.043) 94.53 C-2(1.13) I-1(0.086) 94.64 II-1(1.06) I-1(0.086) 96.45 II-5(1.05) I-1(0.086) 96.6______________________________________
The above data show a clearly discernible improvement in sharpness is obtained when a DIR coupler is used in combination with a 4-equivalent cyan dye-forming phenolic coupler having a para-cyanophenylureido group in the 2-position, and a sulfo containing ballast in the 5-position (II-2) vs a phenoxy ballast (C-1) in the 5-position. A similar result is obtained with the 2-equivalent couplers II-1 and II-5 vs C-2. It should be noted that two-equivalent image couplers give better sharpness than do four-equivalent image couplers.
EXAMPLES 6-7
Color photographic elements were prepared with the following layers, in the order indicated, on a cellulose acetate film support.
Layer 1
A slow cyan dye-forming layer (SC) comprising a blend of a red-sensitized 0.42 μm silver bromoiodide emulsion (6.1 mol % I) at 1.29 g Ag/m 2 and a red-sensitized 0.21 μm AgBrI emulsion (4.8 mole % I) at 0.43 g Ag/m 2 , gelatin (2.69 g/m 2 ), a masking coupler 1-hydroxy-4-(4-[2-(8-acetamido-1-hydroxy-3,6-disulfonaphthyl)azo]phenoxy)-2-(Δ-[2,4-di-tert.-amyl-phenoxy]butyl)naphthamide dipyridine salt (0.041 g/m 2 ), a cyan dye-forming coupler (see SC in Table IV) and a DIR coupler (see SC in Table IV).
Layer 2
A fast cyan dye-forming layer (FC) comprising a 0.76 μm silver bromoiodide emulsion (6 mole % I) at 1.08 g Ag/m 2 , gelatin (1.61 g/m 2 ), a cyan dye-forming coupler (see FC in Table IV) and a DIR coupler (see FC in Table IV).
Layers 3 and 4
Gelatin at 2.85 g/m 2 .
Layer 5
A gelatin overcoat layer (2.8 g/m 2 ) hardened with bisvinylsulfonylmethane at 1.75% by weight of total gelatin. Equimolar quantities of the image coupler (C-1 or II-1) were used and the quantity of DIR coupler (I-2) was chosen to give essentially the same density and gamma in the exposed and processed element.
The dried elements were exposed and processed as in the preceding examples.
TABLE IV______________________________________ Image DIRExam- Coupler Coupler 35 Sys.ple (g/m.sup.2) (g/m.sup.2) AMT.______________________________________ 6 C-1 FC-0.48 I-2 FC-0.033 92.6 SC-0.77 SC-0.019 7 II-1 FC-0.60 I-2 FC-0.059 94.8 SC-0.97 SC-0.050______________________________________
The above data show that a combination of a DIR coupler such as II-2 with a phenolic cyan dye-forming coupler having both a p-cyanophenylureido group in the 2-position, and a sulfo-containing ballast in the 5-position provides a sharpness improvement in comparison to a similar coupler combination in which the cyan dye-forming coupler does not have a sulfo-ballast in the 5-position.
EXAMPLES 7-21
Multicolor photographic elements were prepared having the following schematic structure. In this structure the numbers in parenthesis show the coverage in g/m 2 .
______________________________________UV Absorbing Overcoat LayerFast Yellow Image Forming LayerSlow Yellow Image Forming LayerYellow Filter LayerFast Magenta Image Forming LayerSlow Magenta Image Forming LayerGelatin InterlayerFast Cyan Dye Forming Layer (FC):Fast Red Sensitized Tabular Grain AgBrI, 6 mol % I,(0.81 g Ag/m.sup.2) Emulsioncyan dye forming coupler (see FC in Table V)DIR coupler (see FC in Table V)gelatin (1.13 g/m.sup.2)Slow Cyan Dye forming Layer (SC):Slow Red Sensitized emulsion blend of tabular grainsAgBrI, 3 mol % I, (1.40 g Ag/m.sup.2) and cubic AgBrI, 3mol % I, grains (0.27 g Ag/m.sup.2)cyan dye forming coupler (see SC in Table V)DIR coupler (see SC in Table V) (0.052 g/m.sup.2)Antihalation LayerFilm Support______________________________________
The amounts of couplers in each of the cyan dye forming layers were chosen to give essentially the same density and contrast in the exposed and processed elements. The dried coatings were exposed (1/500 sec), through a graduated density step wedge (Wratten 29 filter), and processed for 31/4 minutes in the C-41 process described in the British Journal of Photography Annual, 1977, pages 201-205. The AMT acutance values for 35 mm film system were calculated as described in the previous example and the red separation and neutral speeds were measured. The following Table V reports AMT acutance for the normal exposure (i.e. the region exposed by a camera calibrated to ANSI standards) and for an average of the normal exposure and one stop on either side. The speed reported is the difference in speed between the comparison coating and the invention, and is for a red separation exposure. Sets of coatings exposed and processed together are separated by a double space.
These data show improvement in acutance for the invention compared with control coatings contain image coupler C-1. In addition it shows an increase in red speed in all cases. It will be noted that in some instances there is a relationship between speed and acutance; i.e. a more dramatic increase in acutance may accompany a less dramatic increase in speed.
TABLE V__________________________________________________________________________ Red 35MM System AMT Imaging Coupler Dir Coupler Speed 35MM System AMT (average of under,EX. Layer (g/m.sub.2) Layer (g/m.sub.2) (Log E) (normal) normal and over)__________________________________________________________________________ 8 C-1 FC(0.32), SC(0.97) I-2 FC(0.028), SC(0.045) Check 89.9 88.5 9 II-3 FC(0.33), SC(1.01) I-2 FC(0.034), SC(0.052) +0.08 91.1 90.710 II-4 FC(0.40), SC(1.23) I-2 FC(0.060), SC(0.080) +0.09 92.9 92.711 C-1 FC(0.32), SC(0.97) I-4 FC(0.031), SC(0.049) Check 89.4 88.112 II-3 FC(0.33), SC(1.01) I-4 FC(0.038), SC(0.057) +0.08 90.7 90.413 II-4 FC(0.40), SC(1.23) I-4 FC(0.067), SC(0.086) +0.08 89.6 90.114 C-1 FC(0.32), SC(0.97) I-3 FC(0.028), SC(0.047) Check 91.3 88.815 II-4 FC(0.40), SC(1.23) I-3 FC(0.054), SC(0.080) +0.05 93.9 93.116 C-1 FC(0.32), SC(0.97) I-1 FC(0.025), SC(0.034) Check 88.6 87.817 II-4 FC(0.40), SC(1.23) I-1 FC(0.042), SC(0.062) +0.08 88.8 88.918 C-1 FC(0.32), SC(0.97) I-2 FC(0.030), SC(0.045) Check 90.9 89.519 II-2 FC(0.33), SC(1.01) I-2 FC(0.038), SC(0.056) +0.07 92.5 91.920 C-1 FC(0.32), SC(0.97) I-1 FC(0.025), SC(0.034) Check 88.5 88.121 II-2 FC(0.33), SC(1.01) I-1 FC(0.032), SC(0.043) +0.09 88.7 89.1__________________________________________________________________________
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. | A color photographic material with good photographic performance, such as sharpness, speed and granularity, contains a development inhibitor releasing compound having the structure: ##STR1## wherein: CAR is a carrier moiety;
TIME is a timing group; and
INH is a development inhibitor moiety,
in association with a cyan dye-forming coupler having the structure: ##STR2## wherein: R 1 , R 2 , R 3 , Q, Z, Y, m, and n are as defined in the specification. | 8 |
FIELD OF THE INVENTION
[0001] This invention relates to the lubrication of 2-stroke and 4-stroke marine diesel internal combustion engines, the former usually being referred to as cross-head engines and the latter as trunk piston engines. Respective lubricants therefor are usually known as marine diesel cylinder lubricants (“MDCL's”) and trunk piston engine oils (“TPEO's”).
BACKGROUND OF THE INVENTION
[0002] Cross-head engines are slow engines with a high to very high power range. They include two separately-lubricated parts: the piston/cylinder assembly lubricated with total-loss lubrication by a highly viscous oil (an MDCL); and the crankshaft lubricated by a less viscous lubricant, usually referred to as a system oil.
[0003] Trunk piston engines may be used in marine, power-generation and rail traction applications and have a higher speed than cross-head engines. A single lubricant (TPEO) is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by means of a pumped circulation system. The cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation systems that finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
[0004] It is known in the art to include brightstock in MDCL's and TPEO's, brightstock being a high viscosity oil that is highly refined and dewaxed and that is produced from residual stocks or bottoms. It may, for example, have a kinematic viscosity at 100° C. of greater than 25, usually greater than 30, mm 2 s −1 , such as a solvent-extracted, de-asphalted product from vacuum residuum generally having a kinematic viscosity at 100° C. of 28-36 mm 2 s −1 .
[0005] Brightstock is however expensive and art describes ways of replacing it. WO 99/64543 describes MDCL's formulated without brightstock and US 2008/0287329 describes a TPEO containing little or no brightstock.
[0006] A problem in the art is to formulate brightstock-free MDCL's and TPEO's at reduced cost and at the same time provide improved antiwear properties.
SUMMARY OF THE INVENTION
[0007] It is now found that the use of olefin copolymers such as an amorphous ethylene-propylene copolymer in an MDCL or a TPEO enables the above problem to be overcome.
[0008] Thus, the present invention provides a two-stroke or four-stroke marine engine lubricating oil composition comprising an oil of lubricating viscosity in a major amount and
(A) additives, in respective minor amounts; and (B) a viscosity modifier in the form of an olefin copolymer in an amount in the range of 0.05-6 mass %,
wherein the composition includes less than 0.5 mass %, preferably less than 0.1 mass %, of brightstock; preferably brightstock is completely or substantially absent from the composition.
[0011] In further aspects the present invention comprises:
[0012] The use of a viscosity modifier (B) to improve the anti-wear properties of a marine diesel cylinder lubricant or of a trunk piston engine oil which includes less than 0.5 mass %, preferably less than 0.1 mass %, of brightstock; preferably brightstock is absent or is substantially absent from the marine diesel cylinder lubricant or the trunk piston engine oil;
[0013] A method of lubricating a cross-head marine diesel engine comprising supplying a lubricating oil composition including viscosity modifier (B) to the piston/cylinder assembly of the engine; and
[0014] A method of lubricating a trunk piston marine diesel engine comprising supplying the composition to the engine.
[0015] In this specification, the following words and expressions, if and when used, have the meanings ascribed below:
[0016] “active ingredients” or “(a.i.)” refers to additive material that is not diluent or solvent;
[0017] “comprising” or any cognate word specifies the presence of stated features, steps, or integers or components, but does not preclude the presence or addition of one or more other features, steps, integers, components or groups thereof; the expressions “consists of” or “consists essentially of” or cognates may be embraced within “comprises” or cognates, wherein “consists essentially of” permits inclusion of substances not materially affecting the characteristics of the composition to which it applies;
[0018] “major amount” means 40 or 50 mass % or more of a composition;
[0019] “minor amount” means less than 50 mass % of a composition;
[0020] “TBN” means total base number as measured by ASTM D2896.
[0000] Furthermore in this specification, if and when used:
[0021] “calcium content” is as measured by ASTM 4951;
[0022] “phosphorus content” is as measured by ASTM D5185;
[0023] “sulphated ash content” is as measured by ASTM D874;
[0024] “sulphur content” is as measured by ASTM D2622;
[0025] “KV100” means kinematic viscosity at 100° C. as measured by ASTM D445.
[0026] Also, it will be understood that various components used, essential as well as optimal and customary, may react under conditions of formulation, storage or use and that the invention also provides the product obtainable or obtained as a result of any such reaction.
[0027] Further, it is understood that any upper and lower quantity, range and ratio limits set forth herein may be independently combined.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The features of the invention will now be discussed in more detail below.
Oil of Lubricating Viscosity
[0029] The lubricant composition contains a major proportion of an oil of lubricating viscosity. Such lubricating oils may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40, such as 3 to 15, mm 2 /sec, as measured at 100° C., and a viscosity index of 80 to 100, such as 90 to 95. The lubricating oil may comprise greater than 60, typically greater than 70. mass % of the composition.
[0030] Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
[0031] Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and homologues thereof.
[0032] Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
[0033] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of such esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
[0034] Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
[0035] Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
[0036] Unrefined, refined and re-refined oils can be used in lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment are unrefined oils.
Marine Diesel Cylinder Lubricant (“MDCL”)
[0037] An MDCL may employ 10-35, preferably 13-30, most preferably 16-24, mass % of a concentrate or additive package, the remainder being base stock. It preferably includes at least 50, more preferably at least 60, even more preferably at least 70, mass % of oil of lubricating viscosity based on the total mass of MDCL. Preferably, the MDCL has a compositional TBN (using ASTM D2896) of 40-100, such as 50-60.
[0038] The following may be mentioned as examples of typical proportions of additives in an MDCL.
[0000]
Mass % a.i.
Mass % a.i.
Additive
(Broad)
(Preferred)
detergent(s)
1-20
3-15
dispersant(s)
0.5-5
1-3
anti-wear agent(s)
0.1-1.5
0.5-1.3
pour point dispersant
0.03-1.15
0.05-0.1
base stock
balance
balance
Trunk Piston Engine Oil (“TPEO”)
[0039] A TPEO may employ 7-35, preferably 10-28, more preferably 12-24, mass % of a concentrate or additives package, the remainder being base stock. Preferably, the TPEO has a compositional TBN (using D2896) of 20-60, such as 25-55.
[0040] The following may be mentioned as typical proportions of additives in a TPEO.
[0000]
Mass % a.i.
Mass % a.i.
Additive
(Broad)
(Preferred)
detergent(s)
0.5-12
2-8
dispersant(s)
0.5-5
1-3
anti-wear agent(s)
0.1-1.5
0.5-1.3
oxidation inhibitor
0.2-2
0.5-1.5
rust inhibitor
0.03-0.15
0.05-0.1
pour point dispersant
0.03-1.15
0.05-0.1
base stock
balance
balance
[0041] When a plurality of additives is employed it may be desirable, although not essential, to prepare one or more additive packages comprising the additives, whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function, in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant. Thus, compounds in accordance with the present invention may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients.
[0042] More detailed description of additive components is given below.
Detergents
[0043] A detergent is an additive that reduces formation of deposits, for example, high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal “soaps”, that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
[0044] A detergent comprises a polar head with a long hydrophobic tail. Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
[0045] The detergent is preferably an alkali metal or alkaline earth metal additive such as an overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a surfactant selected from phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilised by the oil-soluble salt of the surfactant. The metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt. Preferably the metal, whether the metal of the oil-soluble or oil-insoluble salt, is calcium.
[0046] The TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50-150 mg KOH/g, or high, i.e. over 150 mg KOH/g, as determined by ASTM D2896. Preferably the TBN is medium or high, i.e. more than 50 TBN. More preferably, the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350 mg KOH/g, as determined by ASTM D2896.
Anti-Oxidants
[0047] The trunk piston diesel engine lubricant composition may include at least one anti-oxidant. The anti-oxidant may be aminic or phenolic. As examples of amines there may be mentioned secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms. As examples of anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
[0048] Preferably, the anti-oxidant, if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the lubricant composition. Other additives such as pour point depressants, anti-foamants, metal rust inhibitors, pour point depressants and/or demulsifiers may be provided, if necessary.
[0049] The terms ‘oil-soluble’ or ‘oil-dispersable’ as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
[0050] The lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
[0051] It may be desirable, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
[0052] Thus, the additives may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
[0053] The final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
Viscosity Modifier
[0054] In this invention, as stated above, a viscosity modifier (B) is additionally provided.
[0055] Viscosity modifiers impart high and low temperature operability to a lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures.
[0056] In this invention olefin copolymers (OCP's) are used. Examples of ranges in the composition include 0.1-6, 0.1-5, 0.1-4, mass % and lower limits of 1 or 2 mass %.
[0057] These may be copolymers of two or more monomers of C 2 to C 30 , e.g. C 2 to olefins, including both alpha-olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, or cycloaliphatic. Frequently, they are of ethylene with C 3 to C 30 olefins, particularly preferred being copolymers of ethylene and propylene. They may also be copolymers of C 6 and higher alpha olefins and terpolymers of styrene, e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof.
[0058] Preferred OCP's are ethylene copolymers containing 15 to 90, preferably 30 to 80, mass % of ethylene and 10 to 85, preferably 20 to 70, mass % of one or more C 3 to C 28 , preferably C 3 to C 18 , more preferably C 3 to C 8 , alpha-olefins. Such OCP's may have a degree of crystallinity of less than 25 mass %, as determined by x-ray and differential scanning calorimetry. As indicated above, copolymers of ethylene and propylene are most preferred. Other alpha-olefins suitable in place of propylene, or in combination with ethylene and propylene to form a terpolymer or tetrapolymer, for example, include: 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene; and branched chain alpha-olefins such as 4-methyl- 1 -pentene, 4-methyl-1-hexene, 4-methyl pentene-1,4,4-dimethyl- 1 -pentene, 6-methylheptene-1, and mixtures thereof.
[0059] There may also be included terpolymers and tetrapolymers of ethylene, said C3 to C28 alpha-olefin, and a non-conjugated diolefin or mixtures of such diolefins. The non-conjugated diolefin is generally present as 0.5 to 20, preferably 1 to 7, mole percent of the total moles of ethylene and alpha-olefin.
EXAMPLES
[0060] The present invention is illustrated by, but in no way limited to, the following examples.
MDCL's
[0061] A set of MDCL's was formulated, each containing 20.89 mass % of the same additives in the proportions and having a TBN of about 70. The set comprised a control consisting of additives and base oil; a reference consisting of additives, base oil and brightstock; and an inventive MDCL consisting of additives, base oil and viscosity modifier. The additives were additives known in the art and used in proportions known in the art for conferring MDCL properties. The viscosity modifier was an olefin copolymer in the form of amorphous ethylene-propylene copolymer. The brightstock was a Group I bright stock with a kinematic viscosity of >20cSt at 100° C. The base oil was a Group 1 base oil.
TPEO's
[0062] A set of TPEO's was formulated, each containing 16 mass % of the same additives in the same proportions and having a TBN of about 40. The set comprised a control consisting of additives and base oil; a reference consisting of additives, base oil and bright stock; and an inventive MDCL consisting of additives, base oil and viscosity modifier. The additives were additives known in the art and used in proportions known in the art for conforming TPEO properties. The viscosity modifier and brightstock were as used in the MDCL's. The base oil was a Group 1 base oil.
Testing & Results
[0063] Samples of the above formulations were tested using a PCS Instruments high frequency reciprocating rig (HFRR) on a standard protocol comprising the following conditions:
120 minutes 20 Hz reciprocation of 1 mm stroke length 200 g load using standard equipment manufacturer supplied steel substrates.
[0067] Each test was repeated two further times and the recorded wear measurement was the average of these values.
[0068] The HFRR data for the compositions are summarized in the table below.
[0000]
TABLE
Result
Additive
Base oil
Brightstock
OCP
(wear
(mass %)
(mass %)
(mass %)
(mass %)
vol m 3 )
TPEO
Control
16
84
—
—
5,584
Reference 1
16
75.5
8.5
—
8,279
16
82.67
—
1.33
5,359
MDCL
Control
20.89
79.11
—
—
33,960
Reference 2
20.89
58.89
20.22
—
3,940
20.89
77.61
—
3.17
2,953
[0069] The above results show that the use of an amorphous olefin copolymer additive gives advantageous results when compared with brightstock at much lower additive treat levels in the formulation. | A two-stroke or four-stroke marine engine lubricating oil composition comprising an oil of lubricating viscosity in a major amount and (A) additives, in respective minor amounts; and (B) an olefin copolymer viscosity modifier. Preferably, brightstock is completely or substantially absent from the composition. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a divisional of U.S. patent application Ser. No. 07/616,893 filed Nov. 21, 1990 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to heat transfer insulated parts which can be used as heat transfer parts, high heat transfer substrates and..so forth to be provided in Multi Layer Ceramic Packages (FLLCP), etc. and a manufacturing method thereof.
2. Description of the Background Art
Multilayer ceramic packages have a structure in which sintered alumina are stacked. The multilayer cemraic packages are provided with heat transfer substrates on which LSI chips or the like are mounted and heat transfer caps. As conventional heat transfer substrate portions and heat transfer cap portions, Cu-W sintered body, BeO sintered body, SiC sintered body, and AlN sintered body etc. are employed.
The Cu-W sintered body, as it is not an electric insulator, could not be used for package parts having a structure in which electric short of the parts is a problem. Accordingly, a package in which alumina multilayers and the Cu-W sintered body are integrally encapsulated has been mainly used in a product having no problem of electric short through the Cu-W.
However, for some applications, it was desirabale that the excellent heat dissipation capacity of the Cu-W sintered body was utilized. In such a case, an alumina sheet is stacked on a Cu-W sintered body, or an insulating film such as an Al 2 O 3 film is deposited on the surface of the Cu-W sintered body. However, in the case where an alumina sheet is stacked, problems occur such as that the dimension of the entire package is large, the heat dissipation capacity decreases, or a complicated package structure costs much. In the case where an insulating film such as an Al 2 O 3 film is deposited, Cu diffuses from a heat transfer substrate into the insulating film to reach the surface of the insulating film due to heating at 900° C., for example, in the package assembling process, so that they have caused problems such as inferior insulating.
When SiC or AlN sintered body is employed, because of the large difference of thermal expansion coefficient between the heat transfer substrate and multilayered alumina, they had a problem that cracks occur at the junction in the glass encapsulation process.
In case of the BeO sintered body, since it includes harmful beryllium, it is facing a difficult situation which might lead to stop of manufacturing in view of a problem of environmental pollution.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide heat transfer insulated parts having excellent insulating capability and heat dissipation capacity which are not cracked even if glass-encapsulated, and a manufacturing method thereof.
A heat transfer insulated part according to the present invention includes a heat transfer substrate, an insulating ceramic layer, and a barrier layer provided between the heat transfer substrate and the insulating ceramic layer.
According to the present invention, the heat transfer substrate is formed of a sintered alloy of Cu-W or Cu-Mo.
According to the present invention, the barrier layer is formed of at least either one of the metal layers of W and Mo. Accordingly, the barrier layer may include a single layer or a layer structure of a plurality of stacked layers.
in the present invention, the insulating ceramic layer is a layer provided for electrically insulating the heat transfer substrate. The insulating ceramic layer is preferably selected from the group consisting of Al 2 O 3 , SiO 2 and Si 3 N 4 .
The sintered alloys of Cu-W and Cu-Mo employed as a heat transfer substrate in the present invention has an excellent thermal dissipation capability resulted from large thermal conductivity and diffusivity of heat. Furthermore, the thermal expansion coefficients of these sintered alloys are close to that of alumina of the multilayers, so that it has an excellent matching ability in the thermal expansion. These excellent heat dissipation capacity and matching ability of the thermal expansion do not decrease almost at all even when a barrier layer according to the present invention is provided.
In the present invention, the barrier layer is formed of (a) metal layer(s) of W and/or Mo. The barrier layer prevents Cu diffusion from the heat transfer substrate into the insulating ceramic layer due to heating at about 900° C. in the package assembling process, for example. Therefore, according to the present invention, the inferior insulating due to diffusion of Cu into the insulating ceramic layer can be avoided.
The thickness of the barrier layer is preferably 1-10 μm as a whole. If the thickness is smaller than 1 μm, it does not have a sufficient effect as a barrier layer in some cases. If the thickness of the barrier layer exceeds 10 μm, there is a fear that the thermal conductivity decreases as a heat transfer insulated part.
In the present invention, W and Mo are used as a barrier layer because the thermal expansion coefficients of these metals are close to those of Cu-W and Cu-Mo which are materials of a heat transfer substrate, and the constitution does not change considerably due to heating in the manufacturing process as these metals are refractory metals.
In the present invention, the barrier layer may be a metal layer of W or Mo, or may be composite layer of the two. These barrier layers are effective for both of Cu-W and Cu-Mo heat transfer substrate. However, when Cu-W is employed as a heat transfer substrate, W is preferably employed as a barrier layer, and when Cu-Mo is employed as a heat transfer substrate, Mo is preferably employed as a barrier layer.
In the present invention, the selection of the material of the insulating ceramic layer has no special restriction as long as it can electrically insulate a heat transfer substrate. As an insulating ceramic layer, as described above, Al 2 O 3 , SiO 2 or Si 3 N 4 can be preferably used. Al 2 O 3 , with small difference of thermal expansion coefficients from a Cu-W sintered alloy, is the most appropriate as an insulating ceramic layer when the sintered alloy is employed as a heat transfer substrate. However, depending on the application and a heat transfer substrate, SiO 2 or Si 3 N 4 may be employed.
The insulating ceramic layer must be able to electrically insulate a heat transfer substrate from a plating layer even when conductive plating such as Au plating is applied to the surface thereof in the following steps. The thickness of the insulating ceramic layer is preferably 1-20μm. If the thickness of the insulating ceramic layer is less than 1 μm, pinholes are apt to be induced and a desired insulating capability is not obtained in some cases. Also, in view of the withstanding voltage, it is preferable that the thickness thereof is 1 μm or more. If the thickness exceeds 20 μm, cracks occur in some cases due to residual stress in the insulating ceramic layer.
In one preferable embodiment according to the present invention, an insulating ceramic layer is formed directly on a barrier layer.
According to another preferable embodiment of the present invention, an intermediate layer is formed on a barrier layer, and an insulating ceramic layer is formed thereon. The intermediate layer is provided in order to enhance the adhesive properties of an insulating ceramic layer and a barrier layer. As such an intermediate layer, carbide and/or nitride of metals of IV, V or VI groups in a periodic table are preferably used. As such a metal, Ti is especially preferable. Accordingly, as an intermediate layer, TiC, Ti (C, N) and TiN are especially preferable. Such intermediate layers have good affinity not only with W and Mo metals but also with insulating ceramic layers of such as Al 2 O 3 , SiO 2 and Si 3 N 4 , so that it enhances the adhesive properties of the insulating ceramic layer and the barrier layer.
The thickness of an intermediate layer is preferably 1-5 μm. If the thickness of an intermediate layer is less than 1 μm, pinholes are induced in an intermediate layer in some cases. If the thickness of an intermediate layer exceeds 5 μm, the thermal conductivity as a heat transfer insulated part may be decreased.
When an insulating ceramic layer is an oxide film of such as Al 2 O 3 and SiO 2 , TiC is especially preferable as an intermediate layer. When the insulating ceramic layer includes a nitride film of such as Si 3 N 4 , TiN is especially preferable. In this case, a laminating structure in which a TiC layer is formed on the side of the barrier layer and a TiN layer is formed on the side of the insulating ceramic layer, or a structure of graded composition in which the composition gradually changes from TiC to TiN in the direction from a barrier layer to an insulating ceramic layer is more effective in the aspect of improvement in the adhesive properties.
The manufacturing method according to the present invention includes the step of forming a barrier layer composed of at least either one of metal layers of W and Mo above a heat transfer substrate formed of a sintered alloy of Cu-W or Cu-Mo and the step of forming an insulating ceramic layer for electrically insulating a heat transfer substrate above the barrier layer.
Furthermore, when an intermediate layer is formed between a barrier layer and an insulating ceramic layer, the step of forming the insulating ceramic layer includes the step of forming an intermediate layer on the barrier layer.
The Cu-W sintered alloy and the Cu-Mo sintered alloy employed as a heat transfer substrate in the present invention can be manufactured by a conventionally well known technique for manufacturing this kind of sintered alloy.
In the manufacturing method of the present invention, the barrier layer is preferably formed by the thermal CVD method or the plasma CVD method using WF 6 or MoF 6 as a raw material gas.
The insulating ceramic layer is preferably formed by the CVD method, the plasma CVD method or the ion plating method. When a SiO 2 film is formed as an insulating ceramic layer, the ion plating method is especially preferable.
When forming an intermediate layer, it is also preferably formed by the CVD method, the plasma CVD method or the ion plating method.
A barrier layer is formed between an insulating ceramic layer and a heat transfer substrate in a heat transfer insulated part according to the present invention, so that the diffusion of Cu from the heat transfer substrate into the insulating ceramic layer is avoided to prevent a decrease in the insulating capability of the insulating ceramic layer. Accordingly, the heat transfer insulated parts according to the present invention have excellent insulating capability and heat dissipation capacity.
Providing an intermediate layer between an insulating ceramic layer and a barrier layer enhances the adhesive properties of the insulating ceramic layer and the barrier layer and prevents cracks from occurring.
Accordingly, when the heat transfer insulated parts of the present invention are used as insulated heat transfer parts for multilayer packages for mounting LSI, microwave devices, high-frequency large electric power transistors, FE and so forth, packages having extremely excellent airtightness and heat transfer can be obtained, so that it is very useful.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view showing one embodiment according to the present invention.
FIG. 2 is a sectional view showing another embodiment according to the present invention.
FIG. 3 is a sectional view showing a multilayer package to which a heat transfer insulated part of the example 1 according to the present invention is attached.
FIG. 4 is a sectional view showing a package for a microwave device to which a heat transfer insulated part of the example 2 according to the present invention is attached.
FIG. 5 is a sectional view showing a package employing a heat transfer insulated part of the example 5 according to the present invention as a substrate of a transistor.
FIG. 6 is a sectional view showing a multilayer package to which a heat transfer insulated part according to the example 6 according to the present invention is attached.
FIG. 7 is a sectional view showing a package employing as a flange of a FET a heat transfer insulated part of the example 7 according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, according to one embodiment of the present invention, a barrier layer 3 is provided on a heat transfer substrate 1. On barrier layer 3, an insulating ceramic layer 2 is provided. Because of such a barrier layer 3, the diffusion of Cu from heat transfer substrate 1 to insulating ceramic layer 2 is avoided.
Referring to FIG. 2, according to another embodiment of the present invention, a barrier layer 3 is provided on a heat transfer substrate 1 and an intermediate layer 4 is provided on the barrier layer 3. An insulating ceramic layer 2 is provided on the intermediate layer 4. The intermediate layer 4 enhances the adhesive property with respect to the barrier layer 3 and the insulating ceramic layer 2.
Examples for manufacturing heat transfer insulated parts according to the present invention and loading the same in various packages will be described below. In the description below, % means percentage by weight.
EXAMPLE 1
A sintered alloy of composition of 10% Cu-90% W is coated with a W layer as a barrier layer with a thickness of 5 μm by the CVD method employing a mixed gas of WF 6 and H 2 . Subsequently, on the W layer as a barrier layer, an Al 2 O 3 film with a thickness of 7 μm is formed as an insulating ceramic layer.
FIG. 3 is a sectional view showing a multilayer package for LSI in which a heat transfer insulated part obtained in this way is provided as a heat transfer substrate portion. Referring to FIG. 3, a heat transfer substrate portion 11 which is a heat transfer insulated part of this example is provided under a LSI chip 12. One end of a bonding wire 13 is connected to LSI chip 12. A pin 14 is provided in the lower portion of the package.
The multilayer package for LSI had extremely excellent airtightness and heat dissipation capacity.
EXAMPLE 2
A sintered alloy of composition of 15%Cu-85%W is coated with a W layer with a thickness of 10 μm as a barrier layer by the plasma CVD method employing a mixed gas of WF 6 and H 2 . Subsequently, by the CVD method, an Al 2 O 3 film with a thickness of 6 μm is formed as an insulating ceramic layer.
FIG. 4 is a sectional view showing a package for a microwave device manufactured using a heat transfer insulated part obtained in this way. Referring to FIG. 4, the obtained heat transfer insulated part is used in the package as a heat transfer substrate 21. An alumina based microwave circuit 22 and a semiconductor chip 23 are provided on heat transfer substrate 21. The semiconductor chip 23 is a silicon or GaAs chip. 24 denotes a bonding wire, 25 denotes a case, and 26 denotes a pin.
The package for a microwave device has excellent airtightness and heat dissipation capacity.
EXAMPLE 3
A sintered alloy of composition of 15%Cu-85%Mo is coated with Mo to a thickness of 5 μm by the ion plating method to form a barrier layer. Subsequently, by the plasma CVD method, an Al 2 O 3 film with a thickness of 10 μm is formed as an insulating ceramic layer.
Using the heat transfer insulated part obtained as described above in combination with an alumina multilayer substrate, an MLCP similar to that shown in FIG. 3 was manufactured. The MLCP was a package having excellent air-tightness and heat dissipation capacity.
EXAMPLE 4
Except that the coating method of Mo in the example 3 is changed to the CVD method, a heat transfer insulated part was manufactured under conditions same as those of the example 3. The obtained heat transfer insulated part is employed in a FLLCP similar to that in example 3, which served as a package having excellent airtightness and heat dissipation capacity.
EXAMPLE 5
A sintered alloy of composition of 15%Cu-85%W is coated with Mo with a thickness of 7 μm by the CVD method employing a mixed gas of MoF 6 and H 2 to form a barrier layer. Subsequently, on the barrier layer, an Al 2 O 3 film with a thickness of 9 μm is formed as an insulating ceramic layer by the ion plating method.
FIG. 5 is a sectional view showing a package in which the heat transfer insulated part obtained in this way is employed as a substrate of a transistor or a base metal. Referring to FIG. 5, a Si chip 32 is mounted on a base metal 31, and one end of a bonding wire 33 is connected to the connecting pad of Si chip 32 and the other end thereof is connected to the top surface of a pin 25. 34 denotes a case.
The package was a package having excellent airtightness and heat dissipation capacity.
EXAMPLE 6
A sintered alloy of composition of 20%Cu-80%W is coated with W with a thickness of 6 μm to form a barrier layer. On the barrier layer, a TiC film with a thickness of 2 μm is formed by the CVD method to form an intermediate layer. Subsequently, on the intermediate layer, an Al 2 O 3 film with a thickness of 7 μm is formed by the plasma CVD method to form an insulating ceramic layer.
FIG. 6 is a sectional view showing a multilayer package employing a heat transfer insulated part obtained in this way as a heat transfer cap portion. Referring to FIG. 6, a heat transfer cap portion 41 is provided on an LSI chip 42. 43 denotes a bonding wire and 44 denotes a pin.
The MLCP showed excellent airtightness and heat dissipation capacity.
EXAMPLE 7
A sintered alloy of composition of 10%Cu-90%W is coated with W with a thickness of 5 μm to form a barrier layer. Subsequently, by the ion plating method, a SiO 2 film with a thickness of 3 μm is formed to form an insulating ceramic layer.
FIG. 7 is a sectional view showing a package using the heat transfer insulating part obtained in this way as a flange of a FET. Referring to FIG. 7, a Si chip 52 is mounted on a flange 51, and a ceramic frame 54 is provided in the vicinity of flange 51. 53 denotes a bonding wire, and 55 denotes a lead frame.
The package showed excellent airtightness and heat destination capacity.
EXAMPLE 8
A sintered alloy of composition of 20%Cu-80%Mo is coated with Mo with a thickness of 5 μm to form a barrier layer. An intermediate layer with a thickness of 4 μm in which the composition continually changes from TiC to TiN is formed thereon. On the intermediate layer, a Si 3 N 4 film with a thickness of 3 μm is formed by the plasma CVD method to form an insulating ceramic layer.
The obtained heat transfer insulated part used in an MLCP similar to that of Example 1 implemented a package having excellent airtightness and heat transfer ability.
Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. | A heat transfer insulated part including a heat transfer substrate formed of a sintered metal of Cu-W or Cu-Mo, an insulating ceramic layer for electrically insulating the heat transfer substrate, formed of ceramic such as Al 2 O 3 , SiO 2 and Si 3 N 4 , and a barrier layer provided between the heat transfer substrate and an insulating ceramic layer composed of at least either one of metal layers of W and Mo. Furthermore, preferably, an intermediate layer composed of titanium carbide and/or titanium nitride and so forth for enhancing the adhesive property between the insulating ceramic layer and the barrier layer is provided. | 7 |
This application is continuation of Ser. No. 11/042,797, filed Jan. 24, 2005, now issued as U.S. Pat. No. 7,890,189, which claims priority from French Patent Application No. 04 00577, filed Jan. 24, 2005, published Apr. 21, 2006, French Publication No. 2,865,409, all of which are hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to “active implantable medical devices” as defined by the Jun. 20, 1990 Directive 90/385/CEE of the Council of the European Communities.
BACKGROUND OF THE INVENTION
The invention more particularly concerns the family of apparatuses that deliver to the core pulses of high energy (i.e., pulses notably exceeding the energy provided for simple stimulation) to try to put an end to a tachyarrhythmia. These devices are called “implantable defibrillators” or “implantable cardiovertors,” it being understood that the invention also covers implantable defibrillators/cardiovertors or defibrillators/cardiovertors/stimulators.
“Implantable defibrillator” or “implantable cardiovertor” devices have two principal parts—a pulse generator, and a probe or a system of probes. The pulse generator monitors cardiac activity and generates high energy pulses when the heart presents a ventricular arrhythmia that is deemed susceptible to being treated. When the high energy is comprised between approximately 0.1 and 10 J, the therapy is referred to as “cardioversion” and the electric shock is called “cardioversion shock.” When the high energy is greater than approximately than 10 J, the therapy is called defibrillation and the electric shock is called “defibrillation shock.” The pulse generator is connected to one or more probes comprising electrodes whose role is to distribute this energy to the core in a suitable way.
The present invention relates to the particular case where the generator is connected to a “mono-body” probe, that is a single probe carrying the various electrodes making it possible to deliver shocks of defibrillation or cardioversion. The shock electrodes appear as windings of wire supported by a distal tubular extremity of the probe and are intended to come into contact with cardiac tissues at the place where the cardioversion or defibrillation energy must be applied. The windings are connected to a conducting wire traversing the length of the probe.
Mono-body probes generally comprise two shock electrodes: a first electrode, known as “supraventricular,” which will be positioned in the high vena cava to apply the shock to the atrium; and a second electrode, a ventricular one, which will be located more closely to the distal extremity of the probe.
The mono-body probes are generally of the “isodiameter” type, i.e., they have the same diameter over the entire length of the distal part intended to be implanted in the venous network. This facilitates implantation, as well as any later explantation. This means that the external surface of the windings forming the shock electrodes is flush with the external surface of the probe, so as not to present any change in diameter along the implanted length of the probe.
The manufacturing of these mono-body probes is relatively delicate, taking into account the presence of the windings, the requirements for continuity of probe diameter, and the need for carrying the electric connection inside the body of the probe with the electrical conductor allowing delivery of the shock energy.
The technique employed until now to manufacture these probes consists of taking a plurality of tubular sections of encasable sheath, one after another, setting up the windings, and electrically connecting them progressively to their internal conductor at the various sections of the tube of the probe. This structure, which makes it possible to answer the specific constraints associated with manufacturing these probes, has, however, the disadvantage of creating zones and/or electric weaknesses at the places where the various sections are connected, in particular short-circuits on the high voltage conductor supplying the shock energy. However, in practice, it has been noted that the ruptures of the insulated tube support often occur at the places of the connections between the various sections of sheath, because of the zones of weakness locally created at the place of these connections. Moreover, this structure of encased sections implies a relatively complex and long manufacturing process, in particular because of the need for sticking the successive sections together. U.S. Pat. No. 6,374,142 and PCT Application No. WO-A-02/087689 describe such mono-body isodiameter probes produced starting from encased successive sections of sheath.
OBJECTS AND SUMMARY OF THE INVENTION
One of the goals of the present invention is to cure the above-described disadvantages by proposing another structure for the distal part of a mono-body defibrillation probe—a structure that does not present a zone of weakness in the vicinity of the windings and can be manufactured simply and quickly.
The probe of the invention is a mono-body defibrillation probe of the known type described above, i.e., with a probe body that includes at its distal extremity an insulated sheath core of a tubular flexible material, supporting at its periphery at least one winding of wire forming a shock electrode for application of a defibrillation or cardioversion energy, this winding being electrically connected to an electrical conductor extending longitudinally in an internal lumen inside the sheath core.
In a manner characteristic of the invention, the sheath core extends axially without solution of continuity (i.e., without interruption) in the area(s) supporting the winding(s).
Very advantageously, the sheath core locally comprises a crossing cavity located in the vicinity of at least one of the winding ends. It is envisaged moreover that an insert of conducting material, of a size homologous with the aforesaid cavity, is placed therein, with this insert being electrically connected, on the interior side, with the electrical conductor and, on the external side, with the corresponding extremity of the winding.
In particular, the sheath core can comprise a cavity in the vicinity of each extremity of the winding, and it then comprises also a crossing longitudinal slit connecting the two cavities and radially extending from the external surface of the sheath core to the internal lumen thereof, so as to allow, by elastic strain of the material of the sheath core on both sides of the slit, the introduction into the cavities and the internal lumen of the unit formed by the final extremity of the electrical conductor provided beforehand with the two inserts to which it was mechanically and electrically connected.
In one embodiment of the invention, it is envisaged to have junction ring for mechanical and electric connection of the insert to the winding, this ring being a cylindrical ring of conducting material, with an internal surface able to cooperate with a part turned towards the outside of the insert, and an external surface comprising a connection part able to cooperate with a part turned towards the interior of the extremity of the winding. This ring can in particular comprise, in the area of internal surface able to cooperate with the insert, an assembly part capable of allowing mechanical and electric solidarization from the ring to the insert. The assembly part is preferably a part comprising a crossing opening able to allow solidarization of the ring to the insert by welding from the outside. Moreover, the diameter of the assembly part is greater than the diameter of the connection part, the difference of the diameters being approximately equal to double the thickness of the winding, so that the external surface of the ring is approximately level with the external surface of the winding.
Preferably, the probe is provided with an external envelope made of a flexible insulated material sheathing the sheath core along its length, except for the area of the winding, with the diameter of the external envelope being approximately equal to the diameter of winding. In this case, the ring can also comprise, at the opposite side of the connection part, a shafting part receiving the extremity of the external envelope adjacent to the winding. For the assembly, the insert can comprise, on the interior side, a sleeve, axially oriented, for crimping the insert to the electrical wire. Preferably both the space included between the radial walls of the slit and the internal volume of the lumen in the area of the slit are provided with an electrically insulated sealing material, such as polymeric resin that is hardenable, e.g., an adhesive silicone.
BRIEF DESCRIPTION OF THE DRAWINGS
Further benefits, features, and characteristics of the present invention will become apparent to a person of ordinary skill in the art in view of the following detailed description of a preferred embodiment of the invention, made with reference to the annexed drawings, in which like reference characters refer to like elements, and in which:
FIG. 1 is an overall view of a mono-body defibrillation probe according to the present invention;
FIG. 2 is an enlarged perspective view, of the proximal extremity of the tubular sheath, at the place where the sheath terminates to widen and be divided into a plurality of conductors connected to a connector;
FIG. 3 is a perspective view showing the sheath core and the elements that will be there inserted to later allow connection to the defibrillation winding; and
FIG. 4 is a detailed cross-section of the part of the probe at the place of the defibrillation winding, showing the various internal elements and the way that the electric connection with the winding is carried out.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 , reference 10 indicates generally a mono-body probe of which the distal extremity 12 is intended to be introduced by the venous network into the two atrial and ventricular cavities, so as to detect there cardiac activity and apply as needed a defibrillation or cardioversion shock. The probe is provided at its proximal extremity 14 with various elements for connection to an appropriate generator, e.g., a generator of the Defender or Alto or Ovatio type manufactured by the assignee hereof, ELA Medical, Montrouge, France.
Probe 10 carries a first shock electrode 16 , intended to be placed in the right ventricle and constituting, e.g., the negative terminal for application of the potential voltage of defibrillation or cardioversion. This ventricular shock electrode 16 is connected by a connection conductor 18 on a connection terminal 20 to the generator, advantageously a terminal of the DF-1 standard type.
Probe 10 also carries at its distal part 12 a second shock electrode 22 , which is known as a “supra-ventricular” an electrode, intended to be positioned in the high vena cava for application of a shock to the atrium. This supra-ventricular shock electrode 22 is connected by connection conductor 24 on connection terminal 26 to the generator, preferably also with a DF-1 standard connector.
Probe 10 is also equipped with an extremity electrode 28 , which is a detection/stimulation electrode intended to be positioned at the bottom of the right ventricular cavity. This electrode 28 is connected by a conductor 30 on a connection terminal 32 to the pacemaker, advantageously with an IS-1 connector standard.
As shown in FIG. 4 , conductor 30 is a hollow conductor, e.g., a conductor internally wound, having in its center a lumen 34 that allows introduction of a stylet for the guidance of distal extremity 12 by a physician into the venous network at the time of implantation of the probe 10 .
Referring again to FIG. 1 , the defibrillation potential can be applied between the supra-ventricular shock electrode 22 and the generator case, or between the ventricular shock electrode 16 and the generator case, or between electrodes 16 and 22 , in a bipolar mode.
The configuration just described (i.e., two defibrillation electrodes and one stimulation electrode) is, however, not restrictive, and the invention is also applicable to the case of a probe equipped with only one defibrillation electrode winding, or not including a distal stimulation electrode, or including two stimulation electrodes (for a stimulation in bipolar mode, in particular), etc.
FIGS. 2 and 4 more precisely show the configuration of three conductors 18 , 24 , and 30 in the distal tubular extremity 12 of the probe 10 . These conductors are placed in respective lumens of a tubular sheath core 36 made out of a flexible insulated material such as a silicone. The conductors 18 and 24 , which must transmit the defibrillation or cardioversion energy, are micro-cables having their own insulators, respectively 38 and 40 , e.g., in ETFE. The silicone material constituting the sheath core 36 presents excellent properties of fatigue strength. Regardless, it would be difficult to make the sheath core 36 penetrate in the venous network just as it is, and for this reason the sheath core is wrapped outside by a sheath 42 made out of a material with low coefficient of friction, e.g., polyurethane.
The present invention relates more particularly to the way in which the probe 10 is constructed/assembled in the vicinity of the shock electrode windings 16 and 22 . FIGS. 3 and 4 illustrate a preferred structure for the ventricular shock electrode winding 16 . Because this structure is the same supraventricular shock electrode winding 22 , the structure for that winding will not be further described in detail.
In a way characteristic of the invention, the sheath core 36 is a solid tube, without solution of continuity over the entire length of the distal part 12 , in particular in the area of the windings 16 and 22 . This is due to a particular structure of the electric connection system between the winding and its corresponding conductor located inside the sheath core 36 .
Thus, as illustrated in FIGS. 3 and 4 , conductor 18 , intended to feed the winding 16 , is equipped with two metal parts 46 , 46 ′ which function as inserts, solidarized mechanically, and electrically connected, with the conductor 18 by setting of (sliding) sleeves 48 , 48 ′ over a stripped length emerging from insulator 38 .
It is indeed desirable to have an electric connection of conductor 18 with the two ends of winding 16 , in order to produce the most homogeneous possible electric field between these two ends at the time of application of the defibrillation or cardioversion energy. If the winding is fed by its two ends, the current density will be better distributed, thus avoiding the risk of burning the surrounding tissues. For a defibrillation shock that can require application of energy of up to 40 joules, the peak voltage can reach 750 V. For this voltage, the homogeneity of the electric field at the time of the shock is a significant constraint to take into account when designing the probe.
As illustrated in FIG. 3 , the sheath core 36 comprises two cavities 50 , 50 ′, which extend from the external surface of the sheath core to the lumen 44 ( FIG. 4 ) receiving conductor 18 . These two cavities 50 , 50 ′ are joined together by a longitudinal slit 52 ( FIG. 3 ), which extends along the sheath core 36 and radially from the external surface of the sheath core to the lumen 44 ( FIG. 4 ) receiving conductor 18 . The interior dimensions of these cavities 50 , 50 ′ are homologous with the external dimensions of inserts 46 , 46 ′, so that the inserts can be entirely placed into the cavities, with their upper surface 54 ( FIG. 4 ) being level with the upper surface 56 of the sheath core 36 . On the interior side, the lower face 58 of insert 46 preferably rests on the surface 60 of the lumen 44 .
The electric and mechanical connection of inserts 46 , 46 ′, and thus of conductor 18 , with winding 16 , is carried out via junction rings 62 , 62 ′. The junction ring 62 presents a central part 64 , from which interior surface 66 comes in contact with the upper surface 54 of insert 46 . The external surface 68 of the central part 64 has a diameter roughly equal to the external diameter of winding 16 and the external diameter of the polyurethane sheath 42 ; based on that, the external surface 70 of the sheath is level with the external surface 68 of the ring, thus ensuring the required isodiameter configuration. On the side that is farthest from the winding 16 , ring 62 comprises a part of lesser diameter 72 intended to fix with force (friction force fit) in the interior extremity of the external sheath 42 . On the side that is closest to the winding, the ring 62 comprises a part of lesser diameter 74 intended to fix with force in the interior extremity of winding 16 .
To ensure the electric and mechanical solidarization of insert 46 to the connection ring of 62 (and thus winding 16 ), the central part 64 of the ring is equipped with an opening 76 , making it possible to carry out from the outside welding point 78 (like that illustrated on the right FIG. 4 ), preferably a laser welding point.
Lastly, under winding 16 , the remaining space around conductor 18 and around the various contiguous elements is filled with an electrically insulated sealing material, e.g., a setting polymeric resin, such as a resin silicone.
One now will describe the manner of carrying out such a probe structure with a mechanical continuity of the sheath core 36 in the area supporting the electrode.
First of all, the sheath core 36 is prepared with its external sheath 42 only in the proximal area of the probe, i.e., on the left part of FIG. 4 . This external sheath thus stops in the vicinity of cavity 50 on the proximal end of the probe 16 , i.e., toward the left in FIGS. 3 and 4 . Separately (e.g., on another preparation setup) insulator 38 of conductor 18 is stripped on its distal side over an adaptable length, to crimp there two contact blocks 46 , 46 ′ at a desired distance, by means of sleeves 48 , 48 ′. The unit obtained is illustrated partly on the top portion of FIG. 3 . Conductor 18 is then threaded by its proximal extremity (i.e., the one opposed to the contact blocks 46 , 46 ′) into lumen 44 via opening 50 of the sheath core 36 , while letting exceed on the distal side the free part with the inserts 46 , 46 ′. The set formed by this length of wire with the inserts 46 , 46 ′ is then completely introduced inside the sheath core 36 , by placing two inserts 46 , 46 ′ in the two homologous cavities 50 , 50 ′, with the part of conductor 18 connecting these two inserts being introduced by elastic deformation of sheath core material on both sides of slit 52 . Once the unit is thus introduced, sleeves 48 , 48 ′ and conductor 18 find their place inside lumen 44 and the two lips of slit 52 can thus regain their initial shape. The unit is maintained tightly in place with a local injection, via slit 52 , of a resin silicone mass (reference number 80 on FIG. 4 ), which thus comes to fill lumen 44 at the place of slit 52 and cavities 50 , 50 ′, with a tight obturation of lumen 44 on both sides of the unit thus made up.
The following stages consist of, successively:
1. slipping on the ring 62 , 2. fixing the ring 62 in the part of external sheath 42 located on the proximal side of the probe (on the left on FIG. 4 ); 3. slipping on the winding 16 ; 4. fixing the proximal extremity of the winding on the ring 62 ; 5. slipping on the ring 62 ; 6. fixing the ring 62 on the distal extremity of the winding 16 ; 7. slipping the sheath 42 ′ on the distal side of the probe; and 8. fixing on the ring 62 ′.
The unit is thus mechanically assembled. The operation is repeated identically for the other winding. Laser welding points 78 make it possible to perform the electric and mechanical connection of the rings 62 , 62 ′ on the one hand to the ends of winding 16 (in zone 74 ), and on the other hand to the respective inserts 46 , 46 ′.
One skilled in the art will appreciate that the present invention can be practiced by other than the described embodiments, which are presented for purposes of illustration and not of limitation. | A probe including at its distal extremity a tubular flexible sheath core supporting at least a winding forming a shock electrode and connected to an electrical conductor of connection extending in an internal lumen of the sheath core. In one embodiment of the invention, the sheath core extends axially without a solution of continuity in the area supporting the winding. In particular, the sheath core comprises cavities to receive and hold conducting inserts, of homologous size with cavities formed locally close to the ends of the winding, the insert being connected to the interior side to the electrical conductor, and on the external side to the corresponding extremity of winding. A longitudinal slit connects two cavities and allows, by elastic deformation of the sheath core, the introduction into the cavities and in the internal lumen of the unit formed by the final extremity of the electrical conductor beforehand equipped with its two inserts. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a national phase entry under 35 U.S.C. §371 of International Patent Application PCT/EP2011/064734, filed Aug. 26, 2011, designating the United States of America and published in English as International Patent Publication WO 2012/025619 A1 on Mar. 1, 2012, which claims the benefit under Article 8 of the Patent Cooperation Treaty and under 35 U.S.C. §119(e) to U.S. Provisional Patent Application Ser. No. 61/402,307, filed Aug. 26, 2010, and to European Patent Application Serial No. 10175543.7, filed Sep. 7, 2010.
TECHNICAL FIELD
[0002] The present invention relates to an antigen-binding protein, preferably comprising an amino acid sequence that comprises four framework regions and three complementarity-determining regions, wherein the antigen-binding protein is capable of binding a chitinous polysaccharide, and uses thereof.
BACKGROUND
[0003] Polysaccharides are polymeric carbohydrate structures, formed of repeating units of monosaccharides, joined together by glycosidic bonds. Depending on their chemical composition, polysaccharides are further divided into polysaccharides sensu strictu, which contain only hydroxyl and acetyl groups and aminopolysaccharides, which contain also nitrogen (amino or amido-groups). Natural aminopolysaccharides include chitin and chitosan (only containing hydroxyl, amino and acetyl groups) and keratin sulphate, hyaluronic acid, chondroitin, dermatan sulphates and heparin, which contain also carboxyl and sulphate groups.
[0004] Chitin is the most abundant natural aminopolysaccharide and is widely distributed amongst invertebrates including arthropods, nematodes, crustaceans, fungi and some protozoa. Chitin is a polymer of N-acetyl-D-glucosamine. The major form of chitin is α-chitin, as encountered in fungi and arthropods and is characterized by an anti-parallel joining of the polysaccharide chains. The β-form, in which the chains are joined in a parallel way, is rather rare and is found in diatoms and some protists. Chitosan is the N-deacetylated derivative of chitin, although this N-deacetylation is almost never complete. Chitin and chitosan correspond to a family of polymers varying in acetyl content, wherein the degree of acetylation determines whether the aminopolysaccharide is named chitin (degree of acetylation >70%) or chitosan (degree of acetylation <70%).
[0005] Chitin is the second most abundant biopolymer in nature after cellulose and, together with its derivatives, it has applications in a wide variety of fields, including medical, pharmaceutical, cosmetics, biotechnology, food industry, agriculture and environmental protection. Despite its huge annual production, chitin still remains an underutilized biomass resource, primarily because of its intractable bulk structure. Therefore, the determination of the concentration of chitinous polysaccharides, as well as the identification of their structure and possible modifications is extremely important, especially for efficient industrial processing. Moreover, it may be important to target specific chitinous polysaccharides, for removal out of the matrix or for modification of their structure.
[0006] Special attention has been paid to chitin-binding proteins for detection and purification applications. Chitin-binding proteins are rather common and form a highly diverse group, including but not limited to chitinases, hydrolyzing the internal β-1,4-glycosidic linkages of chitin. Chitin-binding proteins have been detected in bacteria (Folders et al., 2000; Joshi et al., 2008), plants (Iseli et al., 1993), invertebrates (Suetake et al, 2000) and vertebrates (Boot et al., 1995). Chitin-binding proteins are characterized by one or more chitin-binding domains; these binding domains may or may not be linked to a catalytic domain. The binding domains can be isolated and fused to other polypeptides, to create novel chitin-binding proteins.
[0007] Chitin-binding domains and chitin-binding proteins do have multiple possible applications: as chitin is absent in vertebrates and plants, chitin-binding domains can be used to detect infection or contamination by chitin-containing organisms, as disclosed in WO 9217786 or WO 2005005955. By fusing a chitin-binding domain to a protein of interest, the protein of interest can be purified on a chitin carrier, using affinity chromatography. Moreover, WO 9411511 discloses biocidal chitin-binding proteins that exert an antifungal activity and can be used as anti-microbial agent. Joshi et al. (2008) describe a chitin-binding protein with insecticidal activity.
[0008] However, notwithstanding their possible value, the use of the chitin-binding domains and chitin-binding proteins is rather limited, due to several drawbacks. Most of the chitin-binding domains show cross reactivity with other polysaccharides, limiting the value of the binding domain for specific detection of chitin (Itoh et al., 2002; Guillen et al., 2010). Several chitin-binding domains bind chitin with rather low affinity (Neeraja et al., 2010b), limiting the applications in all fields. Moreover, chitin-binding domains may bind chitin in an irreversible way (Xu et al., 2000; WO 03074660), complicating the use in affinity purification, because the protein cannot be eluted under non-denaturing conditions.
[0009] To solve the problems, the introduction of mutations in the chitin-binding domains has been proposed to modulate the chitin-binding activity and to create modified chitin-binding domains with reversible binding properties (Ferrandon et al., 2003; WO 03074660). However, there is still a need for better chitin-binding proteins.
[0010] Antibodies are known for their high affinity and specificity. However, production of antibodies against polysaccharides is far from evident, as polysaccharides are hardly immunogenic. Anti-chitin IgA type antibodies have been detected in serum of Crohn's disease, ulcerative colitis and inflammatory bowel disease (WO 2009069007; Dotan et al., 2006; Seow et al., 2008; Seow et al., 2009) and after Candida albicans infection (Sendid et al., 2008). Sales et al. (2001) and Martin et al. (2007) describe the generation of polyclonal rabbit anti-chitin antibodies; U.S. Pat. No. 5,004,699 discloses the use of a mouse serum containing polyclonal anti-chitin antibodies for the detection of fungi and yeasts. However, for the intended uses, monoclonal antibodies, and preferably single chain antibodies are needed. Anti-chitin single chain antibodies have not been disclosed in the art.
[0011] WO 94004678 describes immunoglobulins devoid of light chains. It is demonstrated that such antigen-binding proteins comprising an amino acid sequence that comprises four framework regions (FR) and three complementarity-determining regions (CDR), and more specifically VHH, display superior characteristics over monoclonal antibodies as they are extremely stable and retain binding capacity to the target antigen under high temperature (van der Linden et al., 1999), or denaturing conditions (Dolk et al., 2005) and are resistant to harsh regenerating conditions (Saerens et al., 2005). Therefore, the antigen-binding proteins are particularly well suited to be used in industrial processes. However, up to now, such antigen-binding proteins capable of binding polysaccharide are not described, although attempts to make such anti-bodies have been made. Indeed, WO 94004678 disclosed camelid antibodies against carbohydrates, but those are directed against the variant surface antigen of Trypanosoma evansi , which is a glycoprotein. WO 94004678 is neither disclosing nor suggesting antibodies against polysaccharides sensu strictu, or against aminopolysaccharides. Moreover, when De Simone et al. (2008) analyze the immune response in llamas immunized with different types of antigens, i.e., protein, conjugated hapten or polysaccharide (dextran sulphate), no anti-dextran immune response could be detected in the immunized animals, in contrast to clear immune responses to the protein and conjugated hapten antigens; whereas it is relatively easy to generate classical anti-dextran antibodies (Cisar et al., 1975; Bona, 1993). The lack of antibody response in the immunoglobulins devoid of light chains is not unexpected: indeed anti-polysaccharide responses in humans are clearly dominated by IgM and IgG1 types (Bona, 1993) whereas heavy chain antibodies from camelids belong to the IgG2 and IgG3 classes (Hamers-Casterman et al., 1993; Daley et al., 2010). Moreover, it is known that interactions between polysaccharides and individual binding sites in a protein are typically weak and binding strength and specificity is enhanced through polymeric interactions between polysaccharides and oligomeric polysaccharide-binding proteins (Mammen et al., 1998). Being strictly monomeric binders by nature (Muyldermans et al., 2001), VHH are in this respect not well suited to bind polysaccharides. Therefore, the person skilled in the art would assume that it is extremely difficult, if not impossible to raise immunoglobulins devoid of light chains against chitinous polysaccharides. Another complicating factor is the low water-solubility of chitinous polysaccharides, particularly chitin, which means that many standard techniques used for isolating antibodies that are carried out in aqueous solution, cannot be applied.
[0012] To obtain and isolate antigen-binding proteins specific for chitinous polysaccharides, an original and innovative approach was used. By immunizing llamas with a complex mixture containing chitinous polysaccharides, rather than with a purified antigen, followed by selecting antigen-binding proteins using immobilized solubilized chitin and finally screening with chitin, prepared directly on a solid surface, we were capable of isolating antigen-binding proteins, more specifically, antigen-binding proteins comprising an amino acid sequence that comprises four framework regions (FR) and three complementarity-determining regions (CDR), wherein the antigen-binding proteins are capable to bind chitinous polysaccharides. Preferably, the antigen-binding proteins are binding to chitin.
DISCLOSURE
[0013] A first aspect hereof is an antigen-binding protein capable of binding a chitinous polysaccharide.
[0014] An “antigen-binding protein” as used herein, means the whole or part of a proteinaceous (protein, protein-like or protein-containing) molecule that is capable of binding using specific intermolecular interactions to a target molecule. An antigen-binding protein can be a naturally occurring molecule, it can be derived from a naturally occurring molecule, or it can be entirely artificially designed. An antigen-binding protein can be immunoglobulin-based or it can be based on domains present in proteins, including but not limited to microbial proteins, protease inhibitors, toxins, fibronectin, lipocalins, single chain antiparallel coiled coil proteins or repeat motif proteins. Non-limiting examples of such antigen-binding proteins are carbohydrate antigen-binding proteins (CBD) (Blake et al., 2006), heavy chain antibodies (hcAb), single domain antibodies (sdAb), minibodies (Tramontano et al., 1994), the variable domain of camelid heavy chain antibodies (VHH), the variable domain of the new antigen receptors (VNAR), affibodies (Nygren et al., 2008), alphabodies (WO 2010066740), designed ankyrin-repeat domains (DARPins) (Stumpp et al., 2008), anticalins (Skerra et al., 2008), knottins (Kolmar et al., 2008) and engineered CH2 domains (nanoantibodies; Dimitrov, 2009).
[0015] “Polysaccharides” as used herein are polymeric carbohydrate structures, formed of repeating units of monosaccharides, joined together by glycosidic bonds, including aminopolysaccharides, and derivatives thereof. “Aminopolysaccharides,” as used herein, means nitrogen (amido or amino-groups) containing polysaccharides, but it excludes polysaccharides further containing carboxyl- or sulphate-groups. Preferably, the polysaccharides are not contaminated with other non-polysaccharide compounds, and have a purity of at least 85% w/w, preferably 90% w/w, more preferably 95% w/w, even more preferably 98% w/w, most preferably 99% w/w. Polysaccharides are distinct from oligosaccharides by their size, complexity and degree of polymerization. Polysaccharides as used here comprise at least ten monosaccharides units, preferably at least fifteen monosaccharide units.
[0016] “Chitinous polysaccharides,” as used herein, means aminopolysaccharides and derivatives or modifications thereof, including but not limited to nitration, phosphorylation, sulphation, acylation, deacetylation, hydroxyalkylation, alkylation and/or graft copolymerization. Preferably, the chitinous polysaccharide is a natural aminopolysaccharide.
[0017] “Capable of binding to a chitinous polysaccharide” as used herein, means that the antigen-binding protein can form a stable complex with a chitinous polysaccharide, preferably an insoluble chitinous polysaccharide, wherein the efficacy of the binding can be evaluated by precipitating the chitinous polysaccharide/protein complex, similar to described by Folders et al. (2000). Alternatively, chitinous polysaccharides may be immobilized on an insoluble carrier to allow recruitment of the antigen-binding protein and evaluation of the binding.
[0018] Preferably, the antigen-binding proteins hereof are monoclonal antigen-binding proteins. A “monoclonal antigen-binding protein” as used herein means an antigen-binding protein produced by a single clone of cells and therefore a single pure homogeneous type of antigen-binding protein. More preferably, the antigen-binding proteins hereof consist of a single polypeptide chain. Most preferably, the antigen-binding proteins hereof comprise an amino acid sequence that comprises four framework regions and three complementarity-determining regions, or any suitable fragment thereof, and confer their binding specificity to the chitinous polysaccharide by the amino acid sequence of three complementarity-determining regions or CDRs, each non-contiguous with the others (termed CDR1, CDR2, CDR3), which are interspersed amongst four framework regions or FRs, each non-contiguous with the others (termed FR1, FR2, FR3, FR4), preferably in a sequence FR1-CDR1-FR2-CDR2-FR3-CDR3-FR4). The delineation of the FR and CDR sequences is based on the unique numbering system according to Kabat. The antigen-binding proteins comprising an amino acid sequence that comprises four framework regions and three complementarity-determining regions, are known to the person skilled in the art and have been described, as a non-limiting example in Wesolowski et al. (2009). The length of the CDR3 loop is strongly variable and can vary from 0, preferably from 1, to more than 20 amino acid residues, preferably up to 25 amino acid residues.
[0019] Preferably, the antigen-binding protein hereof is easy to produce at high yield, preferably in a microbial recombinant expression system, and convenient to isolate and/or purify subsequently. Also preferably, the antigen-binding protein is stable, both during storage and during utilization, meaning that the integrity of the antigen-binding protein is maintained under storage and/or utilization conditions, which may include elevated temperatures, freeze-thaw cycles, changes in pH or in ionic strength, UV-irradiation, presence of harmful chemicals and the like. More preferably, the antigen-binding protein is stable in an agrochemical formulation as further defined. Most preferably, the antigen-binding protein remains stable in an agrochemical formulation (as further defined) when stored at ambient temperature for a period of up to two years or when stored at 54° C. for a period of at least two weeks.
[0020] Binding of the antigen-binding protein to a chitinous polysaccharide occurs preferably with high affinity: typically, the dissociation constant of the binding between the antigen-binding protein and the chitinous polysaccharide target molecule is lower than 10 −5 M, more preferably, the dissociation constant is lower than 10 −6 M, even more preferably, the dissociation constant is lower than 10 −7 M, most preferably, the dissociation constant is lower than 10 −8 M. Preferably, binding of the antigen-binding protein to the chitinous polysaccharide is specific, meaning that the antigen-binding protein preferentially binds to a chitinous polysaccharide that is present in a homogeneous or heterogeneous mixture of different polysaccharides or other components. Specificity of binding of an antigen-binding protein can be analyzed by methods such as ELISA, as described in Example 3, in which the binding of the antigen-binding protein to its target molecule is compared with the binding of the antigen-binding protein to an unrelated molecule and with aspecific sticking of the antigen-binding protein to the reaction vessel. In certain embodiments, a specific binding interaction will discriminate between desirable and undesirable antigens in a sample, in some embodiments more than about ten- to 100-fold or more (e.g., more than about 1000- or 10,000-fold). Preferably, the binding of the antigen-binding protein to its target molecule is still functional under harsh conditions, such as low or high temperature, low or high pH, low or high ionic strength, UV-irradiation, presence of denaturing chemicals or the like. In one preferred embodiment, the harsh conditions are defined by a pH range from 4 to 9, more preferably by a pH range from 3 to 10, even more preferably by a pH range from 2 to 10, most preferably by a pH range from 1 to 11. In another preferred embodiment, the harsh conditions are defined by a temperature range from 4-50° C., more preferably, a temperature range from 0-55° C., even more preferably, a temperature range from 0-60° C. In still another preferred embodiment, the harsh conditions are defined as conditions prevalent in an agrochemical formulation as further defined.
[0021] In one preferred embodiment, the chitinous polysaccharide is chitin. “Chitin” as used herein means a natural aminopolysaccharide consisting of a long chain of N-acetylglucosamine, with a degree of deacetylation, which is lower than 70%. It is the main component of the cell walls of fungi, and is also present in the bud scars of Saccharomyces yeasts as well as the exoskeletons of arthropods such as crustaceans (e.g., lobsters and shrimps) and insects.
[0022] In one preferred embodiment, the chitinous polysaccharide, preferably the chitin, is comprised in a solid surface, such as a chitin paramagnetic bead or immobilized onto a solid surface, such as solubilized chitin, which is immobilized on an immunosorbent multi-well plate surface as non-limiting examples.
[0023] In another preferred embodiment, the chitinous polysaccharide, preferably the chitin, is comprised in or derived from an arthropod, preferably from an insect. “Comprised in” as used herein, means contained in, located in or enclosed in an arthropod, preferably an insect, or any particular part or structure thereof, such as the gut of an insect as a non-limiting example; “derived from,” as used herein means prepared from, produced from or isolated from an arthropod, preferably an insect, or any particular part or structure thereof, such as the shell of a crab or the exoskeleton of an insect as non-limiting examples. Preferably, the insect is considered as a pest insect. A “pest insect,” as used herein, is an insect that is detrimental to humans or human concerns, and includes, but is not limited to agricultural pest organisms, including but not limited to aphids, grasshoppers, caterpillars, beetles, etc., household pest organisms, such as cockroaches, ants, etc., and disease vectors, such as malaria mosquitoes.
[0024] In still another preferred embodiment, the chitinous polysaccharide, preferably the chitin, is comprised in or derived from a fungus, including but not limited to filamentous fungi and yeasts. “Comprised in” as used herein, means contained in, located in or enclosed in a fungus or a yeast, or any particular part or structure thereof, such as the hyphae of the fungus or the bud scars of a yeast as a non-limiting example; “derived from,” as used herein, means prepared from, produced from or isolated from a fungus or a yeast, or any particular part or structure thereof, such as the spores of a fungus or the cell wall of a yeast as non-limiting examples. Preferably, the fungus is considered as a fungal disease organism. A “fungal disease organism,” as used herein, is a fungal organism that is detrimental to humans or human concerns, and includes, but is not limited to agricultural fungal diseases, including but not limited to blights, smuts, molds, etc., animal and human fungal diseases, including but not limited to Candida albicans infections.
[0025] In yet another preferred embodiment, the antigen-binding protein binding to a chitinous polysaccharide, preferably to chitin, has an insecticidal activity. “Insecticidal activity,” as used herein, means that the antigen-binding protein is capable of either killing the insect, preferably the pest insect, or is capable of slowing or inhibiting the growth, the reproduction and/or the detrimental activity (such as the feeding on a crop) of the insect, preferably the pest insect. The insecticidal activity of an antigen-binding protein hereof can be determined by feeding the insect with the antigen-binding protein hereof and by monitoring the insect survival, the reproduction rate and/or the result of the detrimental activity (such as the amount of crop leaves that is eaten by the insect). By way of a non-limiting example, the antigen-binding protein hereof can by binding to chitin, lining the insect's gut, interfere with the digestive system of the insect and as such slow down or completely impair feeding of the insect, which may ultimately lead to starvation.
[0026] In still another preferred embodiment, the antigen-binding protein binding to a chitinous polysaccharide, preferably to chitin, has a fungicidal activity. “Fungicidal activity,” as used herein, means that the antigen-binding protein is capable of either partially or completely inhibiting the growth of a fungus or of killing the fungus, preferably the fungal disease organism, as described above. The fungicidal activity of an antigen-binding protein hereof can be determined by adding the antigen-binding protein hereof to the culture medium of a fungus or yeast and by monitoring the fungal growth rates and survival, using any of the methods as described in WO 9411511.
[0027] Preferably, the antigen-binding proteins hereof are derived from camelid antibodies, preferably from heavy chain camelid antibodies, devoid of light chains, such as variable domains of heavy chain camelid antibodies (VHH). Preferably, the VHH comprises, preferably consists of a sequence selected from the group consisting of SEQ ID NO:1 through SEQ ID NO:4 or homologues thereof. Homologues, as used here are sequences wherein each framework region and each complementarity-determining region shows at least 80% identity, preferably at least 85% identity, more preferably 90% identity, even more preferably 95% identity with the corresponding region in the reference sequence (i.e., FR1homologue versus FR1reference, CDR1homologue versus CDR1reference, FR2h versus FR2r, CDR2h versus CDR2r, FR3h versus FR3r, CDR3h versus CDR3r and FR4h versus FR4r) as measured in a BLASTp alignment (Altschul et al., 1997; FR and CDR definitions according to Kabat).
[0028] In still another embodiment, a nucleic acid sequence encoding any of the above antigen-binding proteins or functional fragments thereof is also part of the present invention. The invention also encompasses the use of any antigen-binding protein hereof to isolate amino acid sequences that are responsible for specific binding to a chitinous polysaccharide, preferably chitin, to construct artificial binding domains based on the amino acid sequences. Indeed, in the antigen-binding proteins hereof, the framework regions and the complementarity-determining regions are known, and the study of derivatives of the antigen-binding proteins, binding to the same chitinous polysaccharide, will allow deducing the essential amino acids involved in binding the chitinous polysaccharide. This knowledge can be used to construct a minimal antigen-binding protein and to create derivatives thereof.
[0029] Further, the present invention also envisages expression vectors comprising nucleic acid sequences encoding any of the above antigen-binding proteins or functional fragments thereof, as well as host cells expressing such expression vectors. Suitable expression systems include constitutive and inducible expression systems in bacteria or yeasts, virus expression systems, such as baculovirus, semliki forest virus and lentiviruses, or transient transfection in insect or mammalian cells. Suitable host cells include E. coli, Lactococcus lactis, Saccharomyces cerevisiae, Schizosaccharomyces pombe, Pichia pastoris , and the like. Suitable animal host cells include HEK 293, COS, S2, CHO, NSO, DT40 and the like. The cloning, expression and/or purification of the antigen-binding proteins can be done according to techniques known by the person skilled in the art. Accordingly, the invention encompasses methods of manufacturing antigen-binding proteins hereof, the method comprising the following steps:
(i) Cloning the nucleic acid sequences encoding any of the antigen-binding proteins hereof or functional fragments thereof in a suitable expression vectors, and (ii) Expressing the antigen-binding proteins in a suitable expression host; and (iii) Isolating and/or purifying the antigen-binding proteins from the lysate or supernatant of the expression host.
[0033] Although naive or synthetic libraries of VHH (for examples of such libraries, see WO 9937681, WO 0043507, WO 0190190, WO 03025020 and WO 03035694) may contain suitable binders against chitinous polysaccharides, one embodiment of this invention includes the immunization of an individual of a species of Camelidae with one or a combination of several chitinous polysaccharides, to expose the immune system of the animal to the chitinous polysaccharides. Thus, as further described herein, such VHH sequences can preferably be generated or obtained by suitably immunizing a species of Camelidae with one or a combination of several chitinous polysaccharides, by obtaining a suitable biological sample from the Camelidae species (such as a blood sample, or any sample of B-cells), and by generating V H H sequences directed against the desired chitinous polysaccharide, starting from the sample. Such techniques will be clear to the skilled person. Yet another technique for obtaining the desired VHH sequences involves suitably immunizing a transgenic mammal that is capable of expressing heavy chain antibodies (i.e., so as to raise an immune response and/or heavy chain antibodies directed against a chitinous polysaccharide), obtaining a suitable biological sample from the transgenic mammal (such as a blood sample, or any sample of B-cells), and then generating VHH sequences directed against the chitinous polysaccharide starting from the sample, using any suitable technique known per se. For example, for this purpose, the heavy chain antibody-expressing mice and the further methods and techniques described in WO 02085945 and in WO 04049794 can be used.
[0034] Accordingly, the invention encompasses methods of generating antigen-binding proteins hereof. As a non-limiting example, a method is provided for generating antigen-binding proteins specifically binding to chitinous polysaccharides, preferably to chitin, comprising:
(i) immunizing an animal with a complex mixture containing chitinous polysaccharides, and (ii) selecting antigen-binding proteins that are binding to solubilized chitin immobilized onto a solid surface; and (iii) screening for antigen-binding proteins specifically binding to chitin prepared on an insoluble carrier.
[0038] The screening for antigen-binding proteins, as a non-limiting example, specifically binding to a chitinous polysaccharide may for example be performed by screening a set, collection or library of cells that express heavy chain antibodies on their surface (e.g., B-cells obtained from a suitably immunized Camelid), or bacteriophages that display a fusion of genIII and VHH at their surface, by screening of a (naïve or immune) library of VHH sequences, or by screening of a (naïve or immune) library of nucleic acid sequences that encode VHH sequences, which may all be performed in a manner known per se, and which method may optionally further comprise one or more other suitable steps, such as, for example, and without limitation, a step of affinity maturation, a step of expressing the desired amino acid sequence, a step of screening for binding and/or for activity against the desired chitinous polysaccharide, a step of determining the desired amino acid sequence or nucleotide sequence, a step of introducing one or more nucleic acid substitutions, a step of formatting in a suitable multivalent and/or multispecific format, a step of screening for the desired biological and/or physiological properties (i.e., using a suitable assay known in the art), and/or any combination of one or more of such steps, in any suitable order.
[0039] A second aspect hereof is the use of an antigen-binding protein hereof to determine the presence and/or concentration of a chitinous polysaccharide in a sample.
[0040] Methods to determine the presence and/or concentration of a compound using antigen-binding proteins are known to the person skilled in the art and include, but are not limited to immunoprecipitation, fluorescent immunoassay, radio immunoassay (RIA), enzyme linked immunosorbent assay (ELISA) and magnetic immunoassay (MIA). The antigen-binding protein hereof can be labeled to facilitate the detection and/or quantification of the compound. Labeling of antigen-binding proteins is known to the person skilled in the art, and includes direct labeling and indirect labeling. In direct labeling, the antigen-binding protein itself is labeled by a directly detectable label such as, but not limited to a color label, a fluorescent label, a radioactive label or a magnetic particle. Fluorescent labels are especially useful, and include, but are not limited to fluorescein isothiocyanate (FITC) and other fluorescein derivatives, tetramethylrhodamine isothiocyanate (TRITC) and other rhodamine derivatives, R-pycoerythrin fluorescent protein (R-PE) and R-PE:cyanine-5, and allophycocyanin. Alternatively, the labeling can be carried out in an indirect way. In this case, the antigen-binding protein hereof functions can be bound to a detectable secondary compound, or is fused or bound to a tag, which on its own is not directly detectable, but can be detected by binding to a detectable secondary compound. It is obvious for the person skilled in the art that the detection can be the result of a chain of events, such as but not limited to serial binding of compounds, or activation of the label after binding.
[0041] As used herein a “sample” is a portion, piece or segment representative for a whole that one wants to analyze for the presence and/or concentration of one or more chitinous polysaccharides, preferably chitin. The sample can be a part that is withdrawn from the whole, or it can be the whole, measured at a representative point in place and/or time, as is the case for a sample measured on line by a biosensor during fermentation. As a non-limiting example, the sample can be a food sample, wherein the presence or concentration of the chitinous polysaccharide, preferably chitin, needs to be determined or changed in relation to allergenic capacity of the chitinous polysaccharide, or in relation to wanted or unwanted physical, chemical or microbiological characteristics of the chitinous polysaccharide, preferably chitin, changing the quality parameters of the food stuff, such as an altered shelf life.
[0042] In a similar way, chitin is often used as food additive, for improving the texture of the foodstuff, as thickening and stabilizing agent, and as natural flavor extender. Chitin can be used to improve nutritional quality, such as an increase in dietary fibre, to obtain a hypocholesterolemic effect, to reduce lipid adsorption and as antigastritis agent (Shahidi et al., 1999). Chitin and chitosan are also used as anti-microbials (Yalpani et al., 1992). However, the presence of chitin in food can also be due to fungal or yeast contamination, and detection of chitin has been used as a measure for such contamination, as is disclosed in WO 9217786 and in U.S. Pat. No. 5,004,699. A specific antigen-binding protein is needed to make a distinction between the possible sources and forms of chitin in food; the antigen-binding proteins hereof are specially suited for this kind of applications.
[0043] A third aspect hereof is the use of an antigen-binding protein hereof to isolate or purify a chitinous polysaccharide from a sample.
[0044] Isolation of the chitinous polysaccharide, preferably chitin, may be used to purify the chitinous polysaccharide out of a mixture, or it may be intended to remove a contaminating or otherwise undesirable chitinous polysaccharide out of a sample. Methods to use antigen-binding proteins for isolating compounds are known to the person skilled in the art and include but are not limited to immunoprecipitation and affinity chromatography. Alternatively, the antigen-binding protein hereof may be bound to a membrane, in order to be used in membrane filtration or similar techniques. Non limiting examples of the isolation and/or purification can be found in wastewater treatment.
[0045] One embodiment of the use of an antigen-binding protein hereof in purification is the purification of a fusion protein, comprising an antigen-binding protein hereof, most preferably a chitin-binding VHH. Fusion proteins are known to the person skilled in the art and consist of two or more proteins, protein parts or peptides that are joined together, either by chemical means (such as by crosslinking or by covalent binding) or by recombinant DNA methods. Immobilization and purification of recombinant fusion proteins, comprising a chitin-binding domain, on a chitin matrix is known to the person skilled in the art and has been disclosed in U.S. Pat. No. 5,258,502 and WO 03020745. Replacing or combining the chitin-binding domain by respectively with a chitin antigen-binding protein hereof has the advantage that the affinity for the matrix will be higher, and/or that the elution profile will be sharper and/or that the purification process will be more efficient.
[0046] A fourth aspect hereof is a kit for the detection of the presence and/or the determination of the concentration of a chitinous polysaccharide in a sample, comprising at least an antigen-binding protein hereof.
[0047] Apart from an antigen-binding protein hereof, which is binding to a chitinous polysaccharide, preferably to chitin, the kit may further comprise reagents needed for the labeling and/or detection and/or quantification of the antigen-binding protein. In one embodiment, the kit is used for diagnostic purposes.
[0048] A fifth aspect hereof is a biosensor for the detection of the presence and/or the determination of the concentration of a chitinous polysaccharide in a sample, comprising at least one antigen-binding protein hereof.
[0049] Preferably, the antigen-binding protein is immobilized on the sensing layer of the biosensor; the detection of the binding can be, as a non limiting example, optical, electrochemical, by quartz crystal microbalance, by magneto immune-sensors or by micromechanical cantilever-based immunosensors. The technology for the immobilization of the antigen-binding protein and for the detection of the binding between the target molecule and the antigen-binding protein is known to the person skilled in the art and has been reviewed, amongst others, by Marquette and Blum (2006), Fritz (2008) and Skottrup et al. (2008).
[0050] A sixth aspect hereof is a targeting agent, capable of binding a compound to a chitinous polysaccharide, wherein the targeting agent comprises at least one antigen-binding protein hereof.
[0051] A “targeting agent,” as used herein, is a molecular structure, preferably with a polypeptide backbone, comprising at least one antigen-binding protein hereof. A targeting agent in its simplest form consists solely of one single antigen-binding protein; however, a targeting agent can comprise more than one antigen-binding protein and can be monovalent or multivalent and monospecific or multispecific, as further defined. Apart from one single or multiple antigen-binding proteins, a targeting agent can further comprise other moieties, which can be either chemically coupled or fused, whether N-terminally or C-terminally or even internally fused, to the antigen-binding protein. The other moieties include, without limitation, one or more amino acids, including labeled amino acids (e.g., fluorescently or radioactively labeled) or detectable amino acids (e.g., detectable by an antibody), one or more monosaccharides, one or more oligosaccharides, one or more polysaccharides, one or more lipids, one or more fatty acids, one or more small molecules or any combination of the foregoing. In one preferred embodiment, the other moieties function as spacers or linkers in the targeting agent.
[0052] A “compound” as used here can be any compound, preferably an active substance, including but not limited to proteins and protein complexes such as enzymes, or chemical compounds, including but not limited to agrochemical active substances, as further defined. Preferably, a compound may be comprised in or onto a carrier, preferably a microcarrier, wherein the carrier can be coupled with one or more targeting agents comprising at least one antigen-binding protein hereof. “Comprised in a carrier” as used herein means bound on or contained in by means such as but not limited to embedding, encapsulation and adsorption. Preferably, the carrier is such that the one or more compounds can be incorporated, encapsulated or included into the carrier, e.g., as a nanocapsule, microcapsule, nanosphere, micro-sphere, liposome or vesicle. Preferably the carriers are such that they have immediate or gradual or slow release characteristics, for example over several minutes, several hours, several days or several weeks. Also, the carriers may be made of materials (e.g., polymers) that rupture or slowly degrade (for example, due to prolonged exposure to high or low temperature, sunlight, high or low humidity or other environmental factors or conditions) over time (e.g., over minutes, hours, days or weeks) and so release the compound from the carrier.
[0053] The targeting agent hereof may either be a “mono-specific” targeting agent or a “multi-specific” targeting agent. By a “mono-specific” targeting agent is meant a targeting agent that comprises either a single antigen-binding protein, or that comprises two or more different antigen-binding proteins that each are directed against the same binding site. Thus, a mono-specific targeting agent is capable of binding to a single binding site, either through a single antigen-binding protein or through multiple antigen-binding proteins. By a “multi-specific” targeting agent is meant a targeting agent that comprises two or more antigen-binding proteins that are each directed against different binding sites. Thus, a “bi-specific” targeting agent is capable of binding to two different binding sites; a “tri-specific” targeting agent is capable of binding to three different binding sites; and so on for “multi-specific” targeting agents. Also, in respect of the targeting agents described herein, the term “monovalent” is used to indicate that the targeting agent comprises a single antigen-binding protein; the term “bivalent” is used to indicate that the targeting agent comprises a total of two single antigen-binding proteins; the term “trivalent” is used to indicate that the targeting agent comprises a total of three single antigen-binding proteins; and so on for “multivalent” targeting agents.
[0054] “Capable of binding a compound to a chitinous polysaccharide,” as used herein, means that the binding of the antigen-binding protein, comprised in the targeting agent to the chitinous polysaccharide, is strong enough to bind, the compound, to a chitinous polysaccharide. Preferably, the compound is comprised into or onto a carrier, more preferably a microcarrier. Preferably, the targeting agent is coupled by affinity binding or by covalent binding to the compounds, even more preferably to the carrier containing the compounds. Preferably, the chitinous polysaccharide is chitin. Preferably, the chitinous polysaccharide is comprised in a solid surface or immobilized onto a solid surface.
[0055] Methods to couple the compound, preferably the plant-enhancing agent, and/or carrier to the targeting agent are known to the person skilled in the art, and include, but are not limited to covalent binding and affinity binding. An example of covalent binding is a fusion protein, wherein the targeting agent and a compound of proteinaceous nature are produced, preferably by means of recombinant protein expression, as one unity. An alternative approach to using fusion proteins is to use chemical cross-linking of residues in the targeting agent for covalent attachment to the compound, which can be a second protein or another chemical compound, using conventional coupling chemistry, for example as described by Fipula (2007) and in Bioconjugate Techniques , Hermanson, ed. Academic Press Inc., San Diego, Calif., USA, (2008). Amino acid residues incorporating sulphydryl groups, such as cysteine, may be covalently attached using a bispecific reagent such as succinimidyl maleimidophenylbutyrate (SMPB), for example. Alternatively, lysine groups located at the protein surface may be coupled to activated carboxyl groups on the second protein by conventional carbodiimide coupling using 1-ethyl-3[3-dimethylaminopropyl]carbodiimide (EDC) and N-hydroxysuccinimide (NHS). The coupling between the targeting agent and the compound or carrier wherein the compound is comprised, may be direct, or a spacer or hinge molecule can be used. Examples of such spacers can be found in WO 0024884 and WO 0140310.
[0056] In one embodiment, the antigen-binding protein comprised in the targeting agent hereof is binding a chitinous polysaccharide, preferably chitin, which is comprised in or derived from an arthropod, preferably an insect, and/or the resulting targeting agent is capable of binding a compound to an arthropod, preferably an insect.
[0057] In another preferred embodiment, the antigen-binding protein comprised in the targeting agent hereof is binding a chitinous polysaccharide, preferably chitin, which is comprised in or derived from a fungus or yeast and/or the resulting targeting agent is capable of binding a compound to a fungus or a yeast.
[0058] In still another preferred embodiment, the compound is an agrochemical active substance, as further defined, with an insecticidal or an anti-fungal activity, as earlier defined.
[0059] A seventh aspect hereof is the use of a targeting agent hereof, to target a compound to a chitinous polysaccharide.
[0060] To “target” as used herein means that the compound is delivered at or near its site of action, where it can subsequently bind to a chitinous polysaccharide through the antigen-binding protein hereof which is comprised in the targeting agent. In order to be able to bind, preferably to retain, a compound, preferably an agrochemical active substance to a chitinous polysaccharide, either one single or multiple targeting agents are either fused with or attached to the compound, preferably the agrochemical active substance, either by a covalent bond, by hydrogen bonds, by dipole-dipole interactions, by weak Van der Waals forces or by any combination of the foregoing. “Attached,” as used herein, means coupled to, connected to, anchored in, admixed with or covering. Preferably, the compound, more preferably, the agrochemical active substance is comprised in or onto a carrier, preferably a microcarrier. Preferably, the chitinous polysaccharide, more preferably chitin, is comprised in a solid surface or immobilized onto a solid surface.
[0061] The targeting of a compound or a combination of compounds by the targeting agent hereof can be any targeting known to the person skilled in the art, and includes, but is not limited to targeting of an enzyme to its substrate or targeting fragrance or color to chitinous polysaccharide-containing matrices. Indeed, it is known that chitin-binding domains play an essential role in the specificity of chitinases; Neeraja et al. (2010a) have demonstrated that the activity and conformational stability of chitinase can be improved by fusion to a cellulose-binding domain. A similar effect can be obtained by fusing a chitinous polysaccharide digesting catalytic domain (such as a chitinase catalytic domain) to an antigen-binding protein hereof. Other applications, such as the use of softening agents, polymeric lubricants, photoprotective agents, latexes, resins, dye fixative agents, encapsulated materials antioxidants, insecticides, anti-microbial agents, soil repelling agents or soil release agents, as well as other agents of choice, and ways and time of adding the agents to a polysaccharide-containing matrix are fully within the ordinary skill of a person skilled in the art.
[0062] In one embodiment, the compound, preferably the agrochemical active substance, is targeted to a chitinous polysaccharide, preferably to chitin, which is comprised in or derived from an arthropod, as defined above.
[0063] In another preferred embodiment, the compound, preferably the agrochemical active substance, is targeted to a chitinous polysaccharide, preferably to chitin, which is comprised in or derived from a fungus or yeast. Indeed, chitin is known to be part of the fungal cell wall, and can be used to target a compound or a combination of compounds to the fungal organism. As a non-limiting example, a chitin antigen-binding protein hereof can be coupled to an agrochemical active substance, as further defined, preferably with antifungal activity, as earlier defined, thereby delivering the agrochemical active substance to the fungus without contamination, or with a minimal contamination of the environment, eventually leading to lower residue levels of the agrochemical active substance on the crop that has been treated with the so targeted agrochemical active substance.
[0064] In still another preferred embodiment, the compound is an agrochemical active substance, as further defined, with an insecticidal or an anti-fungal activity, as earlier defined.
[0065] An eighth aspect hereof is a composition, comprising (i) at least one targeting agent hereof, and (ii) one or more compounds.
[0066] Preferably, the compounds are comprised in or onto a suitable carrier, preferably a microcarrier. Preferably, the targeting agent is coupled by affinity binding or by covalent binding to the compounds, even more preferably to the carrier containing the compounds. Preferably, the compound or combination of compounds are agrochemical active substances, as defined below.
[0067] In one embodiment, the composition is an agrochemical composition. An “agrochemical composition” as used herein means a composition for agrochemical use, as further defined, comprising at least one agrochemical active substance, as further defined, optionally with one or more additives favoring optimal dispersion, atomization, deposition, leaf wetting, distribution, retention and/or uptake of agrochemicals. As a non-limiting example such additives are diluents, solvents, adjuvants, surfactants, wetting agents, spreading agents, oils, stickers, thickeners, penetrants, buffering agents, acidifiers, anti-settling agents, anti-freeze agents, photo-protectors, defoaming agents, biocides and/or drift control agents.
[0068] “Agrochemical use,” as used herein, not only includes the use of agrochemical compositions as defined above that are suitable and/or intended for use in field grown crops (e.g., agriculture), but also includes the use of agrochemical compositions that are meant for use in greenhouse grown crops (e.g., horticulture/floriculture) or hydroponic culture systems or uses in public or private green spaces (e.g., private gardens, parks, sports fields), for protecting plants or parts of plants, including but not limited to bulbs, tubers, fruits and seeds (e.g., from harmful organisms, diseases or pests), for controlling, preferably promoting or increasing, the growth of plants; and/or for promoting the yield of plants, or the parts of plants that are harvested (e.g., its fruits, flowers, seeds etc.) and even the use of agrochemical compositions that are suitable and/or intended for non-plant uses such as household uses (for example, herbicides or insecticides for household use or agents to protect fabrics or wood from damage caused by harmful organisms), or industrial uses (for example, agents to prevent fouling or to protect stored goods from damage by harmful organisms) or uses by pest control operators (for example, to control undesirable insects and rodents etc.).
[0069] “Agrochemical active substance,” as used herein, means any active substance or principle that may be used for agrochemical use, as defined above. Examples of such agrochemical active substances will be clear to the skilled person and may for example include compounds that are active as insecticides (e.g., contact insecticides or systemic insecticides, including insecticides for household use), acaricides, miticides, herbicides (e.g., contact herbicides or systemic herbicides, including herbicides for household use), fungicides (e.g., contact fungicides or systemic fungicides, including fungicides for household use), nematicides (e.g., contact nematicides or systemic nematicides, including nematicides for household use) and other pesticides (for example avicides, molluscicides, piscicides) or biocides (for example, agents for killing bacteria, algae or snails); as well as fertilizers; growth regulators such as plant hormones; micro-nutrients, safeners; pheromones; repellants; baits (e.g., insect baits or snail baits); and/or active principles that are used to modulate (i.e., increase, decrease, inhibit, enhance and/or trigger) gene expression (and/or other biological or biochemical processes) in or by the targeted plant (e.g., the plant to be protected or the plant to be controlled). Agrochemical active substances include chemicals, but also nucleic acids (e.g., single stranded or double stranded RNA, as for example used in the context of RNAi technology), peptides, polypeptides, proteins (including antigen-binding proteins) and micro-organisms. “Micro-organisms” as used herein means bacteria, fungi, yeasts, viruses and the like. Examples of such agrochemical active substances will be clear to the skilled person; and for example include, without limitation: glyphosate, paraquat, metolachlor, acetochlor, mesotrione, 2,4-D,atrazine, glufosinate, sulfosate, fenoxaprop, pendimethalin, picloram, trifluralin, bromoxynil, clodinafop, fluoroxypyr, nicosulfuron, bensulfuron, imazetapyr, dicamba, imidacloprid, thiamethoxam, fipronil, chlorpyrifos, deltamethrin, lambda-cyhalotrin, endosulfan, methamidophos, carbofuran, clothianidin, cypermethrin, abamectin, diflufenican, spinosad, indoxacarb, bifenthrin, tefluthrin, azoxystrobin, thiamethoxam, tebuconazole, mancozeb, cyazofamid, fluazinam, pyraclostrobin, epoxiconazole, chlorothalonil, copper fungicides, trifloxystrobin, prothioconazole, difenoconazole, carbendazim, propiconazole, thiophanate, sulphur, boscalid and other known agrochemicals or any suitable combination(s) thereof. Other suitable agrochemicals will be clear to the skilled person based on the disclosure herein, and may for example be any commercially available agrochemical, and for example include each of the compounds listed in Phillips McDougall, AgriService November 2007 V4.0, Products Section—2006 Market, Product Index pp. 10-20. The agrochemical active substances can occur in different forms, including but not limited to, as crystals, as micro-crystals, as nano-crystals, as co-crystals, as a dust, as granules, as a powder, as tablets, as a gel, as a soluble concentrate, as an emulsion, as an emulsifiable concentrate, as a suspension, as a suspension concentrate, as a suspoemulsion, as a dispersion, as a dispersion concentrate, as a microcapsule suspension or as any other form or type of agrochemical formulation clear to those skilled in the art. Agrochemical active substances not only include active substances or principles that are ready to use, but also precursors in an inactive form, which may be activated by outside factors. As a non limiting example, the precursor can be activated by pH changes, caused by plant wounds upon insect damage, by enzymatic action caused by fungal attack, or by temperature changes or changes in humidity.
[0070] The agrochemical composition hereof may be in a liquid, semi-solid or solid form and for example be maintained as an aerosol, flowable powder, wettable powder, wettable granule, emulsifiable concentrate, suspension concentrate, microemulsion, capsule suspension, dry microcapsule, tablet or gel or be suspended, dispersed, emulsified or otherwise brought in a suitable liquid medium (such as water or another suitable aqueous, organic or oily medium) for storage or application. The agrochemical composition hereof comprises at least one, preferably more antigen-binding proteins hereof. The presence of one or more antigen-binding proteins hereof in the agrochemical composition hereof, ensures the binding of the agrochemical active substance to its site of action, such as the plant or plant part (e.g., the fruit, tuber or bulb), the plant seed or other plant-derived organic material, while sticking of the agrochemical active substance to storage containers and/or operator's equipment is avoided. Optionally, the composition further comprises one or more further components such as, but not limited to diluents, solvents, adjuvants, surfactants, wetting agents, spreading agents, oils, stickers, thickeners, penetrants, buffering agents, acidifiers, anti-settling agents, anti-freeze agents, photo-protectors, defoaming agents, biocides and/or drift control agents or the like, suitable for use in the composition hereof.
[0071] In one preferred embodiment, the agrochemical composition comprises exerts an antifungal activity, as earlier defined.
[0072] In another preferred embodiment, the agrochemical composition exerts an insecticidal activity, as earlier defined.
[0073] The invention also encompasses a method for manufacturing a composition, preferably an agrochemical composition, hereof, the method comprising (i) selecting at least one, preferably more, targeting agents hereof, and (ii) coupling the seed targeting agent(s) to a compound, preferably an agrochemical active substance, or a combination of compounds, and optionally (iii) adding further components that may be suitable for such compositions, preferably for agrochemical compositions. Preferably, the compound is comprised in a carrier, more preferably, the targeting agent(s) are coupled to the carrier, comprising the compound, preferably the agrochemical active substance.
[0074] A ninth aspect hereof is a method for improving the resistance of a plant against insect pests and/or fungal disease, the method comprising at least one application of a composition hereof to the plant or to plant parts.
[0075] If needed, the composition is dissolved, suspended and/or diluted in a suitable solution before use. The application to the plant or plant parts is carried out using any suitable or desired manual or mechanical technique for application of an agrochemical composition, including but not limited to spraying, brushing, dressing, dripping, dipping, coating, spreading, applying as small droplets, a mist or an aerosol. “Improving the resistance of a plant,” as used herein, is the protection of the plant against damage or yield decrease, caused by insect pests (as defined earlier) or by fungal disease organisms (as defined earlier). Indeed, as the composition hereof has an insecticidal or a fungicidal activity, the application of the composition to the plant, may help the plant to combat damage, —and as such prevent yield losses—caused by insect pests or fungal disease organisms. “Plant part,” as used herein, means any plant part whether part of an intact living or growing plant or whether isolated or separated from a plant, and even dead plant material can be envisaged. Preferably, the plant parts are selected from the group consisting of leaves, roots, fruits, cones, flowers, seeds, bulbs and tubers.
[0076] In one embodiment, the plant is a crop. “Crop” as used herein means a plant species or variety that is grown to be harvested as food, livestock fodder, fuel raw material, or for any other economic purpose. As a non-limiting example, the crops can be maize, cereals, such as wheat, rye, barley and oats, sorghum, rice, sugar beet and fodder beet, fruit, such as pome fruit (e.g., apples and pears), citrus fruit (e.g., oranges, lemons, limes, grapefruit, or mandarins), stone fruit (e.g., peaches, nectarines or plums), nuts (e.g., almonds or walnuts), soft fruit (e.g., cherries, strawberries, blackberries or raspberries), the plantain family or grapevines, leguminous crops, such as beans, lentils, peas and soya, oil crops, such as sunflower, safflower, rapeseed, canola, castor or olives, cucurbits, such as cucumbers, melons or pumpkins, fiber plants, such as cotton, flax or hemp, fuel crops, such as sugarcane, miscanthus or switchgrass, vegetables, such as potatoes, tomatoes, peppers, lettuce, spinach, onions, carrots, eggplants, asparagus or cabbage, ornamentals, such as flowers (e.g., petunias, pelargoniums, roses, tulips, lilies, or chrysanthemums), shrubs, broad-leaved trees (e.g., poplars or willows) and evergreens (e.g., conifers), grasses, such as lawn, turf or forage grass or other useful plants, such as coffee, tea, tobacco, hops, pepper, rubber or latex plants.
[0077] A tenth aspect hereof is a plant, transformed with a nucleic acid comprising a nucleic acid sequence, encoding an antigen-binding protein hereof, or any suitable fragment thereof.
[0078] In order to transform a plant with a nucleic acid comprising the nucleic acid sequence of an antigen-binding protein hereof or any suitable fragment thereof, the nucleic acid of the antigen-binding protein hereof is first cloned into a suitable expression vector, which is known by the person skilled in the art. Subsequently, the expression vector, comprising the nucleic acid sequence encoding the antigen-binding protein hereof or any suitable fragment thereof, is transformed by methods known to the person skilled in the art, including but not limited to Agrobacterium -mediated transformation, electroporation, microinjection or DNA- or RNA-coated particle bombardment or such other methods known to the person skilled in the art into suitable plant cells or plant tissue and eventually a plant, which incorporates the nucleic acid sequence encoding the antigen-binding protein hereof into its genome, is regenerated from the transformed plant cells or plant tissue.
[0079] In one embodiment, the plant is a crop, as defined above.
[0080] In another preferred embodiment, the plant, preferably the crop, is more resistant to damage from insect pests or fungal disease, as defined above. Indeed, as the plant is expressing an antigen-binding protein hereof, which may have an insecticidal or fungicidal activity as defined earlier, the plant may be better capable to combat damage, —and as such prevent yield losses—caused by insect pests or fungal disease organisms in comparison to a plant, not transformed with a nucleic acid sequence, encoding an antigen-binding protein hereof, or any suitable fragment thereof.
DETAILED DESCRIPTION
Examples
Example 1
Generation and Selection of VHH
[0081] Immunization of Llamas with Insect Homogenates—
[0082] Colorado Potato Beetles ( Leptinotarsa decemlineata ) were dissected, exoskeletons and wings collected, and remainders discarded. Exoskeletons and wings were separately frozen in liquid nitrogen, ground with mortar and pestle, and fine powders collected. Colorado potato beetle larvae, Pea aphids ( Acyrthosiphon pisum ), and Tobacco Budworm larvae ( Heliothis virescens ), were frozen in liquid nitrogen, ground with mortar and pestle, and fine powders collected. Collected insect materials were resuspended in PBS and total protein concentrations of suspensions were determined with Bradford protein assay. Approximate total protein concentrations were 4.2, 0.3, 4.2, 2.7, and 2.3 mg/ml for Colorado potato beetle (CPB) exoskeletons, CPB wings, Pea aphids, CPB larvae, and Tobacco Budworm larvae suspensions, respectively. Suspensions were mixed on basis of equal total protein concentration and aliquots were prepared, stored at −80° C., and suspensions were used for immunization.
[0083] Two Llamas, named Curley Sue and Jean Harlow, were immunized at weekly intervals with six intramuscular injections of mixed insect suspensions using Freund's Incomplete Adjuvant (FIA). Doses for immunizations were 125 μg total protein for days 0 and 6, and 62.5 μg total protein for days 13, 20, 27, and 34. At day 0 and at time of PBL collection at day 38, sera of llamas were collected.
[0084] Library Construction—
[0085] From each immunized llama a separate VHH library was made. RNA was isolated from peripheral blood lymphocytes, followed by cDNA synthesis using random hexamer primers and Superscript III according to the manufacturer's instructions (Invitrogen). A first PCR was performed to amplify VHH and VH DNA fragments using a forward primer mix [1:1 ratio of call001 (5′-gtcctggctgctcttctacaagg-3′) and call001b (5′-cctggctgctcttctacaaggtg-3′)] and reverse primer call002 (5′-ggtacgtgctgttgaactgttcc-3′). After separation of VH and VHH DNA fragments by agarose gel electrophoresis and purification of VHH DNA fragments from gel, a second PCR was performed on VHH DNA fragments to introduce appropriate restriction sites for cloning using forward primer A6E (5′-gatgtgcagctgcaggagtctggrggagg-3′ (SEQ ID NO:_) and reverse primer 38 (5′-ggactagtgcggccgctggagacggtgacctgggt-3′ (SEQ ID NO:_)). The PCR fragments were digested using PstI and Eco911 restriction enzymes (Fermentas), and ligated upstream of the pIII gene in vector pMES3. The ligation products were ethanol precipitated according to standard protocols, resuspended in water, and electroporated into TG1 cells. Library sizes were at least 1E+08 independent clones for each library. Single colony PCR on randomly picked clones from the libraries was performed to assess insert percentages of the libraries. Libraries “Curley Sue” and “Jean Harlow” had ≧80% insert percentages of full-length clones. Libraries were numbered 44 and 45 for llamas “Curley Sue” and “Jean Harlow,” respectively. Phage from each of the libraries were produced using VCSM13 helper phage according to standard procedures.
[0086] Phage Selections Against Chitin—
[0087] For selections against chitin, practical grade chitin (Sigma) was coated in ELISA plates (Maxisorp, Nunc). Chitin was dissolved at 10 mg/ml concentration in 85% phosphoric acid by shaking on a vortex shaker for approximately 3 hours until all particles were dissolved. Serial five-fold dilutions in PBS were prepared, precipitated chitin removed by centrifuging at 20,000 g for 5 minutes and supernatants used for coating of ELISA plates (Maxisorp, Nunc). Wells with 100 μl per well chitin solutions were coated at 4° C. overnight or over weekend. Sera of llamas Curley Sue and Jean Harlow were used to determine optimum chitin concentration for coating in a serum titer ELISA performed according to standard procedures. 25-fold and 3,125-fold diluted chitin solutions were used for selections. Wells were washed three times with PBS/0.05%-TWEEN®-20 and blocked with 5% skimmed milk in PBS (5% MPBS). Phage were suspended in 2.5% MPBS and approximately 1E+12 cfu were used for each well. After binding to the wells at room temperature for 2 hours, unbound phage were removed by extensive washing with PBS/0.05%-TWEEN®-20 and PBS. Bound phage were eluted at room temperature with 0.1 mg/ml trypsin (Sigma) in PBS for 30 minutes. Eluted phage were transferred to a polypropylene 96-well plate (Nunc) containing excess AEBSF trypsin inhibitor (Sigma). The titers of phage from target-coated wells were compared to titers of phage from blank wells to assess enrichments. Phage were amplified using fresh TG1 cells according to standard procedures. Enrichments in selection round 1 were approximately ten-fold for both libraries 44 and 45. Enrichments in selection round 2 were five- and ≧3E+03-fold for libraries 44 and 45, respectively.
[0088] Picking Single Colonies from Selection Outputs—
[0089] Fresh TG1 cells were infected with serially diluted eluted phage and plated on LB agar; 2% glucose; 100 μg/ml ampicillin. Single colonies were picked in 96-well plates containing 100 μl per well 2×TY; 10% glycerol; 2% glucose; 100 μg/ml ampicillin. Plates were incubated at 37° C. and stored at −80° C. as master plates. From selections against chitin 16 clones were picked from 1 st round selections and 30 clones were picked from 2 nd round selections for each library 44 and 45, in total 92 clones.
Example 2
Characterization of VHH
[0090] Single-Point Binding ELISA—
[0091] A single-point binding ELISA was used to identify clones binding to plant extracts. VHH-containing extracts for ELISA were prepared as follows. 96-well plates with 100 μl per well 2×TY, 2% glucose 100 μg/ml ampicillin were inoculated from the master plates and grown at 37° C. overnight. 25 μl per well of overnight culture was used to inoculate fresh 96-well deep-well plates containing 1 ml per well 2×TY; 0.1% glucose; 100 μg/ml ampicillin. After growing at 37° C. in a shaking incubator for 3 hours, IPTG was added to 1 mM final concentration and recombinant VHH were produced during an additional incubation for 4 hours. Cells were spun down by centrifugation at 3,000 g for 20 minutes, supernatants discarded, and pellets stored at −20° C. overnight. Cell pellets were thawed, briefly vortexed, and 125 μl per well of room temperature PBS was added. Cells were resuspended on an ELISA shaker platform at room temperature for 15 minutes. Plates were centrifuged at 3,000 g for 20 minutes and 100 μl per well of VHH-containing extract was transferred to polypropylene 96-well plates (Nunc) and stored at −20° C. until further use. Binding of clones from chitin selections was analyzed using ELISA plates coated with 100 μl per well of 25-fold diluted chitin, prepared similarly as for selections. After coating at 4° C. overnight and continued coating at room temperature for 1 hour on the next day, plates were washed three times with PBS/0.05%-TWEEN®-20 and blocked with 5% skimmed milk in PBS for 1.5 hours. Plates were emptied and filled with 90 μl per well 1% MPBS. Ten μl of VHH-containing extract from each clone was added to (an) antigen-coated well(s) and a blank well. VHH were allowed to bind at room temperature for 1 hour and non-binding VHH were removed by washing three times with PBS/0.05%-TWEEN®-20. Bound VHH were detected with sequential incubations with monoclonal mouse anti-histidine antibodies (Abd Serotec) in 1% MPBS/0.05%-TWEEN®-20 and rabbit anti-mouse IgG whole molecule antibodies conjugated with alkaline phosphatase (RaM/AP) (Sigma) in 1% MPBS/0.05%-TWEEN®-20. Unbound antibodies were removed by washing three times with PBS/0.05%-TWEEN®-20. The plates were washed an additional two times with PBS and 100 μl pNPP disodium hexahydrate substrate (Sigma) was added to each well. The absorbance at 405 nm was measured and the ratio of VHH bound to (a) target-coated well(s) and a non-target-coated well was calculated for each clone. From selections against chitin 28 of 92 (30%) clones had a ratio greater than 2 and these clones were analyzed further by sequencing.
[0092] Single Colony PCR and Sequencing—
[0093] Single colony PCR and sequencing was performed on ELISA positive clones as follows. Cultures from master plate wells with ELISA positive clones were diluted ten-fold in sterile water. Five μl from these diluted clones were used as template for PCR using forward primer MP57 (5′-ttatgcttccggctcgtatg-3′) and reverse primer GIII (5′-ccacagacagccctcatag-3′). PCR products were sequenced by Sanger-sequencing using primer MP57 (VIB Genetic Service Facility, University of Antwerp, Belgium). From selections against chitin clones VHH 15A9, VHH 15D1, VHH 15E4, and VHH 15G2 were found. Clones VHH 15E4 and VHH 15G2 are variants of clone 15D1 with one and two amino acid substitutions, respectively.
[0094] Antibody Production and Purification—
[0095] VHH were produced in E. coli suppressor strain TG1 or non-suppressor strain WK6 (Fritz et al., Nucleic Acids Research , Volume 16 Number 14 1988) according to standard procedures. Briefly, colony streaks were made and overnight cultures from single colonies inoculated in 2×TY; 2% glucose; 100 μg/ml ampicillin. The overnight cultures were used to inoculate fresh cultures 1:100 in 2×TY; 0.1% glucose; 100 μg/ml ampicillin. After growing at 37° C. in a shaking incubator for 3 hours, IPTG was added to a 1 mM final concentration and recombinant VHH were produced during an additional incubation for 4 hours. Cells were spun down and resuspended in 1/50 th of the original culture volume of periplasmic extraction buffer (50 mM phosphate pH 7; 1 M NaCl; 1 mM EDTA) and incubated with head-over-head rotation at 4° C. overnight. Spheroplasts were spun down by centrifugation at 3,000 g and 4° C. for 20 minutes. Supernatants were transferred to fresh tubes and centrifuged again at 3,000 g and 4° C. for 20 minutes. Hexahistidine-tagged VHH were purified from the periplasmic extract using 1/15 th of the extract volume of TALON metal affinity resin (Clontech), according to the manufacturer's instructions. Purified VHH were concentrated and dialyzed to PBS using Vivaspin 5 kDa molecular weight cut-off (MWCO) devices (Sartorius Stedim), according to the manufacturer's instructions.
Example 3
VHH Binding to Chitinous Polysaccharides in ELISA
[0096] VHH Binding to Chitin in ELISA—
[0097] Titration of VHH was performed on ELISA plates (Maxisorp, Nunc) coated with chitin. Chitin was dissolved at 10 mg/ml concentration in 85% phosphoric acid by shaking on a vortex shaker for approximately 3 hours until all particles were dissolved. Dissolved chitin was diluted 25-fold in PBS and precipitated chitin removed by centrifuging at 20,000 g for 5 minutes. 100 μl per well supernatant were used for coating of ELISA plates (Maxisorp, Nunc). Plates were coated at 4° C. overnight and coating was continued at room temperature for 1 hour on the next day. Plates were washed three times with PBS/0.05%-TWEEN®-20 and blocked with 5% skimmed milk in PBS for 1 hour. Four-fold serial dilutions of purified VHH were prepared in 1% MPBS/0.05%-TWEEN®-20 in polypropylene 96-well plates. Antibody concentrations ranged from 3 μg/ml to 12 ng/ml. Antibody dilutions were transferred to the chitin-coated plates and VHH were allowed to bind for 1 hour at room temperature. Bound VHH were detected with sequential incubations with monoclonal mouse anti-histidine antibodies (Abd Serotec) and rabbit anti-mouse IgG whole molecule antibodies conjugated with alkaline phosphatase (RaM/AP) (Sigma) in 1% MPBS/0.05%-TWEEN®-20. Unbound antibodies were removed by washing three times with PBS/0.05%-TWEEN®-20 after each antibody incubation. The plates were washed an additional two times with PBS and 100 μl pNPP disodium hexahydrate substrate (Sigma) was added to each well. The absorbance at 405 nm was measured and plotted as function of antibody concentration (see Table 1).
[0000]
TABLE 1
VHH binding to chitin in ELISA:
[VHH] (μg/ml)
3.0
0.75
0.19
0.047
0.012
0
[VHH] (nM)
200
50
13
3.1
0.78
0
Chitin
+
+
+
+
+
+
1
2
3
4
5
6
VHH15A9
A
=4.000
2.059
0.640
0.225
0.112
0.090
VHH15D1
B
2.669
1.459
0.392
0.121
0.089
0.088
Unrelated VHH
C
0.089
0.086
0.089
0.089
0.085
0.088
Specificity of Chitin-Binding VHH in ELISA
[0098] In order to investigate the specificity of the selected chitin-binding VHH an ELISA with different coatings was used. VHH 15A9 as well as control conditions with other antibodies were tested for binding to chitin, pectin, and potato lectin. ELISA plates (Maxisorp, Nunc) were coated with 100 μl per well chitin similarly as for the titration ELISA, 100 μg/ml 20-34% esterified pectin from citrus fruits (Sigma), or potato lectin (Sigma) in PBS. Plates were coated at 4° C. overnight and coating was continued at room temperature for 1 hour on the next day. Plates were washed three times with PBS/0.05%-TWEEN®-20 and blocked with 5% skimmed milk in PBS for 1 hour. Purified VI-1H 15A9 was diluted to 3 μg/ml in 1% MPBS/0.05%-TWEEN® and added to the coated plate and VHH were allowed to bind for 1 hour at room temperature. Bound VHH were detected with sequential incubations with monoclonal mouse anti-histidine antibodies (Abd Serotec) and rabbit anti-mouse IgG whole molecule antibodies conjugated with alkaline phosphatase (RaM/AP) (Sigma) in 1% MPBS/0.05%-TWEEN®-20. Unbound antibodies were removed by washing three times with PBS/0.05%-TWEEN®-20 after each antibody incubation. The plates were washed an additional two times with PBS and 100 μl pNPP disodium hexahydrate substrate (Sigma) was added to each well. The absorbance at 405 nm was measured and binding obtained binding profile for VHH 15A9 and control antibodies compared (see Table 2). Diverse and distinct binding patterns were observed for VHH 15A9 and control antibodies. VHH 15A9 showed specific binding to chitin only.
[0000]
TABLE 2
Specificity of chitin-binding VHH in ELISA
Control
Control
VHH 15A9
Control
antibody
antibody
specifically
condition
binding
binding to
binding to
without
specifically
potato lectin
chitin
VHH
to pectin
and pectin
Chitin coating
0.846
0.110
0.115
0.114
Pectin coating
0.118
0.114
3.171
0.409
Potato lectin
0.114
0.112
0.118
3.878
coating
No coating
0.109
0.111
0.111
0.116
control condition
Example 4
Binding of VHH to Chitin Beads
[0099] Binding of VHH to Chitin Beads—
[0100] Anti-chitin VHH were analyzed for binding to paramagnetic chitin beads (New England Biolabs). These beads are formed through emulsion chemistry starting with low molecular weight chitosan and encapsulation of magnetite particles during bead formation. Once the beads are formed they are acetylated to ensure that they are chitin beads. Beads were equilibrated by five washes with 500 mM NaCl/20 mM Tris-HCl/1 mM EDTA/0.1%-TWEEN®-20 using a Dynamag spin magnet (Invitrogen) and removing supernatants by pipetting. Equilibrated beads were dispensed and incubated with 5 μg/ml histidine-tagged anti-chitin VHH in 1% BSA/PBS with head-over-head rotation at 4° C. for 2 hours. Control conditions included incubations with unrelated VHH in 1% BSA/PBS or with 1% BSA/PBS alone. Non-bound VHH were washed away by five washes with PBS and bound VHH were detected by consecutive incubations with monoclonal mouse anti-histidine antibodies (Abd Serotec) and rabbit anti-mouse IgG whole molecule antibodies conjugated with alkaline phosphatase (RaM/AP) (Sigma). Antibodies were diluted in 1% BSA/PBS and incubated at room temperature for 1 hour. Non-bound antibodies were removed by washing five times with PBS in between different incubations. After final washes and removal of supernatant pNPP disodium hexahydrate substrate (Sigma) was added to each condition and incubated for 10 minutes. Substrates were transferred to an optical plate and the absorbance at 405 nm was measured. Measured absorbance was 4.0 (saturated), 4.0 (saturated), 3.8, 4.0 (saturated), 0.23, and 0.20 for VHH 15D1, VHH 15E4, VHH 15G2, VHH 15A9, unrelated VHH, and incubation without VHH, respectively. These data show that after selecting and performing primary screens on practical grade chitin VHH 15D1, VHH 15E4, VHH 15G2, and VHH 15A9 are truly binding chitin.
Example 5
Binding of VHH-Coupled Microcapsules to Immobilized Chitinous Polysaccharide
[0101] With the objective to generate VHH-functionalized polyurea microcapsules, VHH were coupled to microcapsules with a core of 1.5% Uvitex OB (Ciba) in benzyl benzoate and a shell with incorporated lysine to surface-expose carboxyl groups. A core of 1.5% Uvitex OB in benzyl benzoate was used for fluorescent visualization of microcapsules. After production of microcapsules, microcapsules were washed with water and stored as capsule suspensions in water. Before coupling of VHH, microcapsules were washed with MES/NaCl buffer (0.1 M MES/0.5 M NaCl pH 6) using a 96-well deep-well filtration plate (Millipore) and vacuum manifold (Millipore). A panel of VHH was dialyzed to MES/NaCl buffer and added to a final concentration of 10-70 μM and incubated with the microcapsules for 15-30 minutes. 1-Ethyl-3-[3-dimethylaminopropyl]carbodiimide Hydrochloride (EDC) (Pierce) was dissolved in MES/NaCl buffer and promptly added to a final concentration of 50 mM. VHH were coupled by incubation with continuous mixing at room temperature for 2 hours. The coupling reactions were stopped by adding glycine or Tris-buffer pH 7.5 to a final concentration of 100 mM and incubation at room temperature for 30 minutes. Non-bound VHH were collected using the filtration plate setup using a deep-well collector plate. Microcapsules were washed three times with PBS and resuspended in PBS and stored at 4° C. until use.
[0102] An ELISA-like assay setup was used to evaluate the interaction of VHH-coupled microcapsules to chitinous polysaccharides-containing surfaces. Wells of a high bind half area microplate (Greiner Bio-One) were coated with chitin. Coating with chitin was performed as before for the titration and specificity ELISAs. 100 μg/ml potato lectin in PBS was coated as control condition. The microplate was washed three times with PBS with 0.05%-TWEEN®-20 and blocked with 5% skimmed milk in PBS for 2 hours. VHH-coupled microcapsules containing a fluorescent tracer were diluted to appropriate density in 1% skimmed milk in PBS with 0.05%-TWEEN®-20. Microcapsules were added in serial dilution to the chitin-coated or control wells and allowed to bind for 1 hour. Unbound microcapsules were removed by washing five times with PBS with 0.05%-TWEEN®-20. The bottoms of ELISA plate wells were analyzed for fluorescence using a multimode microplate reader (Tecan) for bound microcapsules (see Table 3).
[0000]
TABLE 3
Use of VHH for binding of microcapsules to immobilized
chitinous polysaccharides. A bottom scan was performed
to investigate bound fluorescent tracer microcapsules
to chitin or control antigen-coated surfaces.
Fluorescent tracer
Blank
Microcapsule
microcapsules
microcapsules
amount
with VHH 15A9
without VHH
Chitin coating
100%
10621
2101
Chitin coating
20%
985
356
Chitin coating
4%
262
142
Potato lectin coating
100%
837
3206
Potato lectin coating
20%
581
645
Potato lectin coating
4%
157
212
Example 5
Binding of Microcapsules, Coupled with VHH, to Chitin Beads
[0103] Binding of VHH-coupled microcapsules to chitin magnetic beads was investigated with paramagnetic chitin beads (New England Biolabs). Beads were equilibrated by five washes with 500 mM NaCl/20 mM Tris-HCl/1 mM EDTA/0.1%-TWEEN0-20 using a Dynamag spin magnet (Invitrogen) and removing supernatants by pipetting. 1 mg quantities of beads were dispensed and the approximate concentration of beads was calculated from the diameter of the beads (ø 50-70 μm). Chitin beads were incubated with a 100-fold excess of microcapsules (ø 10 μm) over the number of chitin beads in 1% BSA in PBS and binding was allowed for 1 hour with head-over-head rotation at room temperature. Control conditions included incubations with blank microcapsules to which no VHH had been coupled. Five washes were performed with PBS using head-over-head rotation for each wash and using the Dynamag spin magnet to collect the beads in between each wash step. Beads with bound microcapsules were finally resuspended in a small volume and transferred to an 18-well μ slide (Ibidi) and analyzed for bound microcapsules on a macrozoom microscope system (Nikon). Microcapsules were counted using Volocity image analysis software (Perkin Elmer). A DAPI filter was used to visualize Uvitex microcapsules. 2.2E+03 microcapsules were found on 1 mg chitin beads with VHH 15D1-coupled microcapsules. Only 7.1E+02 microcapsules were found on 1 mg chitin beads with blank microcapsules to which no VHH had been coupled. Advantageous binding to chitin magnetic beads was obtained with microcapsules with coupled VHH binding to chitin.
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This application is a continuation of application Ser. No. 08/334,089, filed Nov. 4, 1994.
BACKGROUND OF THE INVENTION
1. Field of the Invention
Erucic acid is a fatty acid which is an important raw material in the oleochemical industry. It is a component of several vegetable oils, the major industrial source of erucic acid at present being high erucic acid rapeseed oil (HEAR oil). Current methods of extraction are costly, however, and the finished product contains by-products which impart undesirable properties. Thus, there is a need for an effective, low cost method of extraction which results in the production of a high-quality product.
2. Description of the Prior Art
Erucic acid (C22:1,δ13) is a naturally-occurring fatty acid found in the storage triglycerides of plants of the family Brassicaceae. Rapeseed is a member of this family and is grown in several countries for its oilseed. Rapeseed oil contains a high content of erucic acid (more than 40%) and is important in industrial applications.
Erucic acid can be isolated from rapeseed oil fatty acids by fractional distillation or multiple solvent crystallization at low temperature (Stage, H., Fette Seifen Anstrichm. 1975. vol. 77, p. 165-204). In the case of fractional distillation, however, temperatures of up to 255° C. must be utilized which may result in by-product formation which imparts an undesirable color to the erucic acid (Stage, H., World Conference on Oleochemicals into the 21st Century. T. H. Applewhite, ed. 1990. American Oil Chemists Society, pp. 142-160).
The search has thus continued for a process for purifying erucic acid from vegetable oils under mild hydrolysis conditions which result in a high-quality product of high yield and high purity.
It was found that lipases having fatty acid selectivity provided a milder, more convenient route to erucic acid production. Lipase from Geotrichum candidum (G. candidum), well known for its preference for C18 fatty acids containing a cis double bond in the δ9 position (Jensen, R. G., Lipids. 1974. vol. 9, pp. 149-157), poorly utilizes fatty acids which are longer than 18 carbons even if a cis double bond is located at the δ9 position in the fatty acid chain (Sonnet et al., J. Am. Oil Chem. Soc. 1993. vol. 70, pp. 1043-1045).
Lipase from Candida rugosa (C. rugosa) also exhibits some fatty acid selectivity, releasing long chain fatty acids more slowly than C16 and C18 acids from fish oil triglycerides (Lie and Lambertson, Fette Seifen Anstrichm. 1986. vol. 88, pp. 365-367; Hoshino et al., Agric. Biol. Chem. 1990. vol. 54, pp. 1459-1467). In addition, it was recently found that this enzyme hydrolyses esters containing erucic acid more slowly than those containing C16 or C18 fatty acids (Sonnet, supra; Ergan et al., Annal. N.Y. Acad. Sci. 1992. vol. 672, pp. 37-44; Kaimal et al., Biotech. Lett. 1993. vol. 15, pp. 353-356). Most fatty acids in rapeseed oil are either C18 or erucic acid. Hydrolysis of rapeseed oil with this lipase should thus result in a glyceride fraction enriched in erucic acid and a free fatty acid fraction containing only C18 acids. These fractions can be easily separated from each other, thus providing a fraction containing a mixture of the glycerides mono- and dierucin. The limited specificity of this lipase is insufficient for a commercially useful process, however, therefore studies were carried out to determine a means of enhancing the process.
SUMMARY OF THE INVENTION
I have discovered that erucic acid may be produced by enzymatic hydrolysis utilizing lipases from Geotrichum candidum or Candida rugosa to catalyze the reaction. Fatty acid substituents with carbon chains shorter than C22 are removed from triglycerides which also contain one or two erucic acid substituents, resulting in a glyceride fraction enriched in erucic acid and a free fatty acid fraction containing the hydrolyzed substituent. The reaction utilizing lipase from C. rugosa is temperature-sensitive, requiring a reaction temperature of less than 20° C. for the procedure to be effective. When using HEAR oil as the source of erucic acid, the glyceride fraction is enriched to approximately 85% compared to 50% in the raw material when utilizing lipase from G. candidum. Little or no erucic acid is found in the free fatty acid fraction. The glyceride fraction is enriched with erucic acid to approximately 95% when utilizing lipase from C. rugosa, with approximately 10% appearing in the free fatty acid fraction.
In accordance with this discovery it is an object of the invention to provide a novel method for producing erucic acid by enzymatic hydrolysis in a two-phase, water/oil reaction system, utilizing lipase from either G. candidum or C. rugosa to catalyze the reaction.
Other objects and advantages will become readily apparent from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the change in composition of glycerides and free fatty acids during lipase catalyzed hydrolysis of HEAR oil at 35° C. for Pseudomonas cepacia (panel A), Candida rugosa (panel B), Geotrichum candidum (C).
FIG. 2 shows the change in concentration of glycerides and free fatty acids during hydrolysis of HEAR oil using Candida rugosa lipase at different temperatures. Panel A shows C62 triglyceride concentrations, panel B shows C44 diglyceride concentrations, panel C shows C22 free fatty acid concentrations.
FIG. 3 shows the effect of concentration of Candida rugosa lipase on the production of C44 (dierucin) during hydrolysis of 5 g of HEAR oil at 10° C.
DETAILED DESCRIPTION OF THE INVENTION
Initially, studies were carried out to compare the ability of three lipases to hydrolyze high erucic acid rapeseed oil (HEAR oil), with the objective of concentrating the erucic acid in a single glyceride fraction. Lipases from Pseudomonas cepacia (P. cepacia), G. candidum and C. rugosa were considered, and the effects of time, temperature, water content and enzyme concentration were evaluated.
In time course of hydrolysis studies carried out at 35° C., lipase from P. cepacia was found to release all fatty acids rapidly and did not result in selective distribution of erucic acid. This non-specific lipase almost completely hydrolyzed the triglyceride to free fatty acid in 48 hours (FIG. 1a). Both monoglycerides and diglycerides appeared as intermediates, reaching a maximum of 35% and 10%, respectively, after 2 hours, and were almost completely hydrolyzed after 48 hours.
Lipase from C. rugosa released erucic acid more slowly than C18 and 20 fatty acids at 35° C. but only resulted in a limited accumulation of the erucic acid in the di- and triglyceride fractions. Hydrolysis using the C. rugosa lipase occurred in two stages (FIG. 1b): a fast release of free fatty acids up to 6 hours reaction time, reaching a level of 60%, and a slow release between 6 and 48 hours, reaching a final concentration of 75%. Decrease in diglyceride concentration was slow compared to that with P. cepacia lipase. After 48 hours reaction time, the hydrolysis of diglycerides was not complete.
G. candidum lipase released C20 and C22 fatty acids extremely slowly at 35° C., resulting in their accumulation in the di- and triglyceride fractions. Less than 2% of the total erucic acid was found in the free fatty acid fraction. Diglyceride concentration reached 45% after 4 hours reaction time and in contrast to the other lipases no hydrolysis of diglyceride occurred beyond this time. A maximum free fatty acid level of 50% was reached, and monoglyceride levels were almost zero throughout the reaction.
A detailed composition of the reaction mixture during hydrolysis of HEAR oil (as shown in FIG. 1) after 4 hours and 24 hours reaction time at 35° C. is shown in Table I. After 4 hours hydrolysis with P. cepacia lipase, the major diglyceride species was C40, corresponding to 1 molecule of erucic acid and 1 molecule of C18 acid bound to glycerol. Triglycerides containing erucic acid (e.g. C60) were hydrolyzed extensively and the major free fatty acid was erucic acid (C22). At 24 hours, release of more than 85% fatty acids had occurred. The relative proportions of the individual free fatty acids is consistent with a non-specific hydrolysis.
The composition of the reaction mixture after 4 hours hydrolysis using C. rugosa lipase is clearly different from that of P. cepacia lipase. The major diglyceride was dierucin (C44) and the concentration of C18 free fatty acid was almost three times greater than C22 free fatty acid. The C22 free fatty acid concentration had increased to approximately 23% after 24 hours reaction time with a corresponding decrease in C44 diglyceride.
TABLE 1______________________________________Composition of the Reaction Mixture (area %) after 4 h and 24 hReaction Time during Lipase-catalysed Hydrolysisof HEAR Oil at 35° C.Acyl HEAR P. cepacia C. rugosa G. candidumCarbon No. oil 4 h 24 h 4 h 24 h 4 h 24 h______________________________________FFAc16 0.0 2.5 3.1 3.7 3.5 3.3 3.2c18 0.0 16.9 32.6 39.0 37.5 35.2 34.1c20 0.0 6.1 8.5 5.0 7.8 0.0 0.8c22 0.5 28.4 39.9 13.8 23.3 0.7 0.8MGc18 0.0 5.1 1.6 0.6 0.8 0.5 0.0c20 0.0 0.8 0.0 0.1 0.2 0.0 0.0c22 0.0 4.1 1.2 0.3 0.3 2.2 2.4DGc34 0.0 0.0 0.0 0.0 0.0 0.0 0.0c36 0.0 4.1 1.5 0.0 0.2 0.0 0.0c38 0.0 2.7 0.8 0.0 0.2 2.0 1.5c40 0.6 10.7 3.4 1.4 0.8 6.3 6.4c42 0.0 1.7 0.6 6.1 1.9 9.6 9.9c44 0.0 3.5 1.3 18.2 13.9 24.4 26.2c46 0.0 0.0 0.0 1.1 0.8 0.8 1.0TGc52 2.7 0.4 0.0 0.0 0.0 0.0 0.0c54 8.8 1.3 0.8 0.0 0.2 0.0 0.0c56 9.3 1.6 0.7 0.0 0.2 0.9 0.7c58 10.4 3.9 2.0 1.4 0.7 2.3 2.0c60 19.4 1.5 0.8 3.7 1.7 4.5 3.7c62 46.3 3.1 1.3 7.3 5.2 10.1 7.3c64 1.9 0.0 0.0 0.1 0.8 0.6 0.0c64 0.0 0.0 0.2 0.0 0.0 0.0 0.0______________________________________
After 4 hours hydrolysis using lipase from G. candidum, diglyceride containing C20 or C22 fatty acids (C40, C42 and C44) had reached a higher level than occurred in the reaction with P. cepacia or C. rugosa lipases. At 24 hours reaction time, the concentration of these diglycerides had increased slightly and approximately 13% of triglycerides remained unhydrolysed. These triglycerides were mainly C58, C60 and C62, each of which must contain 2 or 3 molecules of C20 or C22 fatty acids. In the free fatty acid fraction, the concentration of C20 and C22 fatty acids never exceeded 1% of total reaction mixture throughout the reaction period.
In order to optimize the partial fatty acid hydrolysis selectivity toward C22 fatty acids observed with C. rugosa lipase, the effects of external parameters such as temperature, initial water concentration and enzyme concentration were investigated. To determine the effects of temperature, hydrolysis of HEAR oil was carried out at 35°, 20°, 15°, and 10° C. At 15° and 10° C., the reaction mixture became cloudy after 20 minutes reaction time and after 2 hours was a soft solid. The reaction proceeded, although stirring was no longer possible. At 35° C. no cloudiness or solidification occurred, but at 20° C. the reaction mixture was cloudy and viscous after 2 hours.
In FIG. 2, the appearance of selected products and disappearance of selected triglycerides during the course of the reaction at different temperatures is compared. The decrease in concentration of the C62 triglyceride (FIG. 2a) was similar at all temperatures but complete hydrolysis did not occur at 35° C.
The concentration of C44 diglyceride (dierucin), as shown in FIG. 2b, increased at all temperatures during the first hour of reaction, but thereafter exhibited a strong temperature dependent variation. At 20° C. and 15° C., a level of approximately 30% was reached after 6 hours. At 10° C. this level remained constant throughout the reaction, but at 15° C. it decreased slightly. At 35° C. the C44 concentration peaked at 20% after 2 hours reaction, then steadily decreased to 5% after 48 hours. Reaction at 20° C. was intermediate, with a maximum C44 diglyceride concentration of 27% after 6 hours which gradually decreased to 14% after 48 hours.
The production and final concentration of free erucic acid (C22) was also strongly temperature dependent (FIG. 2c). The final concentration of C22 was lower at the lower temperatures At 20° and 35° C. the relatively large increase in C22 between 6 and 48 hours reaction time corresponds to the decrease in concentration of C44 diglyceride. A small increase in C22 concentration at 10° C. during this period may be caused by the decrease in the C62 triglyceride concentration as shown in FIG. 1a.
Hydrolysis of HEAR oil by C. rugosa lipase at 10° C. was repeated four times and the composition of the reaction mixture after 48 hours was determined by gas chromatography and used to calculate the mean and standard deviation for the major glycerides and free fatty acids (area %±SD):
free fatty acids
C16=3.8±0.2
C18=39.3±0.6
C20=7.7±0.5
C22=12.6±0.5
monoglycerides
C18=0.8±0.1
C20=0.2±0.1
C22=0.1±0.1
diglycerides
C38=0.3±0.1
C40=0.4±0.1
C42=3.6±0.3
C44=29.7±0.7
C46=1.0±0.1
triglycerides
C58=0.1±0.1
C60=0.3±0.1
C62=0.5±0.1.
Hydrolysis of HEAR oil by P. cepacia lipase was also carried out at 10° C. but no difference in the composition of the reaction mixture compared with reaction at 35° C. was observed after 48 hours (data not shown).
Water is present in the reaction mixture due to the requirement for dissolving the lipase before mixing it with the erucic acid-containing oil. In order to determine the minimum amount of water needed for the reaction to proceed, the hydrolysis of HEAR oil was carried out at 10° C. using C. rugosa lipase as catalyst where initial water concentrations of 2, 5, 9, 17, 30, 40 and 60 wt % were present in the reaction mixture. The composition of the reaction mixture after 48 hours is shown in Table 2. At the lowest water content investigated (2% water), hydrolysis of triglycerides was incomplete and the concentration of C44 diglycerides was relatively low (20%). At all other water concentrations, almost total hydrolysis of triglycerides was attained and a concentration of approximately 30% C44 diglyceride was observed. When the water content was less than 30%, the content of C36-C42 diglycerides and C10 monoglyceride was higher, while the content of C18 and C22 free fatty acid was correspondingly lower. The reaction mixture solidified at all concentrations. At the 60% water concentration, the reaction mixture was not homogenous; free aqueous phase was visible in pockets distributed around a semi-solid emulsion of oil and buffer.
TABLE 2______________________________________Effect of Water Content on the Composition of the ReactionMixture (area %) after 24 h Hydrolysis of HEAR Oil (5 g)Using Candida rugosa Lipase (100 mg) at 10° C.Acyl Added WaterCarbon No. 2% 5% 9% 17% 30% 40% 60%______________________________________FFAc16 2.5 3.3 3.2 3.5 3.7 3.7 3.8c18 22.5 34.8 34.8 37.0 38.9 40.1 38.7c20 1.4 4.1 6.2 6.9 7.1 7.6 6.8c22 2.3 6.3 9.0 10.6 10.9 12.2 10.6MGc18 1.2 1.3 1.7 1.2 1.6 0.6 0.4c20 0.2 0.0 0.2 0.1 0.1 0.2 0.1c22 0.6 0.4 0.3 0.2 0.0 0.0 0.2DGc34 0.5 0.0 0.3 0.3 0.0 0.0 0.0c36 2.2 2.1 1.1 0.7 0.2 0.2 0.0c38 2.4 1.4 1.0 0.8 0.4 0.4 0.4c40 3.6 1.4 1.2 1.0 0.5 0.5 0.5c42 5.7 7.7 5.0 4.2 4.2 4.2 4.4c44 17.5 31.3 32.2 30.6 30.5 29.4 32.3c46 0.1 1.1 1.1 1.5 2.2 0.7 1.7TGc52 0.5 0.0 0.0 0.0 0.0 0.0 0.0c54 1.7 0.0 0.4 0.1 0.0 0.0 0.0c56 2.6 0.0 0.3 0.1 0.0 0.0 0.0c58 3.9 0.0 0.4 0.2 0.1 0.0 0.0c60 8.3 1.5 0.6 0.4 0.2 0.4 0.2c62 20.1 3.0 0.8 0.6 0.0 0.6 0.0c64 0.0 0.0 0.2 0.0 0.0 0.0 0.0______________________________________
The hydrolysis of HEAR oil was carried out at 10° C. with increasing concentrations of C. rugosa lipase (from 10 mg to 400 mg). The rate of production of C44 diglyceride increased with increasing concentration as shown in FIG. 3. The rates for 200 mg and 400 mg, however, were almost identical under these particular conditions. At the higher enzyme concentrations, a small decrease in the C44 diglyceride concentration occurred between 24 and 48 hours reaction time. At all enzyme concentrations, a level of approximately 30% C44 diglyceride was reached within the 48-hour reaction period investigated.
Previous studies on the relative reactivity of fatty acids ranging from C16-C22 towards P. cepacia lipase had shown no enzyme selectivity against any particular acid (Sonnet, supra). Analysis of the reaction mixture during hydrolysis of HEAR oil confirmed this finding and showed that the major intermediate was a diglyceride containing one erucic acid molecule and one molecule of C18 fatty acid. Altering the reaction conditions had no effect on this breakdown patter, therefore this enzyme was eliminated as a candidate for use in a process for the purification of erucic acid from HEAR oil.
Lipase from G. candidum, on the other hand, was shown to be a useful candidate for this purpose. Although this lipase was well known for its ability to preferentially hydrolyze esters of cis δ9 unsaturated C18 fatty acids, compared to their saturated counterparts, it had also been shown (Sonnet, supra) that esters of unsaturated fatty acids longer than C18 were also hydrolyzed, though extremely slowly. HEAR oil hydrolysis using this enzyme resulted in almost no release of erucic acid with extensive release of C18 fatty acids, which in HEAR oil are mainly cis δ9 unsaturated. Most of the erucic acid was thus concentrated in the diglyceride fraction as dierucin (C44). In addition, almost no release of C20 fatty acids was observed, resulting in accumulation of these fatty acids in the diglyceride fraction also, but as non-C44 diglycerides. The overall result of the reaction occurs over a short period of time, and the accumulation of erucic acid in the diglyceride fraction reaches an approximately 85% concentration.
The similarity in the specificities of the lipases from C. rugosa and G. candidum is not surprising considering the close homology which has recently been demonstrated between these enzymes on the molecular level (Li et al., J. Biol. Chem. 1993. vol. 268, pp. 12843-12847). However, due to the relatively poor selectivity of the C. rugosa enzyme, erucic acid is poorly concentrated into the diglyceride fraction and a large amount of erucic acid is lost to the free fatty acid fraction at reaction temperatures of 35° and 20° C. Below 20° C., the accumulation of dierucin with the simultaneous solidification of the reaction mixture suggests that dierucin crystallizes as it is being produced. The solid becomes unavailable as a substrate to the enzyme thereby preventing further hydrolysis to free erucic acid. A similar phenomenon was previously observed during low temperature enzymatic glycerolysis of fats and oils where solidification of the reaction mixture with accumulation of monoglycerides was demonstrated to be caused by preferential crystallization of monoglyceride containing a saturated fatty acid (McNeill et al., J. Am. Oil Chem. Soc. 1992. vol. 69, pp. 1098-1103).
The result of dierucin crystallization is an accumulation of erucic acid in the diglyceride fraction at a higher purity than found with the more fatty acid selective G. candidum lipase, i.e. approximately 95%. In spite of the crystallization of dierucin, release of free erucic acid does occur at the early stages of the reaction, causing a loss of about 20% of total erucic acid to the free fatty acid fraction. Both G. candidum and C. rugosa lipases are suitable catalysts for the concentration of erucic acid in specific glyceride fractions during hydrolysis of HEAR oil. The choice of enzyme in a practical situation will depend on the required purity of erucic acid and the relative costs of the enzymes.
The procedure for the production of erucic acid is carried out by adding lipase dissolved in buffer to erucic acid-containing oil, with stirring. Any oil which contains an erucic acid component may be treated with lipase to produce erucic acid as a mono- or diglyceride. Suitable oils are those derived from plants of the Brassicaceae family, for example, rapeseed oil, mustard seed oil, nasturtium oil and crambe seed oil. Preferred are rapeseed oil, mustard seed oil and crambe seed oil. Particularly preferred is high erucic acid rapeseed (HEAR) oil.
Effective concentrations of lipase have been found to range from about 0.2 wt % to about 8.0 wt %. Effective lipases are those isolated from Geotricum candidum and Candida rugosa and are available commercially, such as from Enzeco, New York, N.Y. Preferred concentrations of lipase are about 0.2 wt % to about 2.0 wt %. Particularly preferred is about 0.2 wt %.
The enzyme is dissolved in either water or any buffer which is conventionally used in carrying out enzymatic reactions at a pH of about 7.0. Examples are phosphate or Tris buffers. The enzyme is dissolved in buffer such that the water concentration in the reaction mixture is at least about 5 wt %.
The hydrolysis reaction should be carried out at a constant temperature, and the temperature used depends upon the choice of enzyme. Lipase from G. candidum is effective at temperatures of about 10° C. to about 35° C. Preferred temperatures are from about 20° C. to about 35° C., while particularly preferred is about 35° C. Lipase from C. rugosa is effective at temperatures of about 10° C. to about 20° C. Preferred temperatures are from about 10° C. to about 15° C., while particularly preferred is about 10° C.
The hydrolysis reaction can be carried out up to about 48 hours, however, within about 2 hours, erucic acid-containing glycerides will begin to appear in significant concentrations. As a general rule, higher enzyme concentrations will result in faster accumulation of end product.
Following the hydrolysis procedure, the glyceride fraction is separated from the free fatty acid fraction by any conventional method known and used in the art. For example, glyceride may be extracted from the reaction mixture with acetone, followed by crystallization. This procedure is carried out by warming the reaction mixture to 35° C. to separate the water and oil phases. The oil phase is removed and dissolved in acetone such that oil is approximately 35% of the acetone-oil mixture. The mixture is then cooled to 10° C., filtered, the filtrate redissolved in acetone, and the process is repeated.
Erucic acid may exist either as a glyceride, where the diglyceride is dierucin and the monoglyceride is monerucin, or as the free fatty acid, and may be used in either form. In instances where the free fatty acid is preferred, the acid may be removed from the glycerol by any conventional means, such as, for example, the addition of a sodium hydroxide solution.
Erucic acid has utility for a number of applications. It is a raw material in the oleochemical industry for the synthesis of biodegradable lubricants and slip agents in the plastics industry. It also may be used for textile fiber lubrication (e.g., fabric softeners) and in hair care products.
The following examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
EXAMPLES
Example 1
Production of Erucic Acid from HEAR Oil Utilizing Lipase from Geotrichum candidum
Samples of HEAR oil (5 g) were stirred magnetically at 600 rpm with 3.5 ml of 50 mM phosphate buffer, pH 7, in which was dissolved 100 mg of lipase powder from G. candidum. Stirring took place in a stoppered, flat bottom glass tube, 3 cm×5 cm, which was placed in a glass mantle. The reaction temperature was maintained at 35° C. by circulating water from a constant temperature water-bath through the mantle. After a reaction time of 48 hours, the reaction mixture was heated to 35° C., resulting in the separation of the water and oil phases. The oil phase was removed, dissolved in about 15 ml of acetone and placed at 10° C. overnight. Crystals appeared during the cooling process and were separated from the acetone phase by filtering onto filter paper with a Buchner funnel. After the first filtration, the crystals were redissolved in about 15 ml fresh acetone, and the process was repeated.
Example 2
Production of Erucic Acid from HEAR Oil Utilizing Lipase from Candida rugosa
Samples of HEAR oil (5 g) were stirred magnetically at 600 rpm with 3.5 ml of 50 mM phosphate buffer, pH 7, in which was dissolved 100 mg of lipase powder from C. rugosa. Stirring took place in a stoppered, flat bottom glass tube, 3 cm×5 cm, which was placed in a glass mantle. The reaction temperature was maintained at 10° C. by circulating water from a constant temperature water-bath through the mantle. After a reaction time of 48 hours, the reaction mixture was heated to 35° C., resulting in the separation of the water and oil phases. The oil phase was removed, dissolved in about 15 ml of acetone and placed at 10° C. overnight. Crystals appeared during the cooling process and were separated from the acetone phase by filtering onto filter paper with a Buchner funnel. After the first filtration, the crystals were redissolved in about 15 ml fresh acetone, and the process was repeated. | Erucic acid is produced by enzymatic hydrolysis, the reaction being catalyzed by lipase from Geotrichum candidum or Candida rugosa. Fatty acid substituents having carbon chains shorter than C22 are removed from triglycerides which also contain one or two erucic acid substituents, resulting in a glyceride fraction enriched in erucic acid and a free fatty acid fraction containing the hydrolyzed substituent. | 2 |
[0001] This application is a continuation-in-part of copending U.S. application Ser. No. 10/008,870, filed Nov. 2, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to a device adapted for temporary insertion within the nose for detecting the presence of airborne pathogens and the delivery of aromatherapeutic compositions.
[0004] 2. Description of the Prior Art
[0005] Various forms of nasal airway devices are known in the art. Examples of such devices are disclosed in the following U.S. Pat. Nos.: 851,048; 513,458, 4,414,977; 4,201,207; 2,515,756; 1,255,578; 1,481,581; 1,597,331; 1,672,591; 1,709,740; 1,135,675; 1,014,076; 1,014,758; 1,077,574 and British Patent GB0768488; British Patent 4,148; Italian Patent IT0490828 and French Patent 7807130. While most of these devices provide a means for dilating the nostrils and maintaining an airway permitting improved air flow therethrough, each has limitations producing less than optimum air flow or discomfort which prevents the device from being used for a prolonged period of time. Many devices are unsatisfactory due to non-unitary construction which can result in situ disintegration of the device and possible aspiration of a fragment of the device. The above devices do not have or teach the structural and functional features of the present invention described below which, in combination, enable the device to perform the intended function in a manner which is superior to the prior art devices. In particular, none of the prior art nasal airway devices include means operable for indicating the presence of an airborne pathogen entering the nasal passages, or for delivering an aromatherapeutic composition to a person's air passages.
[0006] The potential for human exposure to dangerous concentrations of noxious airborne pathogens such as anthrax spores has increased dramatically in recent months due to the introduction of pathogenic organisms into the work environment by deliberate criminal intent. Exposure to airborne pathogens such as anthrax spores and sarin gas is highly probable in the future, particularly for members of the military engaged in hostile action. In the case of anthrax, it is imperative that detection means operable for early detection of such human exposure to the airborne pathogen be available to both civilian and military populations. Ideally, such a detection system provides an indication and measure of an individual's exposure to a particular pathogen so that only individuals who have received a dangerously high level of exposure receive preemptive treatment. Accordingly, a detection device adapted to be worn upon the body and disposed to sample air that is actually inhaled by an individual is particularly desirable.
[0007] Aromatherapy has become a popular means for delivering volatile compositions to the airway of a person in order to elicit a desired response. Aromatherapy is the practice of using volatile plant oils, including “essential oils”, for psychological and physical well-being. Essential oils, which are the pure “essence” of a plant, may provide both psychological and physical benefits when used correctly. There are over 90 essential oils. Essential oils that are inhaled into the lungs are believed to offer both psychological and physical benefits. Not only does the aroma of the natural essential oil stimulate the brain to trigger a reaction, but the natural constituents (naturally occurring chemicals) of the essential oil are drawn into the lungs and can also provide physical benefits. There is a need for a device that can fit within the nose of a person, thereafter the device efficiently releasing essential oils or other volatile aromatherapeutic compositions into the person's airstream.
SUMMARY OF THE INVENTION
[0008] It is a primary object of this invention to provide an intranasal device for selectively removing a sample of targeted pathogenic microorganisms from air delivered to the respiration passages and providing an indication of exposure to the targeted pathogenic microorganisms in the respiratory air.
[0009] It is a further object of this invention to provide a device adapted to be comfortably attached to a person's nose, thereafter being operable for releasing aromatherapeutic compositions to the resperatory air for transport and delivery of the aromatherapeutic composition to respiratory passages of the person.
[0010] It is another object of this invention to provide a device meeting the above objectives and which includes a means for controlling and/or limiting the projection of the device into the nostrils while preventing the device from dislodging and being ejected from the nostril.
[0011] It is another object of this invention to provide a device which meets the objectives stated above and which can be easily and inexpensively manufactured, at least in part, by injection molding from an inexpensive hypoallergenic plastic composite, copolymer or elastomer-coated plastic in a variety of sizes.
[0012] The above objects and advantages of the present invention are accomplished by the present nasal airway airborne pathogen indicator device. In a particularly preferred embodiment of an airborne pathogen indicator device in accordance with the present invention, the proximal dilating portion of the device comprises two “U” shaped surfaces adapted to be inserted into the nostrils. The dilating portion of the device is inter-connected by means of a bridging “U” shaped extension portion. The extension portion is a generally “U” shaped having a semicylindrical wall with an inner circumferential surface which is contoured to anatomically and snugly conform to the inferior (most distal) margin of the nasal septum. Thus, overall the device is generally “U” shaped, more or less resembling a cotter pin when viewed in front elevation and “U=U” shaped when the proximal portion is viewed end on from the top. The nasal airway dilating portion of the present device is described in detail in U.S. Pat. No. 5,931,852 to the present inventor. The bifurcated extension portion comprises two identical substantially planar parallel strips oriented with their flat surfaces in parallel planes and connected to one another by the semicylindrical distal septum attachment portion. The symmetrical dilating portion is contoured to anatomically conform to the respective contours of the anterior inner surface of the nostrils. Since inhaled air flowing through the nose contacts the inner surfaces of the “U's”, (i.e., the nontissue-contacting surfaces of the device), a pathogen-adsorbing coating, applied thereto, that is operable for removing at least a portion of the targeted pathogens, from the airflow, is employed to provide evidence of the wearer's exposure to selected, (targeted) airborne pathogens.
[0013] In an aromatheraputic composition delivery device of the present invention, one or more aromatherapeutic composition reservoir(s) are applied to the inner, nontissue-contacting surface(s) of the “U's”. When inhaled air flowing through the nose passes over the reservoir(s), the volatile aromatherapeutic composition is released into the airflow, thereafter to be transported into the person's respiratory passages where it passes into the bloodstream to elicit a desired response.
[0014] The features of the invention believed to be novel are set forth with particularity in the appended claims. However, the invention itself, both as to organization and method of operation, together with further objects and advantages thereof may best be understood by reference to the following description of a preferred embodiment of the invention, taken in conjunction with the accompanying drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a front elevational view of a particularly preferred embodiment of an airborne pathogen indicating device in accordance with the present invention.
[0016] FIG. 2 is a perspective view of the airborne pathogen indicating device shown in FIG. 1 .
[0017] FIG. 3 is a side view of the airborne pathogen indicating device of FIG. 2 viewed in the direction of line 3 - 3 ′.
[0018] FIG. 4 is a perspective inferior view of the airborne pathogen indicating device in accordance with the present invention positioned within the nose of a person and illustrating the disposition of the pathogen-sensitive coating with respect to the nasal airway passages.
[0019] FIG. 5 is a schematic lateral view of the airborne pathogen indicating device positioned within the nose which has been partially cut-a-way for illustration.
[0020] FIG. 6 is a perspective view of an embodiment of the invention having gripping pins adapted for facilitating instrument assisted insertion of the airborne pathogen indicating device into the nose.
[0021] FIG. 7 shows the cooperative functional relationship between the insertion instrument and the airborne pathogen indicating device of FIG. 6 prior to insertion of the device into the nose.
[0022] FIG. 8 is an elevational view of the airborne pathogen indicating device of FIG. 6 looking upward into the nose with the device properly positioned for operation and illustrating the trapping of particulate pathogens in the air by a cilia-like coating on a portion of the device.
[0023] FIG. 9 is a perspective view of an aromatherapeutic composition delivery embodiment of the invention having a pair of aromatherapeutic composition reservoirs affixed to the inner surfaces of the “U”-shaped members.
[0024] FIG. 10 is an elevational view of the aromatherapeutic composition delivery device of FIG. 9 looking upward into the nose with the device properly positioned for operation and illustrating the release of the volatile aromatherapeutic composition from the reservoirs affixed to the inner surface of the “U”-shaped members of the device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] The airborne pathogen indicating device 10 , shown in front (anterior) elevational view in FIG. 1 , is a unitary strip of elastically deformable material, preferably hypoallergenic, elastomer shaped to form a symmetrical 3-dimensional structure as generally shown in FIG. 2 . The airborne pathogen indicating device 10 is bifurcated and symmetrically disposed in structure with respect to the medial septum attachment portion 11 . The septum attachment portion 11 is a semi-cylindrical arcuate distal coterminous for the inferior or distal end of the extension portion 14 and 14 ′ of the device 10 , connecting the tines 14 and 14 ′ of the extension portion to one another and having an inner diameter D. The extension portion consists of tines 14 and 14 ′ and extends proximally, away from the septum attachment portion a distance L, the proximal terminus of the extension portions 14 , 14 ′ being shown at 15 . The dilating portion consists of two “U” shaped projections projecting anteriorly on a plane at right angles to the extension portion 14 , to gracefully and arcuately curve laterally outward and posteriorly to form smooth, anatomically conforming tissue-contacting surfaces 13 and 13 ′ which are mirror images of each other. The side of the dilating portions opposite the tissue contacting surfaces 13 and 13 ′ are coated with a material that interacts with airborne pathogens in such a way as to enable the device to be used for determining exposure to one or more airborne pathogens. The extension portion 14 and 14 ′ preferably be a length L between 1/2 inch and 1 inch. The width W of the device 10 is substantially uniform throughout the device and preferably in the range of ⅛- 0.5/16 inches. The thickness of the device, excluding the thickness of the pathogen adsorbing coating 43 , is also substantially uniform throughout and preferably less than 1/16 of an inch.
[0026] The device may be positioned within the nose 40 ( FIG. 4 ) by inserting the proximal end 15 of the airborne pathogen indicating device 10 into the nasal air passages 42 and advanced by applying pressure on the distal opposing end until the distal septum attachment portion 11 is in contact with the inferior margin of the nasal septum 41 . At this point, the proximal end 15 of the device 10 can be advanced no further into the nasal passages 42 and the anatomically conforming tissue-contacting surfaces 13 and 13 ′ comprising the dilating portion press laterally against the anterior and lateral wall of the nasal passage to dilate the passage and maintain an airway therethrough. A pathogen interactive coating 43 disposed on the inner surface (i.e., the surfaces opposite the tissue-contacting surfaces 13 and 13 ′) of the dilating portion of the airborne pathogen indicating device 10 interacts with airborne pathogens in such a way as to provide an indication that a pathogen is, or was, present in the airflow stream during periods of use. A coating 43 may, for example, have numerous cilia-like filaments extending into the airstream. Such a filamentous coating 43 ( FIGS. 6-8 ) extracts pathogenic microorganisms from the airstream and concentrates the pathogens on an adherent coating on the filaments. The coating 43 may, for example, be a material that releases the pathogen accumulated thereon for assaying or other investigative purposes after treatment with an appropriate reagent, or provide a calorimetric indication of the presence of a particular airborne pathogen in contact therewith either with or without treatment by suitable indicator reagents.
[0027] The above-described embodiment is shown in FIG. 5 wherein the airborne pathogen indicating device 10 is seen to be comfortably positioned within the (partially sectioned) nose 40 of the patient. The surfaces 13 and 13 ′ elastically urge outward to press laterally outward against the wall of the nasal passage and provide a smooth, non-irritating tissue-contacting surface for comfort. The anterior projection 12 ′ of the dilating portion is shown facing the front or anterior portion 51 of the nose 40 and the septum attachment portion 11 is releasably attached to the inferior margin 41 of the nasal septum by medially directed elastic restorative forces.
[0028] FIG. 6 is a perspective view of an embodiment of the airborne pathogen indicating device 10 including gripping pins 61 adapted to be grasped by an instrument 62 for facilitating instrument assisted insertion of the device 10 into the nose. The airborne pathogen interactive coating 43 is applied to a portion of the surface of the device 10 so as to contact air flowing through the nose. FIG. 7 shows the cooperative functional relationship between the insertion instrument 62 and device 10 prior to insertion of the device into the nose. The tines 14 and 14 ′ of the extension portion of the device are urged toward one another in the direction indicated by the broad arrows in FIG. 7 and the proximal end 15 inserted into the person's anterior nasal passages and advanced thereinto by means of the instrument 62 . When the pressure exerted by the instrument 62 on the pins 61 is released, the tines of the extension portion bear against the lateral tissue surfaces of the medial nasal septum to stabilize the device while the proximal arcuate tissue-contacting surfaces of the dilating portion buttress a portion of the inner perimeter of the nasal passages, urging the tissue in contact therewith radially outward to create and maintain symmetrically disposed open nasal airways.
[0029] FIG. 8 is an elevational view looking upward into the nose 40 showing the airborne pathogen indicating device 10 properly positioned in accordance with this invention for maintaining an open airway within the nose, while presenting an interactive surface 43 to adsorb airborne pathogens 81 entrained in the air stream passing thereover. The airborne pathogen interactive coating 43 , which may be a pathogen-specific adsorptive or reactive coating, may be affixed to the outer surface 80 (i.e., the surface in opposition to tissue contacting surface 13 and 13 ′) of the dilating portion of the airborne pathogen indicating device 10 to adsorb or chemically react with airborne pathogens 81 entrained in the air stream. FIG. 8 shows a portion 81 ′ of the airborne pathogens 81 trapped in a hydrophilic or hydrophobic gel coating applied to cilia-like fibrils 43 . In addition to the present invention's utility for maintaining an airway and indicating exposure to an airborne pathogen, the tissue-contacting surfaces 13 and 13 ′ of the device may be open cell or porous and permeated with a medicament that is released into the tissue in contact therewith.
[0030] FIG. 9 is a bottom perspective view of an aromatherapeutic composition delivery embodiment of the invention having at least one, and more preferably a pair of aromatherapeutic composition reservoirs 91 and 91 ′ affixed to the inner (nontissue-contacting) surfaces of the “U”-shaped members 13 and 13 ′ of the airway device 10 . The reservoirs 91 and 91 ′ are operable for storing an aromatherapeutic composition in liquid phase such as a volatile essential oil, and releasing only essential oil vapor into the airstream. The reservoirs, which may be a fabric such as felt or a sponge, preferably have a large surface area capable of adsorbing the liquid phase of the aromatherapeutic composition and releasing the vapor phase of the adsorbate into air. The aromatherapeutic composition stored in the reservoirs 91 and 91 ′ may be replenished when it becomes depleted. FIG. 10 is an elevational view of the aromatherapeutic composition delivery device 90 of FIG. 9 looking upward into the nose 92 with the device properly positioned for operation and illustrating the release (indicated by small arrows) of the volatile aromatherapeutic composition from the reservoirs 91 and 91 ′ affixed to the inner surface of the “U”-shaped members of the device 90 .
[0031] With reference to FIGS. 6-8 , a preferred method for providing a pathogen-adsorbing coating 43 comprises the application of a thin film of an adsorbant or chemically reactive reagent such as a hydrophilic hydrogel or a hydrophobic silicone gel coating containing an indicator reagent that provides, or can be further treated to provide, an indication of exposure to an airborne pathogen to the surface 80 of the airborne pathogen indicating device 10 . After use, the coated surface 43 of the device can be either visually inspected to indicate exposure to an airborne pathogen, or the coating may be further treated by a visualizing reagent as, for example, in a home test kit, to provide an indication of the exposure of the coated surface 43 to a targeted airborne pathogen. In a particularly preferred embodiment, the coating 43 comprises a layer of synthetic polymer having fibrils or a tortuous surface projecting into the air stream. The fibrils are coated with either a hydrophilic hydrogel or a hydrophobic silicone gel, the choice of gel coating depending on the hydrophilicity of the cell wall of the pathogen targeted for detection. Pathogenic bacteria such as Bacillis anthracis, are characterized, at least in part, by having a cell wall. The outer surface of the cell wall comprises lipids and proteins. The cell wall can be either hydrophobic or hydrophilic, depending on structure and distribution of the lipids and proteins within the outer surface of the cell wall of the organism. If the fibers are coated with a hydrophilic material such as a hydrogel (eg., polyvinylpyrrolidone), organisms having a hydrophilic cell wall will be adsorbed and adhere to the coating as air passes over the fibers whereas organisms having a hydrophobic cell wall will have little or no affinity for the coating. Conversely, if the fibers are coated with a hydrophobic material such as silicone gel, organisms having a hydrophobic cell wall will adhere. After use, at the end of a day, for example, the device 10 can be removed from the nose and treated by immersing the coating 43 in a solvent that will dissolve the coating and/or the fibrils and release the pathogenic organsims, entrapped and accumulated therein, into the solvent. The solvent containing the pathogenic organisms in suspension can be mounted on a slide for microscopic examination, cultured, or otherwise analyzed for detection of the presence of, and the determination of the amount of the pathogenic organism, such as, for example, anthrax spores, that may be injurious to health. In addition, a test kit may be used in a home environment for providing a visual indication, such as a color change, of exposure of the coating 43 to an airborne pathogen. Appropriate medicaments such as, for example, antibiotics exhibiting a therapeutic effect, may then be timely administered to the patient if a high level of exposure to a particular pathogen is indicated.
[0032] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. For example, the airborne pathogen indicating device 10 is applicable, or may be adapted to concentrate and/or detect any number of different airborne pathogens, the particular pathogens detected depending on the specificity of the coating 43 . Further, while a particular embodiment of an airway device that is suitable for supporting a pathogen sensitive or adsorbant coating within the nose and present the coating to the air stream passing through the nose, has been described, the particular device 10 is intended to provide a preferred exemplar of the invention. Many other possible geometries are possible for the airborne pathogen indicating device 10 . For example, a single length of elastomeric tubing or a spring-loaded semi or hemi tube dimensioned to fit snugly within the nose and present a reactive surface to the air stream may be used to meet the objectives of the present invention. As a further example, persons such as coroners engaged in the practice of forensic science are subjected to abhorent odors such as decomposing human tissue. It is desireable to mask these objectionable odors with a more intense pleasant scent. The aromatherapeutic composition delivery device of the present invention may be used to deliver masking scents to the airstream. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. | A nasal airway for insertion in the nose for the delivery of volatile compositions into air entering the nose or, in a second embodiment, for the detection of targeted airborne pathogenic organisms present in the respirated airstream. The volatile compositions include aromatherapeutic compositions and scents. | 6 |
FIELD OF THE INVENTION
[0001] This invention relates to dicycloalkylcarbamoyl ureas that are activators of glucokinase and thus may be useful for the management, treatment, control, or adjunct treatment of diseases, where increasing glucokinase activity is beneficial.
BACKGROUND OF THE INVENTION
[0002] Glucokinase (GK) is one of four hexokinases that are found in mammals [Colowick, S. P., in The Enzymes, Vol. 9 (P. Boyer, ed.) Academic Press, New York, N.Y., pages 1-48, 1973]. The hexokinases catalyze the first step in the metabolism of glucose, i.e., the conversion of glucose to glucose-6-phosphate. Glucokinase has a limited cellular distribution, being found principally in pancreatic β-cells and liver parenchymal cells. In addition, GK is a rate-controlling enzyme for glucose metabolism in these two cell types that are known to play critical roles in whole-body glucose homeostasis [Chipkin, S. R., Kelly, K. L., and Ruderman, N. B. in Joslin's Diabetes (C. R. Khan and G. C. Wier, eds.), Lea and Febiger, Philadelphia, Pa., pages 97-115, 1994]. The concentration of glucose at which GK demonstrates half-maximal activity is approximately 8 mM. The other three hexokinases are saturated with glucose at much lower concentrations (<1 mM). Therefore, the flux of glucose through the GK pathway rises as the concentration of glucose in the blood increases from fasting (5 mM) to postprandial (˜10-15 mM) levels following a carbohydrate-containing meal [Printz, R. G., Magnuson, M. A., and Granner, D. K. in Ann. Rev. Nutrition Vol. 13 (R. E. Olson, D. M. Bier, and D. B. McCormick, eds.), Annual Review, Inc., Palo Alto, Calif., pages 463-496, 1993]. These findings contributed over a decade ago to the hypothesis that GK functions as a glucose sensor in β-cells and hepatocytes (Meglasson, M. D. and Matschinsky, F. M. Amer. J. Physiol. 246, E1-E13, 1984). In recent years, studies in transgenic animals have confirmed that GK does indeed play a critical role in whole-body glucose homeostasis. Animals that do not express GK die within days of birth with severe diabetes while animals overexpressing GK have improved glucose tolerance (Grupe, A., Hultgren, B., Ryan, A. et al., Cell 83, 69-78, 1995; Ferrie, T., Riu, E., Bosch, F. et al., FASEB J., 10, 1213-1218, 1996). An increase in glucose exposure is coupled through GK in β-cells to increased insulin secretion and in hepatocytes to increased glycogen deposition and perhaps decreased glucose production.
[0003] The finding that type II maturity-onset diabetes of the young (MODY-2) is caused by loss of function mutations in the GK gene suggests that GK also functions as a glucose sensor in humans (Liang, Y., Kesavan, P., Wang, L. et al., Biochem. J. 309, 167-173, 1995). Additional evidence supporting an important role for GK in the regulation of glucose metabolism in humans was provided by the identification of patients that express a mutant form of GK with increased enzymatic activity. These patients exhibit a fasting hypoglycemia associated with an inappropriately elevated level of plasma insulin (Glaser, B., Kesavan, P., Heyman, M. et al., New England J. Med. 338, 226-230, 1998). While mutations of the GK gene are not found in the majority of patients with type 2 diabetes, compounds that activate GK and, thereby, increase the sensitivity of the GK sensor system will still be useful in the treatment of the hyperglycemia characteristic of all type 2 diabetes. Glucokinase activators will increase the flux of glucose metabolism in β-cells and hepatocytes, which will be coupled to increased insulin secretion. Such agents would be useful for treating type II diabetes. Several GK activators are known, see, for example, US 2004/0014968 (Hofmann-La Roche Inc.) and WO 2004/002481 (Novo Nordisk A/S).
[0004] Diabetes is characterized by an impaired glucose metabolism manifesting itself among other things by an elevated blood glucose level in the diabetic patients. Underlying defects lead to a classification of diabetes into two major groups: Type 1 diabetes, or insulin demanding diabetes mellitus (IDDM), which arises when patients lack β-cells producing insulin in their pancreatic glands, and type 2 diabetes, or non-insulin dependent diabetes mellitus (NIDDM), which occurs in patients with an impaired β-cell function besides a range of other abnormalities.
[0005] Type 1 diabetic patients are currently treated with insulin, while the majority of type 2 diabetic patients are treated either with sulphonylureas that stimulate β-cell function or with agents that enhance the tissue sensitivity of the patients towards insulin or with insulin. Among the agents applied to enhance tissue sensitivity towards insulin, metformin is a representative example.
[0006] Even though sulphonylureas are widely used in the treatment of NIDDM this therapy is, in most instances, not satisfactory. In a large number of NIDDM patients sulphonylureas do not suffice to normalise blood sugar levels and the patients are, therefore, at high risk for acquiring diabetic complications. Also, many patients gradually lose the ability to respond to treatment with sulphonylureas and are thus gradually forced into insulin treatment. This shift of patients from oral hypoglycaemic agents to insulin therapy is usually ascribed to exhaustion of the β-cells in NIDDM patients.
[0007] In normal subjects as well as in diabetic subjects, the liver produces glucose in order to avoid hypoglycemia. This glucose production is derived either from the release of glucose from glycogen stores or from gluconeogenesis, which is a de novo intracellular synthesis of glucose. In type 2 diabetes, however, the regulation of hepatic glucose output is poorly controlled and is increased, and may be doubled after an overnight fast. Moreover, in these patients there exists a strong correlation between the increased fasting plasma glucose levels and the rate of hepatic glucose production. Similarly, hepatic glucose production will be increased in type 1 diabetes, if the disease is not properly controlled by insulin treatment.
[0008] Since existing forms of therapy of diabetes does not lead to sufficient glycemic control and therefore are unsatisfactory, there is a great demand for novel therapeutic approaches.
[0009] Atherosclerosis, a disease of the arteries, is recognized to be the leading cause of death in the United States and Western Europe. The pathological sequence leading to atherosclerosis and occlusive heart disease is well known. The earliest stage in this sequence is the formation of “fatty streaks” in the carotid, coronary and cerebral arteries and in the aorta. These lesions are yellow in colour due to the presence of lipid deposits found principally within smooth-muscle cells and in macrophages of the intima layer of the arteries and aorta. Further, it is postulated that most of the cholesterol found within the fatty streaks, in turn, give rise to development of the “fibrous plaque”, which consists of accumulated intimal smooth muscle cells laden with lipid and surrounded by extra-cellular lipid, collagen, elastin and proteoglycans. The cells plus matrix form a fibrous cap that covers a deeper deposit of cell debris and more extracellular lipid. The lipid is primarily free and esterified cholesterol. The fibrous plaque forms slowly, and is likely in time to become calcified and necrotic, advancing to the “complicated lesion” which accounts for the arterial occlusion and tendency toward mural thrombosis and arterial muscle spasm that characterize advanced atherosclerosis.
[0010] Epidemiological evidence has firmly established hyperlipidemia as a primary risk factor in causing cardiovascular disease (CVD) due to atherosclerosis. In recent years, leaders of the medical profession have placed renewed emphasis on lowering plasma cholesterol levels, and low density lipoprotein cholesterol in particular, as an essential step in prevention of CVD. The upper limits of “normal” are now known to be significantly lower than heretofore appreciated. As a result, large segments of Western populations are now realized to be at particular high risk. Independent risk factors include glucose intolerance, left ventricular hypertrophy, hypertension, and being of the male sex. Cardiovascular disease is especially prevalent among diabetic subjects, at least in part because of the existence of multiple independent risk factors in this population. Successful treatment of hyperlipidemia in the general population, and in diabetic subjects in particular, is therefore of exceptional medical importance.
[0011] Hypertension (or high blood pressure) is a condition, which occurs in the human population as a secondary symptom to various other disorders such as renal artery stenosis, pheochromocytoma, or endocrine disorders. However, hypertension is also evidenced in many patients in whom the causative agent or disorder is unknown. While such “essential” hypertension is often associated with disorders such as obesity, diabetes, and hypertriglyceridemia, the relationship between these disorders has not been elucidated. Additionally, many patients display the symptoms of high blood pressure in the complete absence of any other signs of disease or disorder.
[0012] It is known that hypertension can directly lead to heart failure, renal failure, and stroke (brain hemorrhaging). These conditions are capable of causing short-term death in a patient. Hypertension can also contribute to the development of atherosclerosis and coronary disease. These conditions gradually weaken a patient and can lead to long-term death.
[0013] The exact cause of essential hypertension is unknown, though a number of factors are believed to contribute to the onset of the disease. Among such factors are stress, uncontrolled emotions, unregulated hormone release (the renin, angiotensin aldosterone system), excessive salt and water due to kidney malfunction, wall thickening and hypertrophy of the vasculature resulting in constricted blood vessels and genetic factors.
[0014] The treatment of essential hypertension has been undertaken bearing the foregoing factors in mind. Thus a broad range of beta-blockers, vasoconstrictors, angiotensin converting enzyme inhibitors and the like have been developed and marketed as antihypertensives. The treatment of hypertension utilizing these compounds has proven beneficial in the prevention of short-interval deaths such as heart failure, renal failure, and brain hemorrhaging. However, the development of atherosclerosis or heart disease due to hypertension over a long period of time remains a problem. This implies that although high blood pressure is being reduced, the underlying cause of essential hypertension is not responding to this treatment.
[0015] Hypertension has been associated with elevated blood insulin levels, a condition known as hyperinsulinemia. Insulin, a peptide hormone whose primary actions are to promote glucose utilization, protein synthesis and the formation and storage of neutral lipids, also acts to promote vascular cell growth and increase renal sodium retention, among other things. These latter functions can be accomplished without affecting glucose levels and are known causes of hypertension. Peripheral vasculature growth, for example, can cause constriction of peripheral capillaries, while sodium retention increases blood volume. Thus, the lowering of insulin levels in hyperinsulinemic can prevent abnormal vascular growth and renal sodium retention caused by high insulin levels and thereby alleviates hypertension.
[0016] Cardiac hypertrophy is a significant risk factor in the development of sudden death, myocardial infarction, and congestive heart failure. Theses cardiac events are due, at least in part, to increased susceptibility to myocardial injury after ischemia and reperfusion, which can occur in out-patient as well as perioperative settings. There is an unmet medical need to prevent or minimize adverse myocardial perioperative outcomes, particularly perioperative myocardial infarction. Both non-cardiac and cardiac surgery are associated with substantial risks for myocardial infarction or death. Some 7 million patients undergoing non-cardiac surgery are considered to be at risk, with incidences of perioperative death and serious cardiac complications as high as 20-25% in some series. In addition, of the 400,000 patients undergoing coronary by-pass surgery annually, perioperative myocardial infarction is estimated to occur in 5% and death in 1-2%. There is currently no drug therapy in this area, which reduces damage to cardiac tissue from perioperative myocardial ischemia or enhances cardiac resistance to ischemic episodes. Such a therapy is anticipated to be life-saving and reduce hospitalizations, enhance quality of life, and reduce overall health care costs of high risk patients.
[0017] Obesity is a well-known risk factor for the development of many very common diseases such as atherosclerosis, hypertension, and diabetes. The incidence of obese people and thereby also these diseases is increasing throughout the entire industrialised world. Except for exercise, diet and food restriction no convincing pharmacological treatment for reducing body weight effectively and acceptably currently exists. However, due to its indirect but important effect as a risk factor in mortal and common diseases it will be important to find treatment for obesity and/or means of appetite regulation.
[0018] The term obesity implies an excess of adipose tissue. In this context obesity is best viewed as any degree of excess adiposity that imparts a health risk. The cut off between normal and obese individuals can only be approximated, but the health risk imparted by the obesity is probably a continuum with increasing adiposity. The Framingham study demonstrated that a 20% excess over desirable weight clearly imparted a health risk (Mann G V N. Engl. J. Med 291:226, 1974). In the United States a National Institutes of Health consensus panel on obesity agreed that a 20% increase in relative weight or a body mass index (BMI=body weight in kilograms divided by the square of the height in meters) above the 85th percentile for young adults constitutes a health risk. By the use of these criteria 20 to 30 percent of adult men and 30 to 40 percent of adult women in the United States are obese. (NIH, Ann Intern Med 103:147, 1985).
[0019] Even mild obesity increases the risk for premature death, diabetes, hypertension, atherosclerosis, gallbladder disease, and certain types of cancer. In the industrialised western world the prevalence of obesity has increased significantly in the past few decades. Because of the high prevalence of obesity and its health consequences, its prevention and treatment should be a high public health priority.
[0020] When energy intake exceeds expenditure, the excess calories are stored in adipose tissue, and if this net positive balance is prolonged, obesity results, i.e. there are two components to weight balance, and an abnormality on either side (intake or expenditure) can lead to obesity.
[0021] The regulation of eating behaviour is incompletely understood. To some extent appetite is controlled by discrete areas in the hypothalamus: a feeding centre in the ventrolateral nucleus of the hypothalamus (VLH) and a satiety centre in the ventromedial hypothalamus (VMH). The cerebral cortex receives positive signals from the feeding centre that stimulate eating, and the satiety centre modulates this process by sending inhibitory impulses to the feeding centre. Several regulatory processes may influence these hypothalamic centres. The satiety centre may be activated by the increases in plasma glucose and/or insulin that follow a meal. Meal-induced gastric distension is another possible inhibitory factor. Additionally the hypothalamic centres are sensitive to catecholamines, and beta-adrenergic stimulation inhibits eating behaviour. Ultimately, the cerebral cortex controls eating behaviour, and impulses from the feeding centre to the cerebral cortex are only one input. Psychological, social, and genetic factors also influence food intake.
[0022] At present a variety of techniques are available to effect initial weight loss. Unfortunately, initial weight loss is not an optimal therapeutic goal. Rather, the problem is that most obese patients eventually regain their weight. An effective means to establish and/or sustain weight loss is the major challenge in the treatment of obesity today.
SUMMARY OF THE INVENTION
[0023] The present invention provides compounds of general formula (1)
[0000]
[0000] wherein the substituents are defined below, as well as further embodiments hereof described in the attached embodiments.
[0024] The present invention also provides use of the compounds of the invention for preparation of a medicament for the treatment of various diseases, e.g. for the treatment of type 2 diabetes.
DEFINITIONS
[0025] In the structural formulas given herein and throughout the present specification, the following terms have the indicated meaning:
[0026] The term “optionally substituted” as used herein means that the moiety which is optionally substituted is either unsubstituted or substituted with one or more of the substituents specified. When the moiety in question is substituted with more than one substituent, the substituent may be the same or different.
[0027] The term “adjacent” as used herein regards the relative positions of two atoms or variables, these two atoms or variables sharing a bond or one variable preceding or succeeding the other in a variable specification. By way of example, “atom A adjacent to atom B” means that the two atoms A and B share a bond.
[0028] The term “halogen” or “halo” means fluorine, chlorine, bromine or iodine.
[0029] The term “perhalomethyl” means trifluoromethyl, trichloromethyl, tribromomethyl, or triiodomethyl.
[0030] The use of prefixes of this structure: C x-y -alkyl, C x-y -alkenyl, C x-y -alkynyl, C x-y -cycloalyl or C x-y -cycloalkyl-C x-y -alkenyl- and the like designates radical of the designated type having from x to y carbon atoms.
[0031] The term “alkyl” as used herein, alone or in combination, refers to a straight or branched chain saturated monovalent hydrocarbon radical having from one to ten carbon atoms, for example C 1-8 -alkyl or C 1-6 -alkyl. Typical C 1-8 -alkyl groups and C 1-6 -alkyl groups include, but are not limited to e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylpentyl, neopentyl, n-pentyl, n-hexyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl and the like. The term “C 1-8 -alkyl” as used herein also includes secondary C 3-8 -alkyl and tertiary C 4-8 -alkyl. The term “C 1-6 -alkyl” as used herein also includes secondary C 3-6 -alkyl and tertiary C 4-6 -alkyl.
[0032] The term “alkenyl” as used herein, alone or in combination, refers to a straight or branched chain monovalent hydrocarbon radical containing from two to ten carbon atoms and at least one carbon-carbon double bond, for example C 2-8 -alkenyl or C 2-6 -alkenyl. Typical C 2-8 -alkenyl groups and C 2-6 -alkenyl groups include, but are not limited to, vinyl, 1-propenyl, 2-propenyl, iso-propenyl, 1,3-butadienyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 2,4-hexadienyl, 5-hexenyl and the like.
[0033] The term “alkynyl” as used herein alone or in combination, refers to a straight or branched monovalent hydrocarbon radical containing from two to ten carbon atoms and at least one triple carbon-carbon bond, for example C 2-8 -alkynyl or C 2-6 -alkynyl. Typical C 2-8 -alkynyl groups and C 2-6 -alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 5-hexynyl, 2,4-hexadiynyl and the like.
[0034] The term “cycloalkyl” as used herein, alone or in combination, refers to a saturated mono-, bi-, or tricarbocyclic radical having from three to twelve carbon atoms, for example C 3-8 -cycloalkyl. Typical C 3-8 -cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[3.2.1]octyl, bicyclo[2.2.1]heptyl, norpinyl, norbonyl, norcaryl, adamantyl and the like.
[0035] The term “cycloalkenyl” as used herein, alone or in combination, refers to an non-aromatic unsaturated mono-, bi-, or tricarbocyclic radical having from three to twelve carbon atoms, for example C 3-8 -cycloalkenyl. Typical C 3-8 -cycloalkyl groups include, but are not limited to cyclohexene, cycloheptene and cyclopentene, and the like.
[0036] The term “heterocyclic” or the term “heterocyclyl” as used herein, alone or in combination, refers to a saturated mono-, bi-, or tricarbocyclic group having three to twelve carbon atoms and one or two additional heteroatoms or groups selected from nitrogen, oxygen, sulphur, SO or SO 2 , for example C 3-8 -heterocyclyl. Typical C 3-8 -heterocyclyl groups include, but are not limited to, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyranyl, tetrahydrothiopyranyl, 1,4-dioxanyl, 1,3-dioxanyl, piperidyl, pyrrolidinyl, morpholinyl, piperazinyl, and the like.
[0037] The term “heterocycloalkenyl” as used herein, alone or in combination, refers to a non-aromatic unsaturated mono-, bi-, or tricyclic radical having from three to twelve carbon atoms, and one or two additional heteroatoms or groups selected from nitrogen, oxygen, sulphur, SO or SO 2 , for example C 3-8 -hetereocycloalkenyl. Typical C 3-8 -hetreocycloalkenyl groups include, but are not limited to tetrahydropyridine, azacycloheptene, 2-pyrroline, 3-pyrroline, 2-pyrazoline, imidazoline, 4H-pyran, and the like.
[0038] The term “alkoxy” as used herein, alone or in combination, refers to the monovalent radical R a O—, where R a is alkyl as defined above, for example C 1-8 -alkyl giving C 1-8 -alkoxy. Typical C 1-8 -alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, isohexoxy and the like.
[0039] The term “alkylthio” as used herein, alone or in combination, refers to a straight or branched monovalent radical comprising an alkyl group as described above linked through a divalent sulphur atom having its free valence bond from the sulphur atom, for example C 1-6 -alkylthio. Typical C 1-6 -alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio and the like.
[0040] The term “alkoxycarbonyl” as used herein refers to the monovalent radical R a OC(O)—, where R a is alkyl as described above, for example C 1-8 -alkoxycarbonyl. Typical C 1-8 -alkoxycarbonyl groups include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tertbutoxycarbonyl, 3-methylbutoxycarbonyl, n-hexoxycarbonyl and the like.
[0041] The term “aryl” as used herein refers to a carbocyclic aromatic ring radical or to a aromatic ring system radical. Aryl is also intended to include the partially hydrogenated derivatives of the carbocyclic systems.
[0042] The term “heteroaryl”, as used herein, alone or in combination, refers to an aromatic ring radical with for instance 5 to 7 member atoms, or to a aromatic ring system radical with for instance from 7 to 18 member atoms, containing one or more heteroatoms selected from nitrogen, oxygen, or sulphur heteroatoms, wherein N-oxides and sulphur monoxides and sulphur dioxides are permissible heteroaromatic substitutions; such as e.g. furanyl, thienyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, isothiazolyl, pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothiophenyl, indolyl, and indazolyl, and the like. Heteroaryl is also intended to include the partially hydrogenated derivatives of the heterocyclic systems enumerated below.
[0043] Examples of “aryl” and “heteroaryl” includes, but are not limited to phenyl, biphenyl, indene, fluorene, naphthyl (1-naphthyl, 2-naphthyl), anthracene (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophene (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl, isoxazolyl, thiadiazolyl, oxatriazolyl, thiatriazolyl, quinazolin, fluorenyl, xanthenyl, isoindanyl, benzhydryl, acridinyl, thiazolyl, pyrrolyl (1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), pyrazolyl (1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl), imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl 1,2,3-triazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isooxazolyl (isooxazo-3-yl, isooxazo-4-yl, isooxaz-5-yl), isothiazolyl (isothiazo-3-yl, isothiazo-4-yl, isothiaz-5-yl)thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3- pyridazinyl, 4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl (2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl), 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-dihydro-benzo[b]furanyl)), benzo[b]thiophenyl (benzo[b]thiophen-2-yl, benzo[b]thiophen-3-yl, benzo[b]thiophen-4-yl, benzo[b]thiophen-5-yl, benzo[b]thiophen-6-yl, benzo[b]thiophen-7-yl), 2,3-dihydro-benzo[b]thiophenyl (2,3-dihydro-benzo[b]thiophen-2-yl, 2,3-dihydro-benzo[b]thiophen-3-yl, 2,3-dihydro-benzo[b]thiophen-4-yl, 2,3-dihydro-benzo[b]thiophen-5-yl, 2,3-dihydro-benzo[b]thiophen-6-yl, 2,3-dihydro-benzo[b]thiophen-7-yl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (2-benzoxazolyl, 3-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), benzothiazolyl (2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenz[b,f]azepine (5H-dibenz[b,f]azepin-1-yl, 5H-dibenz[b,f]azepine-2-yl, 5H-dibenz[b,f]azepine-3-yl, 5H-dibenz[b,f]azepine-4-yl, 5H-dibenz[b,f]azepine-5-yl), 10,11-dihydro-5H-dibenz[b,f]azepine (10,11-dihydro-5H-dibenz[b,f]azepine-1-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-2-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-3-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-4-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-5-yl), benzo[1,3]dioxole (2-benzo[1,3]dioxole, 4-benzo[1,3]dioxole, 5-benzo[1,3]dioxole, 6-benzo[1,3]dioxole, 7-benzo[1,3]dioxole), purinyl, and tetrazolyl (5-tetrazolyl, N-tetrazolyl).
[0044] The present invention also relates to partly or fully saturated analogues of the ring systems mentioned above.
[0045] When two or more of the above defined terms are used in combination, such as in aryl-alkyl, heteroaryl-alkyl, cycloalkyl-C 1-6 -alkyl and the like, it is to be understood that the first mentioned radical is a substituent on the latter mentioned radical, where the point of substitution, i.e. the point of attachment to another part of the molecule, is on the latter of the radicals, for example
[0000]
[0000] aryl-alkyl-:
[0000]
[0000] cycloalkyl-alkyl-: and
[0000]
[0000] aryl-alkoxy-:
[0046] The term “fused arylcycloalkyl”, as used herein, refers to an aryl group, as defined above, fused to a cycloalkyl group, as defined above and having the indicated number of carbon atoms, the aryl and cycloalkyl groups having two atoms in common, and wherein the cycloalkyl group is the point of substitution. Examples of “fused arylcycloalkyl” used herein include 1-indanyl, 2-indanyl, 1-(1,2,3,4-tetrahydronaphthyl),
[0000]
[0000] and the like.
[0047] The term “fused heteroarylcycloalkyl”, as used herein, refers to a heteroaryl group, as defined above, fused to a cycloalkyl group, as defined above and having the indicated number of carbon atoms, the aryl and cycloalkyl groups having two atoms in common, and wherein the cycloalkyl group is the point of substitution. Examples of fused heteroarylcycloalkyl used herein include 6,7-dihydro-5H-cyclopenta[b]pyridine, 5,6,7,8-tetrahydroquinoline, 5,6,7,8-tetrahydrisoquinoline, 5,6,7,8-tetrahydroquinazoline and the like
[0048] The term “alkylsulfanyl”, as used herein, refers to the group R a S—, where R a is alkyl as described above.
[0049] The term “alkylsulfenyl”, as used herein, refers to the group R a S(O)—, where R a is alkyl as described above.
[0050] The term “alkylsulfonyl”, as used herein, refers to the group R a SO 2 —, where R a is alkyl as described above.
[0051] The term “alkylsulfamoyl”, as used herein, refers to the group R a NHSO 2 —, where R a is alkyl as described above.
[0052] The term “dialkylsulfamoyl”, as used herein, refers to the group R a R b NSO 2 —, where R a and R b are alkyl as described above.
[0053] The term “alkylsulfinamoyl”, as used herein, refers to the group R a NHSO—, where R a is alkyl as described above.
[0054] The term “dialkylsulfinamoyl”, as used herein, refers to the group R a R b NSO—, where R a and R b are alkyl as described above.
[0055] The term “alkylamino”, as used herein, refers to the group R a NH—, where R a is alkyl as described above.
[0056] The term “acyl”, as used herein, refers to the group R a C(O)—, where R a is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or heterocyclyl as described above.
[0057] The term “heteroaryloxy” as used herein, alone or in combination, refers to the monovalent radical R a O—, where R a is heteroaryl as defined above.
[0058] The term “aryloxycarbonyl”, as used herein, refers to the group R a —O—C(O)—, where R a is aryl as described above.
[0059] The term “acyloxy”, as used herein, refers to the group R a C(O)O—, where R a is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or heterocyclyl as described above.
[0060] The term “aryloxy”, as used herein refers to the group R a —O—, where R a is aryl as described above.
[0061] The term “aroyloxy”, as used herein, refers to the group R a C(O)O—, where R a is aryl as described above.
[0062] The term “heteroaroyloxy”, as used herein, refers to the group R a C(O)O—, where R a is heteroaryl as described above.
[0063] Whenever the terms “alkyl”, “cycloalkyl”, “aryl”, “heteroaryl” or the like or either of their prefix roots appear in a name of a substituent (e.g. arylalkoxyaryloxy) they shall be interpreted as including those limitations given above for “alkyl” and “aryl”. As used herein, the term “oxo” shall refer to the substituent ═O.
[0000] As used herein, the term “mercapto” shall refer to the substituent —SH.
As used herein, the term “carboxy” shall refer to the substituent —C(O)OH.
As used herein, the term “cyano” shall refer to the substituent —CN.
As used herein, the term “nitro” shall refer to the substituent —NO 2 .
As used herein, the term “aminosulfonyl” shall refer to the substituent —SO 2 NH 2 .
As used herein, the term “sulfanyl” shall refer to the substituent —S—.
As used herein, the term “sulfenyl” shall refer to the substituent —S(O)—.
As used herein, the term “sulfonyl” shall refer to the substituent —S(O) 2 —.
[0064] As used herein, the term “direct bond”, where part of a structural variable specification, refers to the direct joining of the substituents flanking (preceding and succeeding) the variable taken as a “direct bond”.
[0065] The term “lower”, as used herein, refers to a group having between one and six carbons, and may be indicated with the prefix C x-6 —. Lower alkyl may thus be indicated as C 1-6 -alkyl, while lower alkylene may be indicated as C 2-6 -alkylene.
[0066] A radical such as C x-y -cycloalkyl-C a-b -alkenyl shall designate that the radical's point of attachment is in part of the radical mentioned last.
[0067] As used herein, the term “optionally” means that the subsequently described event(s) may or may not occur, and includes both event(s) which occur and events that do not occur.
[0068] As used herein, the term “substituted” refers to substitution with the named substituent or substituents, multiple degrees of substitution being allowed unless otherwise stated.
[0069] As used herein, the term “attached” or “-” (e.g. —C(O)R 11 which indicates the carbonyl attachment point to the scaffold) signifies a stable covalent bond.
[0070] As used herein, the terms “contain” or “containing” can refer to in-line substitutions at any position along the above defined alkyl, alkenyl, alkynyl or cycloalkyl substituents with one or more of any of O, S, SO, SO 2 , N, or N-alkyl, including, for example, —CH 2 —O—CH 2 —, —CH 2 —SO 2 —CH 2 —, —CH 2 —NH—CH 3 and so forth.
[0071] Certain of the above defined terms may occur more than once in the structural formulae, and upon such occurrence each term shall be defined independently of the other.
[0072] As used herein, the term “solvate” is a complex of variable stoichiometry formed by a solute (in this invention, a compound of formula (I)) and a solvent. Such solvents for the purpose of the present invention may not interfere with the biological activity of the solute. Solvents may be, by way of example, water, ethanol, or acetic acid.
[0073] As used herein, the term “biohydrolyzable ester” is an ester of a drug substance (in this invention, a compound of formula (I)) which either a) does not interfere with the biological activity of the parent substance but confers on that substance advantageous properties in vivo such as duration of action, onset of action, and the like, or b) is biologically inactive but is readily converted in vivo by the subject to the biologically active principle. The advantage is that, for example, the biohydrolyzable ester is orally absorbed from the gut and is transformed to (I) in plasma. Many examples of such are known in the art and include by way of example lower alkyl esters (e.g., C 1-4 ), lower acyloxyalkyl esters, lower alkoxyacyloxyalkyl esters, alkoxyacyloxy esters, alkyl acylamino alkyl esters, and choline esters.
[0074] As used herein, the term “biohydrolyzable amide” is an amide of a drug substance (in this invention, a compound of general formula (I)) which either a) does not interfere with the biological activity of the parent substance but confers on that substance advantageous properties in vivo such as duration of action, onset of action, and the like, or b) is biologically inactive but is readily converted in vivo by the subject to the biologically active principle. The advantage is that, for example, the biohydrolyzable amide is orally absorbed from the gut and is transformed to (I) in plasma. Many examples of such are known in the art and include by way of example lower alkyl amides, α-amino acid amides, alkoxyacyl amides, and alkylaminoalkylcarbonyl amides.
[0075] As used herein, the term “prodrug” includes biohydrolyzable amides and biohydrolyzable esters and also encompasses a) compounds in which the biohydrolyzable functionality in such a prodrug is encompassed in the compound of formula (I) and b) compounds which may be oxidized or reduced biologically at a given functional group to yield drug substances of formula (I). Examples of these functional groups include, but are not limited to, 1,4-dihydropyridine, N-alkylcarbonyl-1,4-dihydropyridine, 1,4-cyclohexadiene, tert-butyl, and the like.
[0076] The term “pharmacologically effective amount” or shall mean that amount of a drug or pharmaceutical agent that will elicit the biological or medical response of a tissue, animal or human that is being sought by a researcher or clinician. This amount can be a therapeutically effective amount. The term “therapeutically effective amount” shall mean that amount of a drug or pharmaceutical agent that will elicit the therapeutic response of an animal or human that is being sought.
[0077] The term “treatment” and “treating” as used herein means the management and care of a patient for the purpose of combating a disease, disorder or condition. The term is intended to include the full spectrum of treatments for a given disorder from which the patient is suffering, such as the delaying of the progression of the disease, disorder or condition, the alleviation or relief of symptoms and complications, the prevention of the disease and/or the cure or elimination of the disease, disorder or condition. The patient to be treated is preferably a mammal, in particular a human being.
[0078] The term “pharmaceutically acceptable salt” as used herein includes pharmaceutically acceptable acid addition salts, pharmaceutically acceptable base addition salts, pharmaceutically acceptable metal salts, ammonium salts, and alkylated ammonium salts. Acid addition salts include salts of inorganic acids as well as organic acids. Representative examples of suitable inorganic acids include hydrochloric, hydrobromic, hydroiodic, phosphoric, sulfuric, and nitric acids. Representative examples of suitable organic acids include formic, acetic, trichloroacetic, trifluoroacetic, propionic, benzoic, cinnamic, citric, fumaric, glycolic, lactic, maleic, malic, malonic, mandelic, oxalic, picric, pyruvic, salicylic, succinic, methanesulfonic, ethanesulfonic, tartaric, ascorbic, pamoic, bismethylene salicylic, ethanedisulfonic, gluconic, citraconic, aspartic, stearic, palmitic, EDTA, glycolic, p-aminobenzoic, glutamic, benzenesulfonic, p-toluenesulfonic acids, sulphates, nitrates, phosphates, perchlorates, borates, acetates, benzoates, hydroxynaphthoates, glycerophosphates, and ketoglutarates. Further examples of pharmaceutically acceptable inorganic or organic acid addition salts include the pharmaceutically acceptable salts listed in J. Pharm. Sci. 1977, 66, 2, which is incorporated herein by reference. Examples of metal salts include lithium, sodium, potassium, magnesium, zinc, and calcium salts. Examples of amines and organic amines include ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, butylamine, tetramethylamine, ethanolamine, diethanolamine, triethanolamine, meglumine, ethylenediamine, choline, N,N′-dibenzylethylenediamine, N-benzylphenylethylamine, N-methyl-D-glucamine, and guanidine. Examples of cationic amino acids include lysine, arginine, and histidine.
[0079] The pharmaceutically acceptable salts are prepared by reacting the compound of formula I with 1 to 4 equivalents of a base such as sodium hydroxide, sodium methoxide, sodium hydride, potassium t-butoxide, calcium hydroxide, and magnesium hydroxide, in solvents such as ether, THF, methanol, t-butanol, dioxane, isopropanol, ethanol etc. Mixture of solvents may be used. Organic bases such as lysine, arginine, diethanolamine, choline, guandine and their derivatives etc. may also be used. Alternatively, acid addition salts wherever applicable are prepared by treatment with acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulphonic acid, methanesulfonic acid, acetic acid, citric acid, maleic acid salicylic acid, hydroxynaphthoic acid, ascorbic acid, palmitic acid, succinic acid, benzoic acid, benzenesulfonic acid, and tartaric acid in solvents such as ethyl acetate, ether, alcohols, acetone, THF, dioxane etc. Mixture of solvents may also be used.
[0080] The term “combination therapy”, “combined”, “in combination with”, and the like, as used herein refers to the administration of a single pharmaceutical dosage formulation which comprises the glucokinase activator compound of the present invention and another active agent(s), as well as administration of each active agent(s) in its own separate pharmaceutical dosage formulation. Where separate dosage formulations are used, the compound of the present invention and another active agent(s) can be administered to the patient at essentially the same time, i.e. concurrently, or at separate staggered times, i.e. sequentially. When given by different dosage formulations, the route of administration may be the same or different for each agent. Any route of administration known or contemplated for the individual agents is acceptable for the practice of the present invention.
DESCRIPTION OF THE INVENTION
[0081] The present invention provides compounds of formula (I)
[0000]
[0000] wherein R 1 is C 3-8 -cycloalkyl, C 3-8 -cycloalkenyl, C 3-8 -heterocyclyl, C 3-8 -heterocycloalkenyl, fused aryl-C 3-8 -cycloalkyl, or fused heteroaryl-C 3-8 -cycloalkyl, each of which is optionally substituted with one or more substituents R 5 , R 6 , R 7 and R 8 ;
R 2 is C 3-8 -cycloalkyl, C 3-8 -cycloalkenyl, C 3-8 -heterocyclyl, C 3-8 -heterocycloalkenyl, fused aryl-C 3-8 -cycloalkyl or fused heteroaryl-C 3-8 -cycloalkyl, each of which is optionally substituted with one or more substituents R 9 , R 10 , R 11 and R 12 ;
R 3 is hydrogen, C 1-6 -alkyl, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, C 3-6 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryloxyC 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, C 1-6 -alkyl-C(O)—O—C 1-6 -alkyl, C 1-6 -alkylthio-C 1-6 -alkyl, amino-C 1-6 -alkyl, C 1-6 -alkylamino-C 1-6 -alkyl, di-(C 1-6 -alkyl)amino-C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 20 ;
R 4 is hydrogen, C 1-6 -alkyl, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, C 3-6 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryloxyC 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, C 1-6 -alkyl-C(O)—O—C 1-6 -alkyl, C 1-6 -alkylthio-C 1-6 -alkyl, amino-C 1-6 -alkyl, C 1-6 -alkylamino-C 1-6 -alkyl, di-(C 1-6 -alkyl)amino-C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 21 ;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from the group consisting of
halogen, nitro, cyano, hydroxy, oxo, carboxy, —CF 3 ; or —NR 13 R 14 ; or C 1-6 -alkyl, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-6 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, C 1-6 -alkoxy, C 3-6 -cycloalkyl-C 1-6 -alkoxy, aryl-C 1-6 -alkoxy, aryloxy-C 1-6 -alkyl, C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, heteroaryl-C 1-6 -alkoxy, aryloxy, heteroaryloxy, C 3-6 -cycloalkyl-C 1-6 -alkylthio, C 1-6 -alkyl-C(O)—O—C 1-6 -alkyl, C 1-6 -alkylthio-C 1-6 -alkyl, carboxy-C 1-6 -alkyloxy, amino-C 1-6 -alkyl, C 1-6 -alkylamino-C 1-6 -alkyl, di-(C 1-6 -alkyl)amino-C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 15 ; or —C(O)—R 16 , —S(O) 2 —R 16 , —C(O)—NR 17 R 18 , —S(O) 2 —NR 17 R 18 , —C 1-6 -alkyl-C(O)—NR 17 R 18 ; or
R 13 and R 14 independently represent hydrogen, C 1-6 -alkyl, —C(O)—C 1-6 -alkyl, —C(O)—O—C 1-6 -alkyl, carboxy-C 1-6 -alkyl, —C(O)—C 1-6 -alkyl-C(O)OH, —S(O) 2 —C 1-6 -alkyl, or aryl, each of which is optionally substituted with one or more halogens;
R 15 is halogen, cyano, carboxy, hydroxy, —C(O)—O—C 1-6 -alkyl, —CF 3 , C 1-6 -alkyl, C 1-6 -alkoxy, NR 10 R 11 , —S(O) 2 CH 3 , S(O) 2 CH 2 CF 3 , —S(O) 2 CF 3 , or —S(O) 2 NH 2 ;
R 16 is C 1-6 -alkyl, C 1-6 -alkoxy, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, aryloxy-C 1-6 -alkyl, heteroaryl, C 3-8 -heterocyclyl, heteroaryl-C 1-6 -alkyl, C 3-8 -heterocyclyl-C 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, carboxy-C 2-6 -alkenyl, C 1-6 -alkoxy-C 1-6 -alkyl, C 1-6 -alkoxy-C 2-6 -alkenyl, R 13 HN—C 1-6 -alkyl, R 13 R 14 —N—C 1-6 -alkyl, R 13 R 14 —N—C 2-6 -alkenyl, R 13 R 14 —N—S(O) 2 —C 1-6 -alkyl, R 13 R 14 —N—C(O)—C 1-6 -alkyl, C 1-6 -alkyl-C(O)—NH—C 1-6 -alkyl, aryl-C(O)—NH—C 1-6 -alkyl, heteroaryl-C(O)—NH—C 1-6 -alkyl, C 3-8 -cycloalkyl-C(O)—NH—C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 15 ;
R 17 and R 18 are independently selected from the group consisting of hydrogen, C 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, aryl, or heteroaryl, each of which is optionally substituted with one or more substituents independently selected from R 19 ; or R 17 and R 18 together with the nitrogen to which they are attached form a 3 to 8 membered heterocyclic ring with the said nitrogen atom, the heterocyclic ring optionally containing one or two further heteroatoms selected from nitrogen, oxygen and sulphur;
R 19 is halogen, cyano, hydroxy, carboxy, —CF 3 , C 1-6 -alkyl, —S(O) 2 CH 3 , or —S(O) 2 NH 2 ;
R 20 and R 21 are independently selected from the group consisting of halogen, hydroxy, carboxy, oxo, carboxy-C 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkylthio, carboxy-C 2-6 -alkenylthio, carboxy-C 1-6 -alkylsulfonyl, carboxy-C 1-6 -alkylsulfamoyl, C 1-6 -alkoxy, alkylamino, —C(O)—C 1-6 -alkyl.
[0086] Another embodiment of the present invention provides compounds according to formula (I), wherein
[0000] R 1 is C 3-8 -cycloalkyl or C 3-8 -heterocyclyl, each of which is optionally substituted with one or more substituents R 5 , R 6 , R 7 and R 8 ;
R 2 is C 3-8 -cycloalkyl or C 3-8 -heterocyclyl, each of which is optionally substituted with one or more substituents R 9 , R 10 , R 11 and R 12 ;
R 3 is hydrogen, C 1-6 -alkyl, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, C 3-6 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryloxyC 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, C 1-6 -alkyl-C(O)—O—C 1-6 -alkyl, C 1-6 -alkylthio-C 1-6 -alkyl, amino-C 1-6 -alkyl, C 1-6 -alkylamino-C 1-6 -alkyl, di-(C 1-6 -alkyl)amino-C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 20 ;
R 4 is hydrogen, C 1-6 -alkyl, C 2-6 -alkenyl, C 2-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, C 3-6 -cycloalkyl-C 1-6 -alkyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryloxyC 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, C 1-6 -alkyl-C(O)—O—C 1-6 -alkyl, C 1-6 -alkylthio-C 1-6 -alkyl, amino-C 1-6 -alkyl, C 1-6 -alkylamino-C 1-6 -alkyl, di-(C 1-6 -alkyl)amino-C 1-6 -alkyl each of which is optionally substituted with one or more substituents independently selected from R 21 ;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from the group consisting of
halogen, nitro, cyano, hydroxy, oxo, carboxy, —CF 3 ; or —NR 13 R 14 ; or C 1-6 -alkoxy, C 3-6 -cycloalkyl-C 1-6 -alkoxy, aryl-C 1-6 -alkoxy, aryloxy-C 1-6 -alkyl, C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, heteroaryl-C 1-6 -alkoxy, aryloxy, heteroaryloxy, each of which is optionally substituted with one or more substituents independently selected from R 15 ; or —C(O)—R 16 , —S(O) 2 —R 16 , —C(O)—NR 17 R 18 , —S(O) 2 —NR 17 R 18 , —C 1-6 -alkyl-C(O)—NR 17 R 18 ; or
R 13 and R 14 independently represent —C(O)—C 1-6 -alkyl, —C(O)—O—C 1-6 -alkyl, carboxy-C 1-6 -alkyl, —C(O)—C 1-6 -alkyl-C(O)OH, —S(O) 2 —C 1-6 -alkyl, each of which is optionally substituted with one or more halogens;
R 15 is halogen, carboxy, or C 1-6 -alkoxy;
R 16 is C 1-6 -alkyl, C 1-6 -alkoxy, aryloxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, carboxy-C 2-6 -alkenyl, or C 1-6 -alkoxy-C 1-6 -alkyl, each of which is optionally substituted with one or more substituents independently selected from R 15 ;
R 17 and R 18 are independently selected from the group consisting of hydrogen, C 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, aryl, or heteroaryl, each of which is optionally substituted with one or more substituents independently selected from R 19 ; or R 17 and R 18 together with the nitrogen to which they are attached form a 3 to 8 membered heterocyclic ring with the said nitrogen atom, the heterocyclic ring optionally containing one or two further heteroatoms selected from nitrogen, oxygen and sulphur;
R 19 is halogen, cyano, hydroxy, carboxy, —CF 3 , C 1-6 -alkyl, —S(O) 2 CH 3 , or —S(O) 2 NH 2 ;
R 20 and R 21 are independently selected from the group consisting of carboxy, oxo, carboxy-C 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkylthio, carboxy-C 2-6 -alkenylthio, carboxy-C 1-6 -alkylsulfonyl, carboxy-C 1-6 -alkylsulfamoyl, C 1-6 -alkoxy, alkylamino, —C(O)—C 1-6 -alkyl;
or a pharmaceutically acceptable salt thereof.
[0091] Another embodiment of the present invention provides compounds according to formula (I), wherein
[0000] R 1 is cyclopentyl, cyclohexyl, cycloheptyl, or piperidinyl, each of which is optionally substituted with one or more substituents R 5 , R 6 , R 7 and R 8 ;
R 2 is cyclopentyl, cyclohexyl, cycloheptyl, or piperidinyl, each of which is optionally substituted with one or more substituents R 9 , R 10 , R 11 and R 12 ;
R 3 is hydrogen, C 1-6 -alkyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl, heteroaryl, or C 1-6 -alkylthio-C 1-6 -alkyl, each of which is optionally substituted with one or more substituents independently selected from R 20 ;
R 4 is hydrogen, C 1-6 -alkyl, C 3-8 -cycloalkyl, C 3-8 -heterocyclyl, aryl, aryl-C 1-6 -alkyl, heteroaryl-C 1-6 -alkyl, heteroaryloxy-C 1-6 -alkyl, heteroaryl, or C 1-6 -alkylthio-C 1-6 -alkyl, each of which is optionally substituted with one or more substituents independently selected from R 21 ;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently selected from the group consisting of
halogen, nitro, cyano, hydroxy, oxo, carboxy, —CF 3 ; or —NR 13 R 14 ; or C 1-6 -alkoxy, C 3-6 -cycloalkyl-C 1-6 -alkoxy, aryl-C 1-6 -alkoxy, aryloxy-C 1-6 -alkyl, C 3-6 -cycloalkyl-C 1-6 -alkoxy-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, aryl-C 1-6 -alkoxy-C 1-6 -alkyl, heteroaryl, heteroaryl-C 1-6 -alkoxy, aryloxy, heteroaryloxy, each of which is optionally substituted with one or more substituents independently selected from R 15 ; or —C(O)—R 16 , —S(O) 2 —R 16 , —C(O)—NR 17 R 18 , —S(O) 2 —NR 17 R 18 , —C 1-6 -alkyl-C(O)—NR 17 R 18 ; or
R 13 and R 14 independently represent —C(O)—C 1-6 -alkyl, —C(O)—O—C 1-6 -alkyl, carboxy-C 1-6 -alkyl, —C(O)—C 1-6 -alkyl-C(O)OH, —S(O) 2 —C 1-6 -alkyl, each of which is optionally substituted with one or more halogens;
R 15 is halogen, carboxy, or C 1-6 -alkoxy;
R 16 is C 1-6 -alkyl, C 1-6 -alkoxy, aryloxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, carboxy-C 2-6 -alkenyl, or C 1-6 -alkoxy-C 1-6 -alkyl, each of which is optionally substituted with one or more substituents independently selected from R 15 ;
R 17 and R 18 are independently selected from the group consisting of hydrogen, C 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, aryl, or heteroaryl, each of which is optionally substituted with one or more substituents independently selected from R 19 ; or R 17 and R 18 together with the nitrogen to which they are attached form a 3 to 8 membered heterocyclic ring with the said nitrogen atom, the heterocyclic ring optionally containing one or two further heteroatoms selected from nitrogen, oxygen and sulphur;
R 19 is halogen, cyano, hydroxy, carboxy, —CF 3 , C 1-6 -alkyl, —S(O) 2 CH 3 , or —S(O) 2 NH 2 ;
R 20 and R 21 are independently selected from the group consisting of carboxy, oxo, carboxyC 1-6 -alkyl, hydroxy-C 1-6 -alkyl, carboxy-C 1-6 -alkylthio, carboxy-C 2-6 -alkenylthio, carboxy-C 1-6 -alkylsulfonyl, carboxy-C 1-6 -alkylsuIfamoyl, C 1-6 -alkoxy, alkylamino, —C(O)—C 1-6 -alkyl;
or a pharmaceutically acceptable salt thereof.
[0096] In another embodiment, the present invention provides a novel compound wherein the compound is selected from the following:
1,1-Bis-(cyclohexyl)-5-methyl biuret; 1,1-Bis-(cyclohexyl)-5-butyl biuret; 1,1-Bis-(cyclohexyl)-5-(3-pyridylmethyl) biuret; 1,1-Bis-(cyclohexyl)-5-(4-fluorobenzyl) biuret; 1,1-Bis-(cyclohexyl)-5-(3-chlorobenzyl) biuret; 1,1-Bis-(cyclohexyl)-5-(o-tolyl) biuret; 1,1-Bis-(cyclohexyl)-5-(2,2,2-trifluoroethyl) biuret; 1,1-Bis-(cyclohexyl)-5-(2-thiazolyl) biuret; 1,1-Bis-(cyclohexyl)-5-ethyl biuret; 1,1-Bis-(cyclohexyl)-5-cyclohexyl biuret; 1,1-Bis-(cyclohexyl)-5-(2-pyridylmethyl) biuret; 1,1-Bis-(cyclohexyl)-5-(4-methoxybenzyl) biuret; and 1,1-Bis-(cyclohexyl)-5-(2-pyridyl) biuret;
or a pharmaceutically acceptable salt thereof.
[0110] In another embodiment, the present invention provides a novel pharmaceutical composition, comprising: a pharmaceutically acceptable carrier and a compound of the present invention, or a pharmaceutically acceptable salt thereof.
[0111] In another embodiment, the present invention provides a novel method of treating type 2 diabetes, comprising: administering to a subject in need thereof a therapeutically effective amount of a compound of the present invention.
[0112] In one aspect the invention provides a method of preventing hypoglycemia comprising administration of a compound according to the present invention.
[0113] In another aspect the invention provides the use of a compound according to the present invention for the preparation of a medicament for the prevention of hypoglycemia.
[0114] In another aspect the invention provides a compound as described herein, which is an agent useful for the treatment of an indication selected from the group consisting of hyperglycemia, IGT, insulin resistance syndrome, syndrome X, type 2 diabetes, type 1 diabetes, dyslipidemia, hypertension, and obesity.
[0115] In another aspect the invention provides a compound as described herein for use as a medicament.
[0116] In another aspect the invention provides a compound as described herein for treatment of hyperglycemia, for treatment of IGT, for treatment of Syndrome X, for treatment of type 2 diabetes, for treatment of type 1 diabetes, for treatment of dyslipidemia, for treatment of hyperlipidemia, for treatment of hypertension, for treatment of obesity, for lowering of food intake, for appetite regulation, for regulating feeding behaviour, or for enhancing the secretion of enteroincretins, such as GLP-1.
[0117] In another aspect the invention provides a pharmaceutical composition comprising, as an active ingredient, at least one compound as described herein together with one or more pharmaceutically acceptable carriers or excipients.
[0118] In one embodiment such a pharmaceutical composition may be in unit dosage form, comprising from about 0.05 mg to about 1000 mg, preferably from about 0.1 mg to about 500 mg and especially preferred from about 0.5 mg to about 200 mg of the compound according to the present invention.
[0119] In another aspect the invention provides the use of a compound according to the invention for increasing the activity of glucokinase.
[0120] In another aspect the invention provides the use of a compound according to the invention for the preparation of a medicament for the treatment of metabolic disorders, for blood glucose lowering, for the treatment of hyperglycemia, for the treatment of IGT, for the treatment of Syndrome X, for the treatment of impaired fasting glucose (IFG), for the treatment of type 2 diabetes, for the treatment of type 1 diabetes, for delaying the progression of impaired glucose tolerance (IGT) to type 2 diabetes, for delaying the progression of non-insulin requiring type 2 diabetes to insulin requiring type 2 diabetes, for the treatment of dyslipidemia, for the treatment of hyperlipidemia, for the treatment of hypertension, for lowering of food intake, for appetite regulation, for the treatment of obesity, for regulating feeding behaviour, or for enhancing the secretion of enteroincretins. In another aspect the invention provides the use of a compound according to the invention for the preparation of a medicament for the adjuvant treatment of type 1 diabetes for preventing the onset of diabetic complications.
[0121] In another aspect the invention provides the use of a compound according to the invention for the preparation of a medicament for increasing the number and/or the size of beta cells in a mammalian subject, for treatment of beta cell degeneration, in particular apoptosis of beta cells, or for treatment of functional dyspepsia, in particular irritable bowel syndrome.
[0122] In one embodiment the invention provides any of the above uses in a regimen which comprises treatment with a further antidiabetic agent.
[0123] In a further aspect the invention provides the use of a compound according to the invention or a pharmaceutical composition as described above for the treatment of metabolic disorders, for blood glucose lowering, for the treatment of hyperglycemia, for treatment of IGT, for treatment of Syndrome X, for the treatment of impaired fasting glucose (IFG), for treatment of type 2 diabetes, for treatment of type 1 diabetes, for delaying the progression of impaired glucose tolerance (IGT) to type 2 diabetes, for delaying the progression of non-insulin requiring type 2 diabetes to insulin requiring type 2 diabetes, for treatment of dyslipidemia, for treatment of hyperlipidemia, for treatment of hypertension, for the treatment or prophylaxis of obesity, for lowering of food intake, for appetite regulation, for regulating feeding behaviour, or for enhancing the secretion of enteroincretins.
[0124] In a further aspect the invention provides the use of a compound according to the invention or a pharmaceutical composition as described above for the adjuvant treatment of type 1 diabetes for preventing the onset of diabetic complications.
[0125] In a further aspect the invention provides the use of a compound according to the invention or a pharmaceutical composition as described above for increasing the number and/or the size of beta cells in a mammalian subject, for treatment of beta cell degeneration, in particular apoptosis of beta cells, or for treatment of functional dyspepsia, in particular irritable bowel syndrome.
[0126] In another embodiment the invention provides a for the treatment of a glucokinase-deficiency mediated condition/disease which is caused by a glucokinase mutation.
[0127] In another embodiment the invention provides a method wherein the glucokinase-deficiency mediated condition/disease is Maturity-Onset Diabetes of the Young, Neonatal Diabetes Mellitus, or Persistent Neonatal Diabetes Mellitus.
[0128] In another embodiment the invention provides a method for preventing or ameliorating the development of diabetes in subjects exhibiting symptoms of Impaired Glucose Tolerance, Gestational Diabetes Mellitus, Polycystic Ovarian Syndrome, Cushings syndrome or Metabolic Syndrome comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0129] In another embodiment the invention provides a method for preventing or ameliorating microvascular diseases comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0130] In another embodiment the invention provides a method for preventing macrovascular diseases in subjects exhibiting symptoms of Impaired Glucose Tolerance, Gestational Diabetes Mellitus, or Metabolic Syndrome, comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, alone or in combination with lipid-lowering drugs, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0131] In another embodiment the invention provides a method for the preservation of beta-cell mass and function comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0132] In another embodiment the invention provides a method for preventing amyloid beta peptide induced cell death comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0133] In another embodiment the invention provides a method wherein the subject is a veterinary subject.
[0134] In another embodiment the invention provides a method wherein a compound according to the invention is administered as a food additive.
[0135] In another embodiment the invention provides a method for the treatment of hepatic conditions benefiting from blood glucose normalization comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0136] In another embodiment the invention provides a method for the treatment of hepatic conditions benefiting from improved liver function comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0137] In another embodiment the invention provides a method for the treatment of hyperglycemic conditions that result from critical illness, or as a consequence of therapeutic intervention comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0138] In another embodiment the invention provides a method for the treatment of hepatic conditions that result from critical illness like cancer, or are a consequence of therapy, for example cancer therapy or HIV-treatment, comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0139] In another embodiment the invention provides a method of treatment adjuvant to insulin in insulin-requiring diabetes type 2, or as replacement for insulin comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0140] In another embodiment the invention provides a method for the treatment of lipodistrophy comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0141] In another embodiment the invention provides a method for the treatment of hyperglycemia resulting from severe physical stress without signs of liver failure comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0142] In another embodiment the invention provides a method wherein the severe physical stress is multiple trauma, or diabetic ketoacidosis.
[0143] In another embodiment the invention provides a method for preventing apoptotic liver damage comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0144] In another embodiment the invention provides a method for preventing hypoglycemia comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0145] In another embodiment the invention provides a method for increasing beta-cell mass and function comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0146] In another embodiment the invention provides a method of preventing type 1 diabetes comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0147] In another embodiment the invention provides a method of preserving and/or increasing beta-cell mass and function in patients having undergone pancreatic islet transplantation comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0148] In another embodiment the invention provides a method of improving glucose control during and after surgery comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0149] In another embodiment the invention provides a method of improving liver function and/or survival in patients undergoing liver transplantation comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof. In another embodiment hereof the invention provides a method wherein the administration occurs before, during or after transplantation, or any combination thereof.
[0150] In another embodiment the invention provides a method of obtaining blood glucose normalization comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein blood glucose normalization occurs with reduced risk of hypoglycemia.
[0151] In another embodiment the invention provides a method of preventing or ameliorating diabetic late complications comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0152] In another embodiment the invention provides a method of treating type 1 or 2 diabetes comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof, wherein the treatment does not result in a weight gain.
[0153] In another embodiment the invention provides a method of preventing diabetic ketoacidosis comprising administering to a subject in need of such treatment a compound according to the invention or pharmaceutical composition thereof.
[0154] In another embodiment, the present invention provides a novel method of treating a condition or disorder, comprising: administering to a subject in need thereof a therapeutically effective amount of a compound of the present invention, wherein the condition or disorder is selected from a metabolic disorder, blood glucose lowering, hyperglycemia, impaired glucose tolerance (IGT), Syndrome X, Polycystic Ovarian Syndrome, impaired fasting glucose (IFG), type I diabetes, delaying the progression of impaired glucose tolerance (IGT) to type II diabetes, delaying the progression of non-insulin requiring type II diabetes to insulin requiring type II diabetes, dyslipidemia, hyperlipidemia, hypertension, treatment or prophylaxis of obesity, lowering of food intake, appetite regulation, regulating feeding behaviour, and enhancing the secretion of enteroincretins.
[0155] In a further aspect of the present invention the present compounds are administered in combination with one or more further active substances in any suitable ratios. When used in combination with one or more further active substances, the combination of compounds is preferably a synergistic combination. Synergy occurs when the effect of the compounds when administered in combination is greater than the additive effect of the compounds when administered as a single agent. In general, a synergistic effect is most clearly demonstrated at sub-optimal concentrations of the compounds. Such further active agents may be selected from antidiabetic agents, antihyperlipidemic agents, antiobesity agents, antihypertensive agents and agents for the treatment of complications resulting from or associated with diabetes.
[0156] Suitable antidiabetic agents include insulin, GLP-1 (glucagon like peptide-1) derivatives such as those disclosed in WO 98/08871 (Novo Nordisk A/S), which is incorporated herein by reference, as well as orally active hypoglycemic agents.
[0157] Suitable orally active hypoglycemic agents preferably include imidazolines, sulfonylureas, biguanides, meglitinides, oxadiazolidinediones, thiazolidinediones, insulin sensitizers, α-glucosidase inhibitors, agents acting on the ATP-dependent potassium channel of the pancreatic β-cells eg potassium channel openers such as those disclosed in WO 97/26265, WO 99/03861 and WO 00/37474 (Novo Nordisk A/S) which are incorporated herein by reference, potassium channel openers, such as ormitiglinide, potassium channel blockers such as nateglinide or BTS-67582, glucagon antagonists such as those disclosed in WO 99/01423 and WO 00/39088 (Novo Nordisk A/S and Agouron Pharmaceuticals, Inc.), all of which are incorporated herein by reference, GLP-1 agonists such as those disclosed in WO 00/42026 (Novo Nordisk A/S and Agouron Pharmaceuticals, Inc.), which are incorporated herein by reference, DPP-IV (dipeptidyl peptidase-IV) inhibitors, PTPase (protein tyrosine phosphatase) inhibitors, inhibitors of hepatic enzymes involved in stimulation of gluconeogenesis and/or glycogenolysis, glucose uptake modulators, GSK-3 (glycogen synthase kinase-3) inhibitors, compounds modifying the lipid metabolism such as antihyperlipidemic agents and antilipidemic agents, compounds lowering food intake, and PPAR (peroxisome proliferatoractivated receptor) and RXR (retinoid X receptor) agonists such as ALRT-268, LG-1268 or LG-1069.
[0158] In one embodiment of the present invention, the present compounds are administered in combination with a sulphonylurea eg tolbutamide, chlorpropamide, tolazamide, glibenclamide, glipizide, glimepiride, glicazide or glyburide.
[0159] In one embodiment of the present invention, the present compounds are administered in combination with a biguanide eg metformin.
[0160] In one embodiment of the present invention, the present compounds are administered in combination with a meglitinide eg repaglinide or senaglinide/nateglinide.
[0161] In one embodiment of the present invention, the present compounds are administered in combination with a thiazolidinedione insulin sensitizer eg troglitazone, ciglitazone, pioglitazone, rosiglitazone, isaglitazone, darglitazone, englitazone, CS-011/CI-1037 or T 174 or the compounds disclosed in WO 97/41097 (DRF-2344), WO 97/41119, WO 97/41120, WO 00/41121 and WO 98/45292 (Dr. Reddy's Research Foundation), which are incorporated herein by reference.
[0162] In one embodiment of the present invention the present compounds may be administered in combination with an insulin sensitizer eg such as GI 262570, YM-440, MCC-555, JTT-501, AR-H039242, KRP-297, GW-409544, CRE-16336, AR-H049020, LY510929, MBX-102, CLX-0940, GW-501516 or the compounds disclosed in WO 99/19313 (NN622/DRF-2725), WO 00/50414, WO 00/63191, WO 00/63192, WO 00/63193 (Dr. Reddy's Research Foundation) and WO 00/23425, WO 00/23415, WO 00/23451, WO 00/23445, WO 00/23417, WO 00/23416, WO 00/63153, WO 00/63196, WO 00/63209, WO 00/63190 and WO 00/63189 (Novo Nordisk A/S), which are incorporated herein by reference.
[0163] In one embodiment of the present invention the present compounds are administered in combination with an α-glucosidase inhibitor eg voglibose, emiglitate, miglitol or acarbose.
[0164] In one embodiment of the present invention the present compounds are administered in combination with a glycogen phosphorylase inhibitor eg the compounds described in WO 97/09040 (Novo Nordisk A/S).
[0165] In one embodiment of the present invention the present compounds are administered in combination with an agent acting on the ATP-dependent potassium channel of the pancreatic β-cells eg tolbutamide, glibenclamide, glipizide, glicazide, BTS-67582 or repaglinide.
[0166] In one embodiment of the present invention the present compounds are administered in combination with nateglinide.
[0167] In one embodiment of the present invention the present compounds are administered in combination with an antihyperlipidemic agent or a antilipidemic agent eg cholestyramine, colestipol, clofibrate, gemfibrozil, lovastatin, pravastatin, simvastatin, probucol or dextrothyroxine.
[0168] Furthermore, the compounds according to the invention may be administered in combination with one or more antiobesity agents or appetite regulating agents. Such agents may be selected from the group consisting of CART (cocaine amphetamine regulated transcript) agonists, NPY (neuropeptide Y) antagonists, MC3 (melanocortin 3) agonists, MC4 (melanocortin 4) agonists, orexin antagonists, TNF (tumor necrosis factor) agonists, CRF (corticotropin releasing factor) agonists, CRF BP (corticotropin releasing factor binding protein) antagonists, urocortin agonists, β3 adrenergic agonists such as CL-316243, AJ-9677, GW-0604, LY362884, LY377267 or AZ-40140, MSH (melanocyte-stimulating hormone) agonists, MCH (melanocyte-concentrating hormone) antagonists, CCK (cholecystokinin) agonists, serotonin reuptake inhibitors (fluoxetine, seroxat or citalopram), serotonin and norepinephrine reuptake inhibitors, 5HT (serotonin) agonists, bombesin agonists, galanin antagonists, growth hormone, growth factors such as prolactin or placental lactogen, growth hormone releasing compounds, TRH (thyreotropin releasing hormone) agonists, UCP 2 or 3 (uncoupling protein 2 or 3) modulators, leptin agonists, DA (dopamine) agonists (bromocriptin, doprexin), lipase/amylase inhibitors, PPAR modulators, RXR modulators, TR β agonists, adrenergic CNS stimulating agents, AGRP (agouti related protein) inhibitors, H3 histamine antagonists such as those disclosed in WO 00/42023, WO 00/63208 and WO 00/64884, which are incorporated herein by reference, exendin-4, GLP-1 agonists, ciliary neurotrophic factor, and oxyntomodulin. Further antiobesity agents are bupropion (antidepressant), topiramate (anticonvulsant), ecopipam (dopamine D1/D5 antagonist) and naltrexone (opioid antagonist).
[0169] In one embodiment of the present invention the antiobesity agent is leptin.
[0170] In one embodiment of the present invention the antiobesity agent is a serotonin and norepinephrine reuptake inhibitor eg sibutramine.
[0171] In one embodiment of the present invention the antiobesity agent is a lipase inhibitor eg orlistat.
[0172] In one embodiment of the present invention the antiobesity agent is an adrenergic CNS stimulating agent eg dexamphetamine, amphetamine, phentermine, mazindol phendimetrazine, diethylpropion, fenfluramine or dexfenfluramine.
[0173] Furthermore, the present compounds may be administered in combination with one or more antihypertensive agents. Examples of antihypertensive agents are β-blockers such as alprenolol, atenolol, timolol, pindolol, propranolol and metoprolol, ACE (angiotensin converting enzyme) inhibitors such as benazepril, captopril, enalapril, fosinopril, lisinopril, quinapril and ramipril, calcium channel blockers such as nifedipine, felodipine, nicardipine, isradipine, nimodipine, diltiazem and verapamil, and α-blockers such as doxazosin, urapidil, prazosin and terazosin. Further reference can be made to Remington: The Science and Practice of Pharmacy, 19th Edition, Gennaro, Ed., Mack Publishing Co., Easton, Pa., 1995.
[0174] In one embodiment of the present invention, the present compounds are administered in combination with insulin, insulin derivatives or insulin analogues.
[0175] In one embodiment of the invention the insulin is an insulin derivative is selected from the group consisting of B29-N ε -myristoyl-des(B30) human insulin, B29-N ε -palmitoyldes(B30) human insulin, B29-N ε -myristoyl human insulin, B29-N ε -palmitoyl human insulin, B28-N ε -myristoyl LyS B28 Pro B29 human insulin, B28-N ε -palmitoyl LyS B28 Pro B29 human insulin, B30-N ε -myristoyl-Thr B29 LyS B30 human insulin, B30-N ε -palmitoyl-Thr B29 LyS B30 human insulin, B29-N ε -(N-palmitoyl-γ-glutamyl)-des(B30) human insulin, B29-N ε -(N-lithocholyl-γ-glutamyl)des(B30) human insulin, B29-N ε -(ω-carboxyheptadecanoyl)-des(B30) human insulin and B29-N ε -(ω-carboxyheptadecanoyl) human insulin.
[0176] In another embodiment of the invention the insulin derivative is B29-N′-myristoyldes(B30) human insulin.
[0177] In a further embodiment of the invention the insulin is an acid-stabilized insulin. The acid-stabilized insulin may be selected from analogues of human insulin having one of the following amino acid residue substitutions:
A21G
A21G, B28K, B29P
A21G, B28D
A21G, B28E
A21G, B3K, B29E
[0178] A21G, desB27
A21G, B9E
A21G, B9D
[0179] A21G, B10E insulin.
[0180] In a further embodiment of the invention the insulin is an insulin analogue. The insulin analogue may be selected from the group consisting of: An analogue wherein position B28 is Asp, Lys, Leu, Val, or Ala and position B29 is Lys or Pro; and des(B28-B30), des(B27) or des(B30) human insulin.
[0181] In another embodiment the analogue is an analogue of human insulin wherein position B28 is Asp or Lys, and position B29 is Lys or Pro.
[0182] In another embodiment the analogue is des(B30) human insulin.
[0183] In another embodiment the insulin analogue is an analogue of human insulin wherein position B28 is Asp.
[0184] In another embodiment the analogue is an analogue wherein position B3 is Lys and position B29 is Glu or Asp.
[0185] In another embodiment the GLP-1 derivative to be employed in combination with a compound of the present invention refers to GLP-1(1-37), exendin-4(1-39), insulinotropic fragments thereof, insulinotropic analogues thereof and insulinotropic derivatives thereof. Insulinotropic fragments of GLP-1(1-37) are insulinotropic peptides for which the entire sequence can be found in the sequence of GLP-1(1-37) and where at least one terminal amino acid has been deleted. Examples of insulinotropic fragments of GLP-1(1-37) are GLP-1(7-37) wherein the amino acid residues in positions 1-6 of GLP-1(1-37) have been deleted, and GLP-1(7-36) where the amino acid residues in position 1-6 and 37 of GLP-1(1-37) have been deleted. Examples of insulinotropic fragments of exendin-4(1-39) are exendin-4(1-38) and exendin-4(1-31). The insulinotropic property of a compound may be determined by in vivo or in vitro assays well known in the art. For instance, the compound may be administered to an animal and monitoring the insulin concentration over time. Insulinotropic analogues of GLP-1(1-37) and exendin-4(1-39) refer to the respective molecules wherein one or more of the amino acids residues have been exchanged with other amino acid residues and/or from which one or more amino acid residues have been deleted and/or from which one or more amino acid residues have been added with the proviso that said analogue either is insulinotropic or is a prodrug of an insulinotropic compound. Examples of insulinotropic analogues of GLP-1(1-37) are e.g. Met 8 -GLP-1(7-37) wherein the alanine in position 8 has been replaced by methionine and the amino acid residues in position 1 to 6 have been deleted, and Arg 34 -GLP-1(7-37), wherein the valine in position 34 has been replaced with arginine and the amino acid residues in position 1 to 6 have been deleted. An example of an insulinotropic analogue of exendin-4(1-39) is Ser 2 Asp 3 -exendin-4(1-39) wherein the amino acid residues in position 2 and 3 have been replaced with serine and aspartic acid, respectively (this particular analogue also being known in the art as exendin-3). Insulinotropic derivatives of GLP-1(1-37), exendin-4(1-39) and analogues thereof are what the person skilled in the art considers to be derivatives of these peptides, i.e. having at least one substituent which is not present in the parent peptide molecule with the proviso that said derivative either is insulinotropic or is a prodrug of an insulinotropic compound. Examples of substituents are amides, carbohydrates, alkyl groups and lipophilic substituents. Examples of insulinotropic derivatives of GLP-1(1-37), exendin-4(1-39) and analogues thereof are GLP-1(7-36)-amide, Arg 34 , Lys 26 (NE-(γ-Glu(N α-hexadecanoyl)))-GLP- 1(7-37) and Tyr 31 -exendin-4(1-31)-amide. Further examples of GLP-1(1-37), exendin-4(1-39), insulinotropic fragments thereof, insulinotropic analogues thereof and insulinotropic derivatives thereof are described in WO 98/08871, WO 99/43706, U.S. Pat. No. 5,424,286 and WO 00/09666.
[0186] In another aspect of the present invention, the present compounds are administered in combination with more than one of the above-mentioned compounds e.g. in combination with metformin and a sulphonylurea such as glyburide; a sulphonylurea and acarbose; nateglinide and metformin; acarbose and metformin; a sulfonylurea, metformin and troglitazone; insulin and a sulfonylurea; insulin and metformin; insulin, metformin and a sulfonylurea; insulin and troglitazone; insulin and lovastatin; etc.
[0187] It should be understood that any suitable combination of the compounds according to the invention with diet and/or exercise, one or more of the above-mentioned compounds and optionally one or more other active substances are considered to be within the scope of the present invention. In one embodiment of the present invention, the pharmaceutical composition according to the present invention comprises e.g. a compound of the invention in combination with metformin and a sulphonylurea such as glyburide; a compound of the invention in combination with a sulphonylurea and acarbose; nateglinide and metformin; acarbose and metformin; a sulfonylurea, metformin and troglitazone; insulin and a sulfonylurea; insulin and metformin; insulin, metformin and a sulfonylurea; insulin and troglitazone; insulin and lovastatin; etc.
Pharmaceutical Compositions
[0188] The compounds of the present invention may be administered alone or in combination with pharmaceutically acceptable carriers or excipients, in either single or multiple doses. The pharmaceutical compositions according to the invention may be formulated with pharmaceutically acceptable carriers or diluents as well as any other known adjuvants and excipients in accordance with conventional techniques such as those disclosed in Remington: The Science and Practice of Pharmacy, 19 th Edition, Gennaro, Ed., Mack Publishing Co., Easton, Pa., 1995.
[0189] The pharmaceutical compositions may be specifically formulated for administration by any suitable route such as the oral, rectal, nasal, pulmonary, topical (including buccal and sublingual), transdermal, intracisternal, intraperitoneal, vaginal and parenteral (including subcutaneous, intramuscular, intrathecal, intravenous and intradermal) route, the oral route being preferred. It will be appreciated that the preferred route will depend on the general condition and age of the subject to be treated, the nature of the condition to be treated and the active ingredient chosen.
[0190] Pharmaceutical compositions for oral administration include solid dosage forms such as hard or soft capsules, tablets, troches, dragees, pills, lozenges, powders and granules. Where appropriate, they can be prepared with coatings such as enteric coatings or they can be formulated so as to provide controlled release of the active ingredient such as sustained or prolonged release according to methods well known in the art.
[0191] Liquid dosage forms for oral administration include solutions, emulsions, aqueous or oily suspensions, syrups and elixirs.
[0192] Pharmaceutical compositions for parenteral administration include sterile aqueous and non-aqueous injectable solutions, dispersions, suspensions or emulsions as well as sterile powders to be reconstituted in sterile injectable solutions or dispersions prior to use. Depot injectable formulations are also contemplated as being within the scope of the present invention.
[0193] Other suitable administration forms include suppositories, sprays, ointments, creams, gels, inhalants, dermal patches, implants, etc.
[0194] A typical oral dosage is in the range of from about 0.001 to about 100 mg/kg body weight per day, preferably from about 0.01 to about 50 mg/kg body weight per day, and more preferred from about 0.05 to about 10 mg/kg body weight per day administered in one or more dosages such as 1 to 3 dosages. The exact dosage will depend upon the frequency and mode of administration, the sex, age, weight and general condition of the subject treated, the nature and severity of the condition treated and any concomitant diseases to be treated and other factors evident to those skilled in the art.
[0195] The formulations may conveniently be presented in unit dosage form by methods known to those skilled in the art. A typical unit dosage form for oral administration one or more times per day such as 1 to 3 times per day may contain from 0.05 to about 1000 mg, preferably from about 0.1 to about 500 mg, and more preferred from about 0.5 mg to about 200 mg.
[0196] For parenteral routes such as intravenous, intrathecal, intramuscular and similar administration, typically doses are in the order of about half the dose employed for oral administration.
[0197] The compounds of this invention are generally utilized as the free substance or as a pharmaceutically acceptable salt thereof. Examples are an acid addition salt of a compound having the utility of a free base and a base addition salt of a compound having the utility of a free acid. The term pharmaceutically acceptable salts refers to non-toxic salts of the compounds of this invention which are generally prepared by reacting the free base with a suitable organic or inorganic acid or by reacting the acid with a suitable organic or inorganic base. When a compound according to the present invention contains a free base such salts are prepared in a conventional manner by treating a solution or suspension of the compound with a chemical equivalent of a pharmaceutically acceptable acid. When a compound according to the present invention contains a free acid such salts are prepared in a conventional manner by treating a solution or suspension of the compound with a chemical equivalent of a pharmaceutically acceptable base. Physiologically acceptable salts of a compound with a hydroxy group include the anion of said compound in combination with a suitable cation such as sodium or ammonium ion. Other salts which are not pharmaceutically acceptable may be useful in the preparation of compounds of the present invention and these form a further aspect of the present invention.
[0198] For parenteral administration, solutions of the novel compounds of the formula (I) in sterile aqueous solution, aqueous propylene glycol or sesame or peanut oil may be employed. Such aqueous solutions should be suitably buffered if necessary and the liquid diluent first rendered isotonic with sufficient saline or glucose. The aqueous solutions are particularly suitable for intravenous, intramuscular, subcutaneous and intraperitoneal administration. The sterile aqueous media employed are all readily available by standard techniques known to those skilled in the art.
[0199] Suitable pharmaceutical carriers include inert solid diluents or fillers, sterile aqueous solution and various organic solvents. Examples of solid carriers are lactose, terra alba, sucrose, cyclodextrin, talc, gelatine, agar, pectin, acacia, magnesium stearate, stearic acid and lower alkyl ethers of cellulose. Examples of liquid carriers are syrup, peanut oil, olive oil, phospholipids, fatty acids, fatty acid amines, polyoxyethylene and water. Similarly, the carrier or diluent may include any sustained release material known in the art, such as glyceryl monostearate or glyceryl distearate, alone or mixed with a wax. The pharmaceutical compositions formed by combining the novel compounds of the present invention and the pharmaceutically acceptable carriers are then readily administered in a variety of dosage forms suitable for the disclosed routes of administration. The formulations may conveniently be presented in unit dosage form by methods known in the art of pharmacy.
[0200] Formulations of the present invention suitable for oral administration may be presented as discrete units such as capsules or tablets, each containing a predetermined amount of the active ingredient, and which may include a suitable excipient. Furthermore, the orally available formulations may be in the form of a powder or granules, a solution or suspension in an aqueous or non-aqueous liquid, or an oil-in-water or water-in-oil liquid emulsion.
[0201] Compositions intended for oral use may be prepared according to any known method, and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents, and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets may contain the active ingredient in admixture with non-toxic pharmaceutically-acceptable excipients which are suitable for the manufacture of tablets. These excipients may be for example, inert diluents, such as calcium carbonate, sodium carbonate, lactose, calcium phosphate or sodium phosphate; granulating and disintegrating agents, for example corn starch or alginic acid; binding agents, for example, starch, gelatin or acacia; and lubricating agents, for example magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate may be employed. They may also be coated by the techniques described in U.S. Pat. Nos. 4,356,108; 4,166,452; and 4,265,874, incorporated herein by reference, to form osmotic therapeutic tablets for controlled release.
[0202] Formulations for oral use may also be presented as hard gelatin capsules where the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin, or a soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, for example peanut oil, liquid paraffin, or olive oil.
[0203] Aqueous suspensions may contain the active compounds in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients are suspending agents, for example sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia; dispersing or wetting agents may be a naturally-occurring phosphatide such as lecithin, or condensation products of an alkylene oxide with fatty acids, for example polyoxyethylene stearate, or condensation products of ethylene oxide with long chain aliphatic alcohols, for example, heptadecaethyl-eneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate, or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides, for example polyethylene sorbitan monooleate. The aqueous suspensions may also contain one or more coloring agents, one or more flavoring agents, and one or more sweetening agents, such as sucrose or saccharin.
[0204] Oily suspensions may be formulated by suspending the active ingredient in a vegetable oil, for example arachis oil, olive oil, sesame oil or coconut oil, or in a mineral oil such as a liquid paraffin. The oily suspensions may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. Sweetening agents such as those set forth above, and flavouring agents may be added to provide a palatable oral preparation. These compositions may be preserved by the addition of an anti-oxidant such as ascorbic acid.
[0205] Dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water provide the active compound in admixture with a dispersing or wetting agent, suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients, for example, sweetening, flavoring, and coloring agents may also be present.
[0206] The pharmaceutical compositions of the present invention may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil, for example, olive oil or arachis oil, or a mineral oil, for example a liquid paraffin, or a mixture thereof. Suitable emulsifying agents may be naturally-occurring gums, for example gum acacia or gum tragacanth, naturally-occurring phosphatides, for example soy bean, lecithin, and esters or partial esters derived from fatty acids and hexitol anhydrides, for example sorbitan monooleate, and condensation products of said partial esters with ethylene oxide, for example polyoxyethylene sorbitan monooleate. The emulsions may also contain sweetening and flavoring and elixirs may be formulated with sweetening agents, for example glycerol, propylene glycol, sorbitol or sucrose. Such formulations may also contain a demulcent, a preservative and flavoring and coloring agents. The pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to the known methods using suitable dispersing or wetting agents and suspending agents described above. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution, and isotonic sodium chloride solution. In addition, sterile, fixed oils are conveniently employed as solvent or suspending medium. For this purpose, any bland fixed oil may be employed using synthetic mono- or diglycerides. In addition, fatty acids such as oleic acid find use in the preparation of injectables.
[0207] The compositions may also be in the form of suppositories for rectal administration of the compounds of the present invention. These compositions can be prepared by mixing the drug with a suitable non-irritating excipient which is solid at ordinary temperatures but liquid at the rectal temperature and will thus melt in the rectum to release the drug. Such materials include cocoa butter and polyethylene glycols, for example.
[0208] For topical use, creams, ointments, jellies, solutions of suspensions, etc., containing the compounds of the present invention are contemplated. For the purpose of this application, topical applications shall include mouth washes and gargles.
[0209] The compounds of the present invention may also be administered in the form of liposome delivery systems, such as small unilamellar vesicles, large unilamellar vesicles, and multilamellar vesicles. Liposomes may be formed from a variety of phospholipids, such as cholesterol, stearylamine, or phosphatidylcholines.
[0210] In addition, some of the compounds of the present invention may form solvates with water or common organic solvents. Such solvates are also encompassed within the scope of the present invention.
[0211] Thus, in a further embodiment, there is provided a pharmaceutical composition comprising a compound according to the present invention, or a pharmaceutically acceptable salt, solvate, or prodrug thereof, and one or more pharmaceutically acceptable carriers, excipients, or diluents.
[0212] If a solid carrier is used for oral administration, the preparation may be tabletted, placed in a hard gelatine capsule in powder or pellet form or it can be in the form of a troche or lozenge. The amount of solid carrier will vary widely but will usually be from about 25 mg to about 1 g. If a liquid carrier is used, the preparation may be in the form of a syrup, emulsion, soft gelatine capsule or sterile injectable liquid such as an aqueous or non-aqueous liquid suspension or solution.
[0213] A typical tablet that may be prepared by conventional tabletting techniques may contain:
Core:
[0214]
[0000]
Active compound (as free compound or salt thereof)
5.0
mg
Lactosum Ph. Eur.
67.8
mg
Cellulose, microcryst. (Avicel)
31.4
mg
Amberlite ® IRP88*
1.0
mg
Magnesii stearas Ph. Eur.
q.s.
*Polacrillin potassium NF, tablet disintegrant, Rohm and Haas.
[0000]
Hydroxypropyl methylcellulose
approx.
9
mg
Mywacett 9-40 T**
approx.
0.9
mg
**Acylated monoglyceride used as plasticizer for film coating.
[0215] If desired, the pharmaceutical composition of the present invention may comprise a compound according to the present invention in combination with further active substances such as those described in the foregoing.
[0216] The present invention also provides a method for the synthesis of compounds useful as intermediates in the preparation of compounds of formula (I) along with methods for the preparation of compounds of formula (I). The compounds can be prepared readily according to the following reaction Schemes (in which all variables are as defined before, unless so specified) using readily available starting materials, reagents and conventional synthesis procedures. In these reactions, it is also possible to make use of variants which are themselves known to those of ordinary skill in this art, but are not mentioned in greater detail.
Pharmacological Methods
Glucokinase Activity Assay (I)
[0217] Glucokinase activity is assayed spectrometrically coupled to glucose 6-phosphate dehydrogenase to determine compound activation of glucokinase. The final assay contains 50 mM Hepes, pH 7.1, 50 mM KCl, 5 mM MgCl 2 , 2 mM dithiothreitol, 0.6 mM NADP, 1 mM ATP, 0.195 μM G-6-P dehydrogenase (from Roche, 127671), 15 nM recombinant human glucokinase. The glucokinase is human liver glucokinase N-terminally truncated with an N-terminal His-tag ((His) 8 -VEQILA . . . Q466) and is expressed in E. coli as a soluble protein with enzymatic activity comparable to liver extracted GK.
[0218] The purification of His-tagged human glucokinase (hGK) was performed as follows: The cell pellet from 50 ml E. coli culture was resuspended in 5 ml extraction buffer A (25 mM HEPES, pH 8.0, 1 mM MgCl 2 , 150 mM NaCl, 2 mM mercaptoethanol) with addition of 0.25 mg/ml lysozyme and 50 μg/ml sodium azide. After 5 minutes at room temperature 5 ml of extraction buffer B (1.5 M NaCl, 100 mM CaCl 2 , 100 mM MgCl 2 , 0.02 mg/ml DNase 1, protease inhibitor tablet (Complete® 1697498): 1 tablet pr. 20 ml buffer) was added. The extract was then centrifugated at 15.000 g for 30 minutes. The resulting supernatant was loaded on a 1 ml Metal Chelate Affinity Chromatography (MCAC) Column charged with Ni 2+ . The column is washed with 2 volumes buffer A containing 20 mM imidazole and the bound his-tagged hGK is subsequently eluted using a 20 minute gradient of 20 to 500 mM imididazol in buffer A. Fractions are examined using SDS-gel-electrophoresis, and fractions containing hGK (MW: 52 KDa) are pooled. Finally a gelfiltration step is used for final polishing and buffer exhange. hGK containing fractions are loaded onto a Superdex 75 (16/60) gelfiltration column and eluted with Buffer B (25 mM HEPES, pH 8.0, 1 mM MgCl 2 , 150 mM NaCl, 1 mM Dithiothreitol). The purified hGK is examined by SDS-gel electrophoresis and MALDI mass spectrometry and finally 20% glycerol is added before freezing. The yield from 50 ml E. coli culture is generally approximately 2-3 mg hGK with a purity >90%.
[0219] The compound to be tested is added into the well in final 2.5% DMSO concentration in an amount sufficient to give a desired concentration of compound, for instance 1, 5, 10, 25 or 50 μM. The reaction starts after glucose is added to a final concentration of 2, 5, 10 or 15 mM. The assay uses a 96-well UV plate and the final assay volume used is 200 μl/well. The plate is incubated at 25° C. for 5 min and kinetics is measured at 340 nm in SpectraMax every 30 seconds for 5 minutes. Results for each compound are expressed as the fold activation of the glucokinase activity compared to the activation of the glucokinase enzyme in an assay without compound after having been subtracted from a “blank”, which is without glucokinase enzyme and without compound. The compounds in each of the Examples exhibit activation of glucokinase in this assay. A compound, which at a concentration of at or below 30 μM gives 1.5-fold higher glucokinase activity than the result from the assay without compound, is deemed to be an activator of glucokinase.
[0220] The glucose sensitivity of the compounds are measured at a compound concentration of 10 μM and at glucose concentrations of 5 and 15 mM.
Glucokinase Activity Assay (II)
Determination of Glycogen Deposition in Isolated Rat Hepatocytes:
[0221] Hepatocytes are isolated from rats fed ad libitum by a two-step perfusion technique. Cell viability, assessed by trypan blue exclusion, is consistently greater than 80%. Cells are plated onto collagen-coated 96-well plates in basal medium (Medium 199 (5.5 mM glucose) supplemented with 0.1 μM dexamethasone, 100 units/ml penicillin, 100 mg/ml streptomycin, 2 mM L-glutamine and 1 nM insulin) with 4% FCS at a cell density of 30,000 cells/well. The medium is replaced with basal medium 1 hour after initial plating in order to remove dead cells. Medium is changed after 24 hours to basal medium supplemented with 9.5 mM glucose and 10 nM insulin to induce glycogen synthesis, and experiments are performed the next day. The hepatocytes are washed twice with prewarmed (37° C.) buffer A (117.6 mM NaCl, 5.4 mM KCl, 0.82 mM Mg 2 SO 4 , 1.5 mM KH 2 PO 4 , 20 mM HEPES, 9 mM NaHCO 3 , 0.1% w/v HSA, and 2.25 mM CaCl 2 , pH 7.4 at 37° C.) and incubated in 100 μl buffer A containing 15 mM glucose and increasing concentrations of the test compound, such as for instance 1, 5, 10, 25, 50 or 100 μM, for 180 minutes. Glycogen content is measured using standard procedures (Agius, L. et al, Biochem J. 266, 91-102 (1990). A compound, which when used in this assay gives an significant increase in glycogen content compared to the result from the assay without compound, is deemed to have activity in this assay.
Glucokinase Activity Assay (III)
Stimulation of Insulin Secretion by Glucokinase Activators in Ins-1E Cells
[0222] The glucose responsive β-cell line INS-1E is cultivated as described by Asfari M et al., Endocrinology, 130, 167-178 (1992). The cells are then seeded into 96 well cell culture plates and grown to a density of approximately 5×10 4 per well. Stimulation of glucose dependent insulin secretion is tested by incubation for 2 hours in Krebs Ringer Hepes buffer at glucose concentrations from 2.5 to 15 mM with or without addition of glucokinase activating compounds in concentrations of for instance 1, 5, 10, 25, 50 or 100 μM, and the supernatants collected for measurements of insulin concentrations by ELISA (n=4). A compound, which when used in this assay gives an significant increase in insulin secretion in response to glucose compared to the result from the assay without compound, is deemed to have activity in this assay.
[0223] 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 (to the maximum extent permitted by law).
[0224] 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.
[0225] 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) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
[0226] 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 and should be read as encompassing the phrases “consisting”, “substantially comprised of,” and “consisting essentially of” (e.g., where a disclosure of a composition “comprising” a particular ingredient is made, it should be understood that the invention also provides an otherwise identical composition characterized by, in relevant part, consisting essentially of the ingredient and (independently) a composition consisting solely of the ingredient).
[0227] 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. Unless otherwise stated, all exact values provided herein are representative of corresponding approximate values (e.g., all exact exemplary values provided with respect to a particular factor or measurement can be considered to also provide a corresponding approximate measurement, modified by “about,” where appropriate).
[0228] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.
[0229] 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.
[0230] The citation and incorporation of patent documents herein is done for convenience only and does not reflect any view of the validity, patentability, and/or enforceability of such patent documents.
[0231] While the invention has been described and illustrated with reference to certain preferred embodiments thereof, those skilled in the art will appreciate that various changes, modifications and substitutions can be made therein without departing from the spirit and scope of the present invention. For example, effective dosages other than the preferred dosages as set forth herein may be applicable as a consequence of variations in the responsiveness of the mammal being treated for glucokinase-deficiency mediated disease(s). Likewise, the specific pharmacological responses observed may vary according to and depending on the particular active compound selected or whether there are present pharmaceutical carriers, as well as the type of formulation and mode of administration employed, and such expected variations or differences in the results are contemplated in accordance with the objects and practices of the present invention.
EXAMPLES
[0232] Abbreviations used in the Schemes and Examples are as follows:
d=day(s)
g=gram(s)
h=hour(s)
MHz=mega hertz
L=liter(s)
M=molar
mg=milligram(s)
min=minute(s)
mL=milliliter(s)
mM=millimolar
mmol=millimole(s)
mol=mole(s)
N=normal
ppm=parts per million
i.v.=intravenous
m/z=mass to charge ratio
mp=melting point
MS=mass spectrometry
HPLC=high pressure liquid chromatography
HPLC-MS=high pressure liquid chromatography-mass spectrometry
NMR=nuclear magnetic resonance spectroscopy
p.o.=per oral
R t =retention time
rt=room temperature
s.c.=subcutaneous
TLC=thin layer chromatography
BuOK=Potassium tert-butoxide
Boc=tert-Butyloxcarbonyl
CDI=carbonyldiimidazole
DBU=1,8-Diazabicyclo[5.4.0]-undec-7-en
DCM (CH 2 Cl 2 )=dichloromethane, methylenechloride
DHOBt=3,4-Dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine
DIC=1,3-Diisopropyl carbodiimide
DCC=1,3-Dicyclohexyl carbodiimide
DIEA=N,N-diisopropylethylamine
DIPEA=N,N-diisopropylethylamine
DMA=N,N-dimethylacetamide
DMAP=4-(N,N-dimethylamino)pyridine
DMF=N,N-dimethylformamide
DMF=N,N-dimethylformamide
[0233] DMPU=NN′-dimethylpropyleneurea, 1,3-dimethyl-2-oxohexahydropyrimidine
EDAC=1-(3-Dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride
Et 2 O=diethyl ether
EtOAc=ethyl acetate
HMPA=hexamethylphosphoric acid triamide
HOBt=N-Hydroxybenzotriazole
HOAt=7-Aza-1-Hydroxybenzotriazole
[0234] LAH, (LiAlH 4 )=Lithiumaluminium hydride
LDA=lithium diisopropylamide
MeCN=acetonitrile
MeOH=methanol
NMP=N-methylpyrrolidin-2-one
NaH=Sodium Hydride
NH 2 OH=Hydroxylamine
[0235] PyBroP=Bromotrispyrrolidinophosphonium hexafluorophosphate
TEA (Et 3 N)=triethylamine
TFA=trifluoroacetic acid
THF=tetrahydrofuran
CDCl 3 =deuterio chloroform
CD 3 OD=tetradeuterio methanol
DMSO-d 6 =hexadeuterio dimethylsulfoxide
NMR
[0236] Proton NMR spectra were recorded at ambient temperature using a Brucker Avance DPX 200 (200 MHz), Brucker Avance DPX 300 (300 MHz) and Brucker Avance DPX 400 (400 MHz) with tetramethylsilane as an internal standard. Chemical shifts (δ) are given in ppm
HPLC-MS
[0237] The following instrumentation is used:
[0000] Hewlett Packard series 1100 G1312A Bin Pump
Hewlett Packard series 1100 Column compartment
Hewlett Packard series 1100 G1315A DAD diode array detector
Hewlett Packard series 1100 MSD
Sedere 75 Evaporative Light Scattering detector
[0238] The instrument is controlled by HP Chemstation software.
[0239] The HPLC pump is connected to two eluent reservoirs containing:
[0000]
Methode A:
0.01% TFA in water
Methode B:
0.01% TFA in acetonitrile
[0240] The analysis is performed at 40° C. by injecting an appropriate volume of the sample (preferably 1 μl) onto the column which is eluted with a gradient of acetonitrile.
[0241] The HPLC conditions, detector settings and mass spectrometer settings used are given in the following table.
[0000]
Column
Waters Xterra MS C-18 X 3 mm id 5 μm
Gradient
5%-100% acetonitrile linear during 7.5 min at 1.5
mL/min
Detection
210 nm (analogue output from DAD)
ELS (analogue output from ELS)
MS
ionisation mode API-ES
Scan 100-1000 amu step 0.1 amu
[0242] After the DAD the flow is divided yielding approximately 1 mL/min to the ELS and 0.5 mL/min to the MS.
General
[0243] The following examples and general procedures refer to intermediate compounds and final products for general formula (I) identified in the specification and in the synthesis schemes.
[0244] The preparation of the compounds of general formula (I) of the present invention is described in detail using the following examples. Occasionally, the reaction may not be applicable as described to each compound included within the disclosed scope of the invention. The compounds for which this occurs will be readily recognised by those skilled in the art. In these cases the reactions can be successfully performed by conventional modifications known to those skilled in the art, which is, by appropriate protection of interfering groups, by changing to other conventional reagents, or by routine modification of reaction conditions. Alternatively, other reactions disclosed herein or otherwise conventional will be applicable to the preparation of the corresponding compounds of the invention. In all preparative methods, all starting materials are known or may be prepared by a person skilled in the art in analogy with the preparation of similar known compounds or by the General procedures A through G described herein.
[0245] The structures of the compounds are confirmed by either by nuclear magnetic resonance (NMR) and/or by HPLS-MS.
General Reaction Schemes
[0246] The compounds of formula (I) according to the invention wherein R 1 , R 2 , R 3 and R 4 are as defined in formula (I) can be prepared as outlined in Scheme 1 and Scheme 2. The starting material can be either commercial available compounds or compounds that can be prepared following procedures described in the literature or prepared as described in the relevant examples and general procedures.
[0247] In Scheme 1 a secondary amine of general structure (II) can be treated with phosgene or related analogue (for example triphosgene, carbonyl diimidazole etc) in a solvent such as tetrahydrofuran or dichloromethane. The product carbamoyl chloride (III) can be treated with the anion prepared via reaction of urea (IV) and sodium hydride (J. Org. Chem. 1973, 38, 3868) to give compounds of general formular (Ia).
[0000]
[0248] In Scheme 2, chlorocarbonyl isocyanate can be treated sequentially with amines (II) and (VI) in a solvent such as tetrahydrofuran or dichloromethane to give compounds of general structure (I). (Tetrahedron 1993, 49, 3227).
[0000]
General Procedures
General Procedure 1
[0249] To urea (IV) (Scheme 1) in tetrahydrofuran was added sodium hydride (1-3 equivalents) and the reaction mixture stirred for 50 min at room temp. The carbamoyl chloride (III) was then added (ice bath cooling used during addition) and the mixture was stirred overnight at room temperature. The reaction mixture was added to 0.5 ml water, partially concentrated in vacuo and water (2 mL) and ethyl acetate (10 mL) was added. The non soluble material was filtered off and the organic layer collected and concentrated in vacuo. The crude product was then dissolved in tetrahydrofuran and purified by chromatography to give the desired product (Ia) wherein R 1 , R 2 , R 3 and R 4 are as defined in formula (Ia).
General Procedure 2.
[0250] To compound (V) (Scheme 2) (commercially available) in tetrahydrofuran at −20-0° C. was added amine (II) and triethylamine. After 20 min amine (VI) was added and the reactionallowed to warm to room temperature over 3 h. The reaction mixture was partially concentrated. The crude product was then dissolved in tetrahydrofuran and purified by LCMS to the desired product (Ia) wherein R 1 , R 2 , R 3 and R 4 are as defined in formula (Ia).
Example 1
1,1-Bis-(cyclohexyl)-5-methyl biuret
[0251]
[0252] Prepared as described in General Procedure 1. To methyl urea (0.24 g) in tetrahydrofuran was added sodium hydride (22 mg of 60% in oil) and the reaction mixture stirred for 50 min at room temp. Dicyclohexyl carbamoyl chloride (0.8 g) was then added (ice bath cooling used during addition) and the mixture was stirred overnight. The reaction mixture was then added to 0.5 ml water, partially concentrated in vacuo and water (2 mL) and ethyl acetate (10 mL) was added. The non soluble material was removed by filtration and the organic layer collected and concentrated in vacuo. An aliquot of the crude was then dissolved in THF and purified by preparative LCMS to give the desired product (8 mg).
[0253] 1 H NMR (CDCl 3 ): δ 1.10-1.90 (m, 20H), 2.33 (d, 3H), 3.22-3.40 (m, 2H), 6.65 (s, 1H), 8.45 (s, 1H).
[0254] HPLC-MS: m/z=282.1 (M+1)
Example 2
1,1-Bis-(cyclohexyl)-5-butyl biuret
[0255]
[0256] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and butyl urea.
[0257] HPLC-MS (Method A): m/z=324.2 (M+1)
Example 3
1,1-Bis-(cyclohexyl)-5-(3-pyridylmethyl) biuret
[0258]
[0259] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and 1-(3-pyridylmethyl)urea.
[0260] HPLC-MS (Method B): m/z=359.2 (M+1)
Example 4
1,1-Bis-(cyclohexyl)-5-(4-fluorobenzyl) biuret
[0261]
[0262] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and 4-fluorobenzyl urea.
[0263] HPLC-MS (Method A): m/z=376.2 (M+1)
Example 5
1,1-Bis-(cyclohexyl)-5-(3-chlorobenzyl) biuret
[0264]
[0265] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and 3-chlorobenzyl urea.
[0266] HPLC-MS (Method A): m/z=392.2 (M+1)
Example 6
1,1-Bis-(cyclohexyl)-5-(o-tolyl) biuret
[0267]
[0268] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and otolylurea.
[0269] HPLC-MS (Method A): m/z=358.2 (M+1)
Example 7
1,1-Bis-(cyclohexyl)-5-(2,2,2-trifluoroethyl) biuret
[0270]
[0271] Prepared as described in General Procedure 1 using dicyclohexyl carbamoyl chloride and N-2,2,2-trifluoroethylurea.
[0272] HPLC-MS (Method A): m/z=350.1 (M+1)
Example 8
1,1-Bis-(cyclohexyl)-5-(2-thiazolyl) biuret
[0273]
[0274] Prepared as described in General Procedure 2. To chlorocarbonyl isocyanate (0.2 g) in tetrahydrofuran at −20-0° C. was added dicyclohexylamine (1 equivalent) and triethylamine (0.27 mL). After 20 min 2-aminothiazole (0.2 g) was added and the reaction allowed to warm to room temperature over 3 h and stirred overnight at room temperature. The reaction mixture was partially concentrated. The crude product was then dissolved in tetrahydrofuran and purified by flash chromatography (Eluant 20 dichloromethane:1 methanol).
[0275] HPLC-MS (Method A): m/z=351.6 (M+1)
Example 9
1,1-Bis-(cyclohexyl)-5-ethyl biuret
[0276]
[0277] Prepared as described in General Procedure 2 using dicyclohexylamine and ethylamine.
[0278] HPLC-MS (Method A): m/z=296.7 (M+1)
Example 10
1,1-Bis-(cyclohexyl)-5-cyclopropyl biuret
[0279]
[0280] Prepared as described in General Procedure 2 using dicyclohexylamine and cyclopropylamine.
[0281] HPLC-MS (Method A): m/z=308.6 (M+1)
Example 11
1,1-Bis-(cyclohexyl)-5-(2-pyridylmethyl) biuret
[0282]
[0283] Prepared as described in General Procedure 2 using dicyclohexylamine and 2-(aminomethyl)pyridine.
[0284] HPLC-MS (Method A): m/z=359.7(M+1)
Example 12
1,1-Bis-(cyclohexyl)-5-(4-methoxybenzyl) biuret
[0285]
[0286] Prepared as described in General Procedure 2 using dicyclohexylamine and 4-methoxybenzylamine.
[0287] HPLC-MS (Method A): m/z=388.6 (M+1)
Example 13
1,1-Bis-(cyclohexyl)-5-(2-pyridyl) biuret
[0288]
[0289] Prepared as described in General Procedure 2 using dicyclohexylamine and 2-aminopyridine.
[0290] HPLC-MS (Method A): m/z=345.5 (M+1)
Example 14
1,1-Bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0291]
[0292] 1,1-Bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid ethyl ester) biuret was prepared as described in General Procedure 2 and 3 using chlorocarbonyl isocyanate, dicyclohexylamine and 2-aminothiazole-5-sulfanylacetic acid ethyl ester. Ester hydrolysis using sodium hydroxyide (1 N) in methanol at room temperature afforded the title compound.
[0293] HPLC-MS (Method A): m/z=441, R t =2.29 min
Example 15
1-(trans-4-Methylcyclohexyl)-1-isobutyl-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0294]
[0295] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using 1-(trans-4-methylcyclohexyl)-1-isobutylamine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate.
[0296] HPLC-MS (Method A): m/z=433, R t =2.35 min
Example 16
1-(trans-Methylcyclohexyl)-1-cyclohexyl-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0297]
[0298] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate.
[0299] HPLC-MS (Method A): m/z=455, R t =2.43 min
Example 17
1-(trans-Propyloxycyclohexyl)-1-cyclohexyl-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0300]
[0301] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using 1-(trans-4-ethyloxycyclohexyl)-1-cyclohexylamine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate.
[0302] HPLC-MS (Method A): m/z=499, R t =2.28 min
Example 18
1-(trans-4-Methylcyclohexyl)-1-butyl-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0303]
[0304] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using 1-(trans-4-methylcyclohexyl)-1-butylamine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate.
[0305] HPLC-MS (Method A): m/z=429, R t =2.24 min
Example 19
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(propionic acid) biuret
[0306]
[0307] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine,
3-amino propionic acid ethyl ester and chlorocarbonyl isocyanate.
[0309] HPLC-MS (Method A): m/z=354, R t =2.03 min
Example 20
1-(trans-4-Methylcyclohexyl)-1-cyclohexylmethyl-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0310]
[0311] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using 1-(trans-4-methylcyclohexyl)-1-cyclohexylmethylamine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate.
[0312] HPLC-MS (Method A): m/z=469, R t =1.39 min
Example 21
1-(trans-4-Methylcyclohexyl)-1-cyclopentylmethyl5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret
[0313]
[0314] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using 1-(trans-4-methylcyclohexyl)-1-cyclopentylmethylamine, 2-aminothiazole-5-sulfanylacetic acid ethyl ester and chlorocarbonyl isocyanate
[0315] HPLC-MS (Method A): m/z=368, R t =2.09 min
Example 22
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(butanoic acid) biuret
[0316]
[0317] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, 4-aminobutanoic acid ethyl ester and chlorocarbonyl isocyanate.
[0318] HPLC-MS (Method A): m/z=368, R t =2.09 min
Example 23
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(1-trifluoromethyl-propionic acid) biuret
[0319]
[0320] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, 3-amino-2-trifluoropropionic acid ethyl ester and chlorocarbonyl isocyanate.
[0321] HPLC-MS (Method A): m/z=422, R t =2.30 min
Example 24
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(methyl-4-carboxybenzoic acid) biuret
[0322]
[0323] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, 4-aminomethyl-benzoic acid ethyl ester and chlorocarbonyl isocyanate.
[0324] HPLC-MS (Method A): m/z=416, R t =2.31 min
Example 25
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(trans-4-carboxycyclohexylmethyl) biuret
[0325]
[0326] The title compound was prepared in a similar manner as described for 1,1-bis-(cyclohexyl)-5-(2-thiazolyl-5-sulfanyl-acetic acid) biuret using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, 4-aminomethyl-cyclohexanoic acid ethyl ester and chlorocarbonyl isocyanate.
[0327] HPLC-MS (Method A): m/z=422, R t =2.31 min
Example 26
1-(trans-4-Methylcyclohexyl)-1-cyclohexyl-5-(pyrrolidone-N-propyl)) biuret
[0328]
[0329] The title compound was prepared in a similar manner as described in General Procedure 2 using cyclohexyl-(4-trans-methyl-cyclohexyl)-amine, aminopropylpyrrolidine and chlorocarbonyl isocyanate.
[0330] HPLC-MS (Method A): m/z=407, R t =2.10 min | This invention relates to dicycloalkylcarbamoyl ureas of formula (I), which are activators of glucokinase and thus may be useful for the management, treatment, control, or adjunct treatment of diseases, where increasing glucokinase activity is beneficial. | 2 |
PRIORITY DATA
[0001] This application is a divisional of U.S. patent application Ser. No. 10/228,785 filed on Aug. 26, 2002 which claims priority from Swedish Pat. Appln. No. 0200911-6, filed Mar. 22, 2002, all of which are incorporated herein in their entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a phytase active yeast, in particular a modified Saccharomyces cerevisiae used for fermentation purposes, fermented products after fermentation using said modified Saccharomyces cerevisiae, the use of phytase obtained using said strain, as well as derived inositol phosphate derivatives including myoinositol.
[0003] Iron deficiency is one of the most common nutrition disorders worldwide. In addition to affecting a large proportion of infants, children and women in the developing world, iron deficiency is the only nutrient deficiency of significant prevalence in all developed nations as well. Deficiency of iron and probably zinc are highly prevalent in developing countries, where the diet is based on cereals and legumes but also in vulnerable population groups, in industrialized countries, with high requirements such as women of fertile age, infants and adolescents. In developing countries iron deficiency, due to poor bioavailability, retards normal brain development in infants and effects the success of a pregnancy by increasing premature deliveries, as well as morbidity of mother and child at or around child-birth. Zinc deficiency prevents normal child growth and greatly weakens the immune system leading to more infections. The body requires a high amount of calcium during growth. The amount of bone in later years is determined by the starting amount (the peak bone mass) and it's subsequent loss. Both are directly relevant for the subsequent development of osteoporosis.
[0004] Mild to moderate iron deficiency is often not recognized, but nevertheless may affect poorly defined parameters such as normal vigour, physical and mental endurance, and quality of life.
[0005] Iron deficiency is caused primarily by chronic blood loss. Using approximate values, inescapable loss of iron in sweat and cellular desquamation amounts to 1-2 mg per day. This is readily balanced in men by the absorption of 10% of the average dietary intake of 10-15 mg daily. In women of fertile ages, however, menstrual bleeding adds another 1 mg to the daily loss, making it more difficult to achieve an adequate balance.
[0006] Several haematologic and biochemical tests are well established for screening or diagnosis of iron deficiency individuals as well as for population based assessment.
[0007] The amount of iron absorbed from the diet at any one time is dependent on three factors: the quantity of iron, the composition of the diet and the behavior of the mucosa of the upper small bowel. Variation in the bioavailability (the portion of total iron in the diet absorbed and utilized by the organism) of food iron are of greater importance for iron nutrition than is the amount of iron in the diet. The haem iron in meat, poultry and fish is easily absorbed whatever the dietary composition whereas non-heme iron is markedly influenced by other ingredients in the diet. A number of promoters and inhibitors of iron absorption have been identified. The bioavailability of the iron in any particular diet ultimately depends on the relative quantities of promoters and inhibitors of iron absorption present in that diet.
[0008] Although the element is the second most abundant metal in the earth's crust, its low solubility makes its acquisition for metabolic use a major challenge. Most environmental iron exists as insoluble salts. Gastric acidity assists the conversion to absorbable forms, but the efficiency of this process is limited. Many plants produce powerful chelators, such as the phytate (organic polyphosphate), which are potent inhibitors of iron absorption found in e.g., cereals and legumes.
[0009] Zinc is a component of more than 300 enzymes needed to repair wounds, maintain fertility in adults and growth in children, synthesize protein, help cells reproduce, preserve vision, boost immunity, and protect against free radicals, among other functions.
[0010] Zinc deficiency is common in individuals or populations whose diets are low in sources of readily bioavailable zinc, such as meat, and high in unrefined cereals that are rich in phytate, a diet common in the poorer areas of the world. Vegetarian or lacto-vegetarian diets overall result in high intake of phytate, which is accompanied by a greater risk of zinc deficiency. Zinc deficiency in human caused by nutrition was first described in adolescent boys and girls in Egypt and Iran in the late 1960:s and early 1970's. The symptoms were severe growth failure, hypogonadism with delayed sexual maturation. The cause of the deficiency was a diet based on unleavened wholemeal bread with a high content of phytate and low intake of animal protein. Treatment with zinc and an adequate intake of other nutrients improved growth and sexual maturation. Dietary zinc deficiency has later been described among the children of many countries, such as Turkey, China and Yugoslavia,. Another group at risk are pregnant women.
[0011] Other clinical manifestations of zinc deficiency than mentioned above are suppressed immunity, poor healing, dermatitis and impairments in neuropsychological functions.
[0012] The diagnosis of zinc deficiency is a problem while sensitive indices of zinc status are lacking. The most widely used indices of zinc status are levels of zinc in plasma or serum. These parameters may be decreased in cases of severe and moderate deficiency. Dietary data and indirect measures of bone health indicate that the bioavailability of calcium is important when habitual intakes are low, especially during periods of bone growth or loss. Bioavailability of calcium was found to be low in diets high in unrefined cereals, that are rich in phytate.
[0013] Cereals, together with oil seeds and legumes, supply a majority of the dietary protein, calories, vitamins, and minerals to the bulk population. Phosphorous, potassium, magnesium, calcium and traces of iron and other minerals are found in cereals. Barley and wheat provide 50 and 36 mg Ca/100 g respectively. Barley provides 6 mg of iron per 100 g; millet provides 6.8; oats, 4.6 and wheat, 3.1.
[0014] Inositol hexaphosphate, IP6, is ubiquitous in nature and comprises the bulk of eukaryotic cell inositol phosphate content. In plants, IP6 constitutes the principal storage form of phosphorous, in particular whole grains of cereals and legumes are rich in IP6. In cereals phytate is located in bran and germ, whereas in legume seeds phytate occurs in the protein bodies in the endosperm. The highly negatively charged IP6 forms various complexes with minerals and proteins, commonly known as phytate. Phytate is considered an anti-nutrient due to the formation of precipitated complexes that strongly reduces the absorption of essential dietary minerals such as iron, zinc, calcium and magnesium. A dose dependent inhibition of iron, zinc and calcium absorption by phytate has been demonstrated in humans. Moreover, inositol penta phosphate has been identified as an inhibitor of iron and zinc absorption. In addition, it has been suggested that IP6 may influence negatively on solubility, digestibility and activity of proteins such as digesting enzymes Reddy et al. Reduction in antinutritional and toxic components in plant foods by fermentation. Food Res. Int. 27, 281-290. Degradation of phytate to low levels in cereal and legume meals was demonstrated to markedly improve iron and zinc absorption in humans. To improve iron absorption the degradation has to be virtually complete. Thus, once phytate is degraded these foods become a good source of dietary minerals.
[0015] Degradation of phytate is possible with phytases. Native phytase in some cereals may be active during traditional processing such as soaking, germination, malting and fermentation and phytate degradation can be improved by process optimization, selection of specific starter cultures, or phytase can be added. It has also been demonstrated that phytate degradation in the stomach and small intestine of humans occurs as a result of activity of dietary phytase of plant or microbial origin thereby improving iron and zinc absorption. Consumption of foods containing active phytase enzymes is therefor an alternative to phytate removal during food processing. The plant phytase is less stable than the microbial phytase at the physiological conditions of the gastro-intestine and is therefor less effective in this respect.
[0016] Since IP6 is such a common compound in nature some microorganisms would be expected to have the ability to degrade IP6 and utilize the hydrolyzed phosphorous. This is true for certain bacteria, Riedereret al. (1991) Removal of N - glycosylation sites of the yeast acid phosphatase severely affects protein folding. J. Bacteriol. 173, 3539-3546 and many fungi, Shieh et al. (1968) Survey of microorganism for the production of extracellular phytase. Appl. Microbiol. 16, 1348-1351; Dvoráková et al. (1997) Characterization of phytase produced by Aspergillus niger. Folia Microbiol. 42, 349-352; Wyss et al. (1998) Comparison of the thermostability properties of three acid phosphatases from molds: Aspergillus fumigatus phytase, A. niger phytase, and A. niger pH 2.5 acid phosphatase. Appl. Environ. Microbiol. 64, 4446-4451, that are well known to synthesize secretory so called phytases, i.e. phosphatases hydrolyzing IP6 to inositol pentaphosphate (IP5) and inorganic ortho-phosphate (P i ). Phytases, derived from Aspergillus sp are frequently used in animal feeds to improve phosphorous and mineral availability, and much research is devoted to further improve these by e.g. molecular enzyme engineering, Wyss et al. (1999) Biophysical characterization of fungal phytases ( myo - inositol hexakisphosphate phosphohydrolases ): molecular size, glycosylation pattern, and engineering of proteolytic resistance. Appl. Environ. Microbiol. 65, 359-366. For humans, however, no corresponding approved (food grade) enzyme is available. One way to improve the mineral state in vulnerable human populations may be to explore yeasts, that with their GRAS—(generally regarded as safe) status are preferable microorganisms in human foods. The natural yeast phytase activity during for instance bread leavening, however, seems too low to significantly influence the iron absorption when eating foods fermented by yeast, such as bread, Türk et al. (1996) Reduction in the levels of phytate during wholemeal bread making; Effect of yeast and wheat phytases. J. Cereal Science. 23, 257-264.
[0017] It is further noted that it is known from the patent literature that yeasts, such as Pichia rhodanensis (JP2000050864), Arxula adeninivorans (JP2000050863), Candida boidinii (EP 0 931 837), Saccharomyces cerevisiae (WO2001036607) may comprise genes for expression of phytase.
[0018] Greiner et al, J. Agric. Food Chem. (2001) 49(5), 2228-2233 relates to production of stereospecific myo-inositol hexaphosphate by using baker's yeast phytase.
[0019] Nakamura, et al, Biosci. Biotechnol. Biochem (2000), 64(4), 841-844 describe dephosphorylation of inositol using baker's yeast.
[0020] Turk et al, J. Agric. Food Chem. (2000), 48(1), 100-104 describes that phosphorous is stored in plants as phytates, and discusses the negative effect on mineral bioavailability and shows the ability of Saccharomyces cerevisiae to reduce phytate by its phytase production.
[0021] The PHO gene family has been extensively studied in Saccharomyces cerevisiae, Yoshida et al. (1989) Function of the PHO regulatory genes for repressible acid phosphatase synthesis in Saccharomyces cerevisiae. Mol. Gen. Genet. 217, 40-46; Ogawa et al. (2000) New components of a system for phosphate accumulation and polyphosphate metabolism in Saccharomyces cerevisiae revealed by genomic expression analysis. Mol. Biol. Cell. 11, 4309-4321, however, not in the context of IP6 as the substrate. The secretory acid phosphatases encoded by the structural genes PH03, PH05, PH010 and PH011 all seem to be aimed for hydrolyzing extracellular organic phosphorous compounds allowing the yeast to grow in the absence of inorganic phosphate. All except PH03 are repressed by inorganic phosphate, whereas PH03 is repressed by thiamine present in the external environment, Praekelt et al. (1994) Regulation of THI4 (MOL1), a thiamine-biosynthetic gene of Saccharomyces cerevisiae. Yeast. 10, 481-490. PH03 is therefore suggested to primarily hydrolyze phosphate from thiamine phosphate or thiamine pyro-phosphate; Nosakaet al. (1989) A possible role for acid phosphatase with thiamin-binding activity encoded by PHO3 in yeast. FEMS Microbiol. Lett. 51, 55-59; Nosaka (1990) High affinity of acid phosphatase encoded by PHO3 gene in Saccharomyces cerevisiae for thiamin phosphates. Biochim. Biophys. Acta. 1037, 147-154
[0022] PH05 is often described as responsible for the major fraction of secretory acid phosphatase activity whereas PH010 and PH011 encode a minor fraction of secretory phosphatase, Rogers, D. T., Lemire, J. M. and Bostian, K. A. (1982) Acid phosphatase polypeptides in Saccharomyces cerevisiae are encoded by a differentially regulated multigene family. Proceedings of the National Academy of Sciences of the United States of America. 79, 2157-2161; Lemire et al. (1985) Regulation of repressible acid phosphatase gene transcription in Saccharomyces cerevisiae. Mol. Cell Biol. 5, 2131-2141, that may be lowly and constitutively expressed. In addition to the enzymes, several components within the PHO system are regulatory proteins, such as Pho4p and Pho2p which are transcriptional activators for PH05, PH010 and PH011, Vogel et al. (1989) The two positively acting regulatory proteins Pho2p and Pho4p physically interact with PHO5 upstream activation regions. Mol. Cell. Biol. 9, 2050-2057
[0023] A single study approaches the question of level of phytase activity derived from specific S. cerevisiae phosphatase encoding genes, Moore et al. (1995) Molecular cloning, expression and evaluation of phosphohydrolases for phytate-degrading activity. J. Ind. Microbiol. 14, 396-402. In that work, however, the yeast genes were all expressed in Aspergillus leading to uncertainty in factors such as copy number, levels of glycosylation and secretion as well as to what extent the genes contribute to phytase activity in S. cerevisiae. The opposite approach was taken by Han et al, Han et al. (1999) Expression of an Aspergillus niger phytase gene (phyA) in Saccharomyces cerevisiae. Appl. Environ. Microbiol. 65, 1915-1918, who instead expressed the Aspergillus niger phytase gene (phyA) in S. cerevisiae, to explore an alternative expression system for a well-known phytase.
SUMMARY OF INVENTION
[0024] Broadly, the invention includes a process for preparing a Saccharomyces cerevisiae yeast strain having improved phytase activity comprising modifying the strain by inserting one or more of the PHO5, PHO10, PHO11, DIA3, PHO2 and/or PHO4 genes, and/or by deleting one or more of the negative regulatory genes PHO80, PHO85, and/or PHO23, whereby the insertion is either chromosomal or by transforming the strain using a plasmid containing the gene/s. The modified strain overexpresses one or more the PHO5, PHO10, PHO11, DIA3, PHO2 and/or PHO4 genes.
[0025] In a preferred embodiment the modified Saccharomyces cerevisiae overexpresses PHO5.
[0026] In another preferred embodiment the modified Saccharomyces cerevisiae overexpresses PHO10.
[0027] In a further preferred embodiment the modified Saccharomyces cerevisiae overexpresses PHO11.
[0028] In another preferred embodiment the modified Saccharomyces cerevisiae overexpresses PHO2.
[0029] In another preferred embodiment the modified Saccharomyces cerevisiae overexpresses PHO4.
[0030] In another preferred embodiment the modified Saccharomyces cerevisiae overexpresses DIA3.
[0031] In a further preferred embodiment of the invention the modified Saccharomyces cerevisiae is a strain, wherein the negatively regulating gene PHO80 has been deleted to form a mutant pho80Δ.
[0032] In order to further increase phytase activity, other genes belonging to the PHO family like the genes encoding for phytase or some transcription regulators, such as PHO2 and PHO4, may eventually have to be over-expressed alone or in combination with other genetic modifications, such as pho80 or pho85 mutations.
[0033] In another preferred embodiment of the invention the modified Saccharomyces cerevisiae is a strain, wherein the negatively regulating gene PHO85 has been deleted to form a mutant pho85Δ.
[0034] In a further preferred embodiment of the invention the modified Saccharomyces cerevisiae over expresses the positively regulating gene PHO2.
[0035] In a further preferred embodiment of the invention the modified Saccharomyces cerevisiae over expresses the positively regulating gene PHO4.
[0036] In accordance with a further aspect of the invention, the invention includes a fermented product having been fermented using a Saccharomyces cerevisiae strain identified above, and having a reduced content of inositol hexaphosphate.
[0037] In one embodiment the fermented product is a bakery product.
[0038] In accordance with another embodiment the fermented product is a gruel product, preferably for infants.
[0039] In a further embodiment the fermented product is a brewed product.
[0040] In yet another aspect of the invention, a method for the preparation of phytase is provided wherein one or more of the strains identified above are grown in a growth medium that facilitates phytase expression, whereupon produced phytase is isolated.
[0041] In accordance with a further aspect of the invention such a phytase preparation can be used as an additive in foodstuffs or feedstuffs to improve the utilization of minerals.
[0042] In accordance with a further aspect of the invention such a phytase preparation can be used to produce specific isomers of lower inositol phosphates
[0043] In yet another aspect of the invention, the invention provides a method for the preparation of phytase wherein one or more of the strains identified above are grown in a medium under conditions optimized for phytase expression whereupon lower inositol phosphates are produced as a result of yeast phytase activity on added inositol hexaphosphate.
[0044] Besides fermented products for human use the present Saccharomyces cerevisiae strains can be used for the production of animal feedstuffs to increase mineral uptake, and to reduce the phosphate amounts in faeces. Phosphorous in the form of IP6 can not be resorbed in the intestines and thus animal feedstuffs are enriched using inorganic phosphates. IP6 together with excess of phosphates follow the faeces, which leads to high amounts/concentrations of phosphorous in the manure.
[0045] Besides the foodstuff and feedstuff applications the enzyme phytase can be used for the manufacture of specific inositol phosphates for pharmacological use. One example is 1,2,6IP3, which may stimulate the release of insuline, to reduce thrombocyte aggregation and to have anti-inflammatory properties. Such inositol phosphates may be developed into pharmaceuticals.
[0046] The enzyme phytase can also be added to foodstuffs and feedstuffs to obtain the effects specified above. Thus a further aspect of the present invention is to grow the modified Saccharomyces cerevisiae and to isolate the phytase enzyme produced. Such isolation is readily carried out as the phytase is present extracellularly. Primarily the addition of phytase is made to improve availability of iron and zinc to the body.
[0047] The invention also includes a modified strain of Saccharomyces cereviaisae exhibiting increased phytase activity, the strains being designated as YM-p5 and YD80.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] FIG. 1 is a graph depicting the growth of S. cerevisiae SKQ2n (squares) and extracellular concentration of inositol hexaphosphate (IP6; triangles), measured by HPIC, as a function of time;
[0049] FIG. 2 is a graph depicting the chromatographic profiles (HPIC) of chemical acid hydrolysate of sodium phytate (first line), and supernatant from S. cerevisiae cultures (second and third lines) after 15 h of growth;
[0050] FIGS. 3A and 3B are graphs depicting the growth (squares) of S. cerevisiae parent strain YS18 (open symbols) and S. cerevisiae YMR4 pho5Δpho3Δ double deletion mutant (filled symbols) and extracellular concentration of IP6 (circles) as determined by HPIC;
[0051] FIG. 4 is a graph depicting the concentration of inositol hexaphosphate (IP6) in yeast culture supernatant as a function of growth in CBS medium with IP6 as the sole phosphorous source;
[0052] FIG. 5 is a graph depicting the concentration of inositol hexaphosphate (IP6) in yeast culture supernatant as a function of growth in complex YPD medium with IP6 as the added phosphorous source;
[0053] FIG. 6 is a vector construct consisting of plasmid pYX212 containing the insert PHO5 used for transformation of YS18 and YMR4;
[0054] FIGS. 7A and 7B are graphs depicting the extracellular concentration of IP6 as a function of growth time of S. cerevisiae YMR4 (A) and YS18 (B), with and without the PHO5 containing plasmid pYX212;
[0055] FIG. 8 is a graph depicting a direct comparison of phytate degrading capacity between PHO5 overexpressing strains, and pho80Δ and pho85Δ deletions mutants;
[0056] FIG. 9 is a graph depicting phytate degrading capacity of pho2Δ deletion mutant;
[0057] FIG. 10 is a graph depicting the extracellular concentration of para-nitrophenyl phosphate (pNPP, squares) and IP6 (triangles) as a function of growth of S. cerevisiae SKQ2n in CBS medium with 2% glucose as carbon and energy source;
[0058] FIG. 11 is a graph depicting the content of inositol hexaphosphate (IP6, triangles) and inorganic phosphate (P i ; squares), expressed as μmol per gram wet dough, as a function of leavening time in two types of wheat based dough; and
[0059] FIG. 12 is a graph depicting phytate degradation capacity of the pho80Δ deletion mutant SD80 (YS18 without PHO80) compared with S. cerevisiae YS18 in YPD supplemented with 0.25 mM IP6 and 30 mM Pi.
DETAILED DESCRIPTION OF INVENTION
[0060] The invention will now be described in reference to the following non-limiting examples.
[0000] Materials and methods
[0000] Organisms
[0061] Saccharomyces cerevisiae SKQ2n, Bataille et al. (1987) Identification of polypeptides of the carbon metabolism machinery on the two-dimensional map of Saccharomyces cerevisiae. Location of 23 additional polypeptides. Yeast. 3, 11-21,. S. cerevisiae YS18 (MATα; his3-11, 3-15; leu2-3, 2-112; ura3Δ5; canR) and S. cerevisiae YMR4 were used in most experiments as indicated. YS18 and YMR4 were previously constructed by Riederer and Hinnen; Riederer et al. (1991) Removal of N-glycosylation sites of the yeast acid phosphatase severely affects protein folding. J. Bacteriol. 173, 3539-3546. YS18 and YMR4 were in the present work both transformed with a PHO5 containing plasmid (see below) and the resulting transformant strains were designated YS-p5 and YM-p5, respectively. Strain YS-p5 was deposited with DSMZ—Deutsche Sammilung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, 38124 Braunschweig, Germany on Apr. 18, 2002 and was assigned accession number DSM-No. 14929.
[0062] YS18 and YMR4 were further deleted for PHO10 yielding strains named YS10 and YM10, respectively. YS18 was also used for construction of the pho80Δ strain labeled YD80. In addition, pho80Δ, pho85Δ and pho2Δ mutant strains were retrieved from the German EUROSCARF collection. pho80 (YOL001w), pho85 (YPL031c) and pho2 (YDL106c) strains originates from the laboratory BY4741 strain (MATa; his3Δ1, leu2Δ0, met15Δ0, ura3Δ0). The PHO80, PHO85 and PHO2 genes were deleted with kan::MX4 disruption cassette.
[0063] Yeast cultures were maintained on YPD-plates (yeast extract 10 g, peptone 20 g, glucose 20 g and agar 20 g in one liter of water) and stored long-term in glycerol at −70° C. Escherichia coli DH5α was used for propagating the plasmid containing the inserted PHO5 (see below). The yeast strains and their expression profiles of relevant genes are listed in Table 1.
TABLE 1 Strains of Saccharomyces cerevisiae used in this study, their relevant genotype and expression profiles of secretory phosphatases in repressing and non-repressing media. Secretory phosphates a Secretory phosphates Relevant expressed in IP 6 expressed in IP 6 + P i Reference for Strain genotype medium medium strain SKQ2n all PHO genes Pho5p, Pho10p, Pho11p none Bataille et al. intact (1987) YS18 all PHO genes Pho5p, Pho10p, Pho11p none Riederer et et al. intact. Parent (1991) strain for YMR4 YMR4 pho5,3::uraΔ1 Pho10p, Pho11p none Riedereret et al. (1991) YM-p5 pho5,3::uraΔ1 Pho5p b , Pho10p, Pho5p b This work pYX-PHO5 Pho11p YS-p5 pYX-PHO5 Pho5p b , Pho5p, Pho10p, Pho5p b This work Pho11p YM10 pho5,3::ura3Δ1 Pho11p none This work pho10::his3Δ YS10 pho10::his3Δ Pho5p, Pho11p none This work BY4741 All PHO genes Pho5p, Pho10p, Pho11p none EUROSCARF intact YOL001w pho80Δ Pho5p, Pho10p, Pho11p Pho5p, Pho10p, Pho11p EUROSCARF YPL031c pho85Δ Pho5p, Pho10p, Pho11p Pho5p, Pho10p, Pho11p EUROSCARF YDL106c pho2Δ none none EUROSCARF YD80 pho80Δ::hph Pho5p, Pho10p, Pho11p Pho5p, Pho10p, Pho11p This work a A small constitutive expression may occur b On the plasmid pYX212 under the control of TP11 promoter
Growth Media and Culture Conditions
[0064] The growth medium used in most experiments was a modified version of the defined yeast minimal medium developed by CBS (Centralbueau voor Schimmelcultures, Delft, the Netherlands) which has been described previously, Albers et al. (1996) Influence of the nitrogen source on Saccharomyces cerevisiae anaerobic growth and product formation. Appl. Environ. Microbiol. 62, 3187-3195 using ammonium sulfate (7.5 mg/ml) as nitrogen source. As phosphorus source, either IP6 in the form of sodium phytate (C 6 H 6 (OPO 3 Na 2 ) 6 : 0.5 or 0.25 mg/ml), inorganic phosphate (KH 2 PO 4 : 3.5 mg/ml), para-nitrophenyl phosphate (PNPP; to a final concentration of 2.25 or 0.25 mM), or combinations of these were used. Depending on the phosphorous source used the media were designated CBSIP6, CBSP i , CBSIP6+P i and CBSpNPP. CBSIP6 and CBSpNPP were supplemented with KCl (3 mg/ml) to compensate for the potassium present in the inorganic P-source (KH 2 PO 4 ), but absent in the organic P-sources. In all experiments glucose (either 2% (w/v) or 1% (w/v) as indicated) was used as carbon and energy source. When appropriate, histidine, leucine and uracil were supplied at 120 mg/l. Most experiments were also performed in YPD media (per liter: yeast extract, 10 g; peptone 20 g and glucose 20 g) supplemented with the appropriate P-sources as indicated in results and figure legends. Succinic acid/NaOH, pH 5.3, was used as buffer in the CBS based media. Medium components were autoclaved, with the exception for IP6, pNPP, vitamins, growth factors and FeCl 2 , which were sterilized by filtration through a 0.2 μm filter. Experimental cultures containing 100 ml in 250 ml E-flasks were inoculated with primary cultures grown for approximately 20 h in medium of the same composition as the respective experiment culture. The inoculation level was set to OD 610 =0.2. The experimental cultures were grown at 30° C. in a rotary shaker set to 210 rpm. The growth was monitored as optical density at 610 nm (OD 610 ) using a spectrophotometer (Hitachi, model U-100). Experiments aimed at PHO3 expression were performed in CBS medium as described above with the exception of excluding thiamine (to avoid repression of the thiamine phosphatase PHO3), with and without addition of thiamine monophosphate.
[0000] Construction of PHO5 Overexpressing Strain.
[0065] Chemicals and enzymes for the procedures were purchased from New England Biolabs Inc., USA, and the PCR primers used for amplification of PHO5 were purchased from Life Technologies AB, Taby, Sweden. Extraction of genomic DNA from S. cerevisiae YS18 was carried out according to standard procedures. The nucleotide sequences of the primers are shown in upper case letters and the added restriction enzyme sites are shown in lower case letters.
Primers for overexpression of PHO5 Forward primer: 5′: CG GAATTC ATGTTTAAATCTGTTGTTTATTC, appended as SEQ ID NO:1 Backwards primer: 3′: CG CTCGAG CTATTGTCTCAATAGACTGGC, appended as SEQ ID NO:2
Underlined sequences are EcoRI and Aval (yields end compatible to XhoI used to cut the pYX212 plasmid) restriction sites, respectively. The remaining sequences complement the beginning (from ATG) and end of PHO5.
[0066] The PCR reaction was performed in 100 μl reaction mixtures, using VENT polymerase and was carried out according to standard procedures.
[0067] The PCR produced PHO5 was purified with a PCR purification kit (Qiagen, Cat, No. 28104, Merck Eurolab AB, Sweden) according to the manufacturer's protocol and 50 pl was cut with AvaI and EcoRI in EcoRI buffer for 12 h at 37° C. The cut PCR product was loaded on a preparative agarose gel and run together with a DNA ladder in TAE buffer. The appropriate band was cut out and purified using DNA gel extraction kit (Qiagen, Cat. No. 28704). A 20 μl ligation mixture was prepared by mixing 16 μl purified insert (PHO5), 2 μl T4 DNA ligase buffer (10×) 1 μl ligase and 2 μl vector DNA (pYX212). The plasmid pYX212 containing the selection markers AmP R for E. coli and URA3 for S. cerevisiae had previously been cut with EcoRI and XhoI (yields ends compatible with AvaI). Two μl of the DNA construct was added to 40 μl of cold competent E. coli DH5α and transformed by electroporation using a Gene Pulser II (Biorad) set to the 25 μF capacitator, 2.5 kV and the pulse controller to 200Ω. Cells were plated on NB plates containing 100 μg/ml ampicillin. Clones were cultivated over night in liquid NB medium and plasmids were prepared according to standard procedures.
Sequence of the plasmid pYX212 with insert PHO5: GAATTCATGTTTAAATCTGTTGTTTATTC×AATTTTAGCCGCTTCTTTGGC CAATGCAGGTACCATTCCCTTAGGCAAACTAGCCGATGTCGACAAGATTG GTACCCAAAAAGATATCTTCCCATTTTTGGGTGGTGCCGGACCATACTAC TCTTTCCCTGGCGACTATGGTATTTCTCGTGATTTGCCTGAAGGTTGTGA AATGAAGCAACTGCAAATGGTTGGTAGACATGGTGAAAGATACCCTACTG TCAGTCTGGCTAAGACTATCAAGAGTACATGGTATAAGTTGAGCAATTAC ACTCGTCAATTCAACGGCTCATTGTCATTCTTGAACGATGATTACGAGTT TTTCATCCGTGATGACGATGATTTGGAAATGGAAACCACTTTTGCCAACT CGGACGATGTTTTGAACCCATACACTGGTGAAATGAACGCCAAGAGACAT GCTCGTGACTTCTTGGCTCAATACGGTTACATGGTCGAAAACCAAACCAG TTTCGCCGTTTTTACCTCTAATTCTAAGAGATGTCATGACACTGCTCAAT ATTTCATTGATGGTTTAGGTGACCAATTCAACATCACCTTGCAGACTGTC AGTGAAGCTGAATCCGCTGGTGCCAACACTTTGAGTGCTTGTAACTCATG TCCTGCTTGGGACTACGATGCCAATGATGACATTGTAAATGAATACGACA CAACCTACTTGGATGACATTGCCAAGAGATTGAACAAGGAAAACAAGGGT TTGAACTTGACCTCAACTGACGCTAGTACTTTATTCTCGTGGTGTGCATT TGAAGTGAACGCTAAAGGTTACAGTGATGTCTGTGATATTTTCACCAAGG ATGAATTAGTCCATTACTCCTACTACCAAGACTTGCACACTTATTACCAT GAGGGTCCAGGTTACGACATTATCAAGTCTGTCGGTTCCAACTTGTTCAA TGCCTCAGTCAAATTATTAAAGCAAAGTGAGATTCAAGACCAAAAGGTTT GGTTGAGTTTTACCCACGATACCGATATCCTAAACTTTTTGACCACCGCT GGTATAATTGACGACAAAAACAACTTAACTGCCGAATACGTTCCATTCAT GGGCAACACTTTCCACAGATCCTGGTACGTTCCTCAAGGTGCTCGTGTCT ACACCGAAAAATTCCAATGTTCTAACGACACCTACGTCAGATACGTCATT AACGATGCTGTTGTTCCAATTGAAACCTGTTCCACTGGTCCAGGGTTCTC TTGTGAAATCAATGACTTCTACGACTATGCTGAAAAGAGAGTAGCCGGTA CTGACTTCCTAAAGGTCTGTAACGTCAGCAGCGTCAGTAACTCTACTGAA TTGACCTTCTACTGGGACTGGAACACTACTCATTACAAC GCCAGTCTATT GAGACAATAG CCCGGGTATCCGTATGATGTGCCTGACTACGCATGATATC TCGAGCTCAGCTAGCTAACTGAATAAGGAACAATGAACGTTTTTCCTTTC TCTTGTTCCTAGTATTAATGACTGACCGATACATCCCTTTTTTTTTTTGT CTTTGTCTAGCTCCAGCTTTTGTTCCCTTTAGTGAGGGTTAATTCAATTC ACTGGCCGTCGTTTTACAACGTCGTGACTGGGAAAACCCTGGCGTTACCC AACTTAATCGCCTTGCAGCACATCCCCCTTTCGCCAGCTGGCGTAATAGC GAAGAGGCCCGCACCGATCGCCCTTCCCAACAGTTGCGCAGCCTGAATGG CGAATGGCGCGACGCGCCCTGTAGCGGCGCATTAAGCGCGGCGGGTGTGG TGGTTACGCGCAGCGTGACCGCTACACTTGCCAGCGCCCTAGCGCCCGCT CCTTTCGCTTTCTTCCCTTCCTTTCTCGCCACGTTCGCCGGCTTTCCCCG TCAAGCTCTAAATCGGGGGCTCCCTTTAGGGTTCCGATTTAGTGGTTTAC GGCACCTCGACCCCAAAAAACTTGATTAGGGTGATGGTTCACGTAGTGGG CCATCGCCCTGATAGACGGTTTTTCGCCCTTTGACGTTGGAGTCCACGTT CTTTAATAGTGGACTCTTGTTCCAAACTGGAACAACACTCAACCCTATCT CGGTCTATTCTTTTGATTTATAAGGGATTTTGCCGATTTCGGCCTATTGG TTAAAAAATGAGCTGATTTAACAAAAATTTAACGCGAATTTTAACAAAAT ATTAACGTTTACAATTTCCTGATGCGGTATTTTCTCCTTACGCATCTGTG CGGTATTTCACACCGCATAGGGTAATAACTGATATAATTAAATTGAAGCT CTAATTTGTGAGTTTAGTATACATGCATTTACTTATAATACAGTTTTTTA GTTTTGCTGGCCGCATCTTCTCAAATATGCTTCCCAGCCTGCTTTTCTGT AACGTTCACCCTGTACCTTAGCATCCCTTCCCTTTGCAAATAGTCCTCTT CCAACAATAATAATGTCAGATCCTGTAGAGACCACATCATCCACGGTTCT ATACTGTTGACCCAATGCGTCTCCCTTGTCATCTAAACCCACACCGGGTG TCATAATCAACCAATCGTAACCTTCATCTCTTCCACCCATGTCTCTTTGA GCAATAAAGCCGATAACAAAATCTTTGTCGCTCTTCGCAATGTCAACAGT ACCCTTAGTATATTCTCCAGTAGATAGGGAGCCCTTGCATGACAATTCTG CTAACATCAAAAGGCCTCTAGGTTCCTTTGTTACTTCTTCTGCCGCCTGC TTCAAACCGCTAACAATACCTGGCCCCAGCACACCGTGTGCATTCGTAAT GTCTGCCCATTCTGCTATTCTGTATACACCCGCAGAGTACTGCAATTTGA CTGTATTACCAATGTCAGCAAATTTTCTGTCTTCGAAGAGTAAAAAATTG TACTTGGCGGATAATGCCTTTAGCGGCTTAACTGTGCCCTCCATCGAAAA ATCAGTCAATATATCCACATGTGTTTTTAGTAAACAAATTTTGGGACCTA ATGCTTCAACTAACTCCAGTAATTCCTTGGTGGTACGAACATCCAATGAA GCACACAAGTTTGTTTGCTTTTCGTGCATGATATTAAATAGCTTGGCAGC AACAGGACTAGGATGAGTAGCAGCACGTTCCTTATATGTAGCTTTCGACA TGATTTATCTTCGTTTCCTGCAGGTTTTTGTTCTGTGCAGTTGGGTTAAG AATACTGGGCAATTTCATGTTTCTTCAACACTACATATGCGTATATATAC CAATCTAAGTCTGTGCTCCTTCCTTCGTTCTTCCTTCTGTTCGGAGATTA CCGAATCAAAAAAATTTCAAAGAAACCGAAATCAAAAAAAAGAATAAAAA AAAAATGATGAATTGAATTGAAAAGCTGTGGTATGGTGCACTCTCAGTAC AATCTGCTCTGATGCCGCATAGTTAAGCCAGCCCCGACACCCGCCAACAC CCGCTGACGCGCCCTGACGGGCTTGTCTGCTCCCGGCATCCGCTTACAGA CAAGCTGTGACCGTCTCCGGGAGCTGCATGTGTCAGAGGTTTTCACCGTC ATCACCGAAACGCGCGAGACGAAAGGGCCTCGTGATACGCCTATTTTTAT AGGTTAATGTCATGATAATAATGGTTTCTTAGACGTGCGGCCGCTCTAGA ACTAGTGGATCAATTCCACGGACTATAGACTATACTAGTATACTCCGTCT ACTGTACGATACACTTCCGCTCAGGTCCTTGTCCTTTAACGAGGCCTTAC CACTCTTTTGTTACTCTATTGATCCAGCTCAGCAAAGGCAGTGTGATCTA AGATTCTATCTTCGCGATGTAGTAAAACTAGCTAGACCGAGAAAGAGACT AGAAATGCAAAAGGCACTTCTACAATGGCTGCCATCATTATTATCCGATG TGACGCTGCAGCTTCTCAATGATATTCGAATACGCTTTGAGGAGATACAG CCTAATATCCGACAAACTGTTTTACAGATTTACGATCGTACTTGTTACCC ATCATTGAATTTTGAACATCCGAACCTGGGAGTTTTCCCTGAAACAGATA GTATATTTGAACCTGTATAATAATATATAGTCTAGCGCTTTACGGAAGAC AATGTATGTATTTCGGTTCCTGGAGAAACTATTGCATCTATTGCATAGGT AATCTTGCACGTCGCATCCCCGGTTCATTTTCTGCGTTTCCATCTTGCAC TTCAATAGCATATCTTTGTTAACGAAGCATCTGTGCTTCATTTTGTAGAA CAAAAATGCAACGCGAGAGCGCTAATTTTTCAAACAAAGAATCTGAGCTG CATTTTTACAGAACAGAAATGCAACGCGAAAGCGCTATTTTACCAACGAA GAATCTGTGCTTCATTTTTGTAAAACAAAAATGCAACGCGAGAGCGCTAA TTTTTCAAACAAAGAATCTGAGCTGCATTTTTACAGAACAGAAATGCAAC GCGAGAGCGCTATTTTACCAACAAAGAATCTATACTTCTTTTTTGTTCTA CAAAAATGCATCCCGAGAGCGCTATTTTTCTAACAAAGCATCTTAGATTA CTTTTTTTCTCCTTTGTGCGCTCTATAATGCAGTCTCTTGATAACTTTTT GCACTGTAGGTCCGTTAAGGTTAGAAGAAGGCTACTTTGGTGTCTATTTT CTCTTCCATAAAAAAAGCCTGACTCCACTTCCCGCGTTTACTGATTACTA GCGAAGCTGCGGGTGCATTTTTTCAAGATAAAGGCATCCCCGATTATATT CTATACCGATGTGGATTGCGCATACTTTGTGAACAGAAAGTGATAGCGTT GATGATTCTTCATTGGTCAGAAAATTATGAACGGTTTCTTCTATTTTGTC TCTATATACTACGTATAGGAAATGTTTACATTTTCGTATTGTTTTCGATT CACTCTATGAATAGTTCTTACTACAATTTTTTTGTCTAAAGAGTAATACT AGAGATAAACATAAAAAATGTAGAGGTCGAGTTTAGATGCAAGTTCAAGG AGCGAAAGGTGGATGGGTAGGTTATATAGGGATATAGCACAGAGATATAT AGCAAAGAGATACTTTTGAGCAATGTTTGTGGAAGCGGTATTCGCAATAT TTTAGTAGCTCGTTACAGTCCGGTGCGTTTTTGGTTTTTTGAAAGTGCGT CTTCAGAGCGCTTTTGGTTTTCAAAAGCGCTCTGAAGTTCCTATACTTTC TAGAGAATAGGAACTTCGGAATAGGAACTTCAAAGCGTTTCCGAAAACGA GCGCTTCCGAAAATGCAACGCGAGCTGCGCACATACAGCTCACTGTTCAC GTCGCACCTATATCTGCGTGTTGCCTGTATATATATATACATGAGAAGAA CGGCATAGTGCGTGTTTATGCTTAAATGCGTACTTATATGCGTCTATTTA TGTAGGATGAAAGGTAGTCTAGTACCTCCTGTGATATTATCCCATTCCAT GCGGGGTATCGTATGCTTCCTTCAGCACTACCCTTTAGCTGTTCTATATG CTGCCACTCCTCAATTGGATTAGTCTCATCCTTCAATGCTATCATTTCCT TTGATATTGGATCATATGCATAGTACCGAGAAACTAGTGCGAAGTAGTGA TCAGGTATTGCTGTTATCTGATGAGTATACGTTGTCCTGGCCACGGCAGA AGCACGCTTATCGCTCCAATTTCCCACAACATTAGTCAACTCCGTTAGGC CCTTCATTGAAAGAAATGAGGTCATCAAATGTCTTCCAATGTGAGATTTT GGGCCATTTTTTATAGCAAAGATTGAATAAGGCGCATTTTTCTTCAAAGC TGCGGCCGCACTCTCACTAGTACGTCAGGTGGCACTTTTCGGGGAAATGT GCGCGGAACCCCTATTTGTTTATTTTTCTAAATACATTCAAATATGTATC CGCTCATGAGACAATAACCGTGATAAATGCTTCAATAATATTGAAAAAGG AAGAGTATGAGTATTCAACATTTCCGTGTCGCCCTTATTCCCTTTTTTGC GGCATTTTGCCTTCCTGTTTTTGCTCACCCAGAAACGCTGGTGAAAGTAA AAGATGCTGAAGATCAGTTGGGTGCACGAGTGGGTTACATCGAACTGGAT CTCAACAGCGGTAAGATCCTTGAGAGTTTTCGCCCCGAAGAACGTTTTCC AATGATGAGCACTTTTAAAGTTCTGCTATGTGGCGCGGTATTATCCCGTA TTGACGCCGGGCAAGAGCAACTCGCTCGCCGCATACACTATTCTCAGAAT GACTTGGTTGAGTACTCACCAGTCACAGAAAAGCATCTTACGGATGGCAT GACAGTAAGAGAATTATGCAGTGCTGCCATAACCATGAGTGATAACACTG CGGCCAACTTACTTCTGACAACGATCGGAGGACCGAAGGAGCTAACCGCT TTTTTGGACAACATGGGGGATCATGTAACTCGCCTTGATCGTTGGGAACC GGAGCTGAATGAAGCCATACCAAACGACGAGCGTGACACCACGATGCCTG TAGCAATGGCAACAACGTTGCGCAAACTATTAACTGGCGAACTACTTACT CTAGCTTCCCGGCAACAATTAATAGACTGGATGGAGGCGGATAAAGTTGC AGGACCACTTCTGCGCTCGGCCCTTCCGGCTGGCTGGTTTATTGCTGATA AATCTGGAGCCGGTGAGCGTGGGTCTCGCGGTATCATTGCAGCACTGGGG CCAGATGGTAAGCCCTCCCGTATCGTAGTTATCTACACGACGGGGAGTCA GGCAACTATGGATGAACGAAATAGACAGATCGCTGAGATAGGTGCCTCAC TGATTAAGCATTGGTAACTGTCAGACCAAGTTTACTCATATATACTTTAG ATTGATTTAAAACTTCATTTTTAATTTAAAAGGATCTAGGTGAAGATCCT TTTTGATAATCTCATGACCAAAATCCCTTAACGTGAGTTTTCGTTCCACT GAGCGTCAGACCCCGTAGAAAAGATCAAAGGATCTTCTTGAGATCCTTTT TTTCTGCGCGTAATCTGCTGCTTGCAAACAAAAAAACCACCGCTACCAGC GGTGGTTTGTTTGCCGGATCAAGAGCTACCAACTCTTTTTCCGAAGGTAA CTGGCTTCAGCAGAGCGCAGATACCAAATACTGTCCTTCTAGTGTAGCCG TAGTTAGGCCACCACTTCAAGAACTCTGTAGCACCGCCTACATACCTCGC TCTGCTAATCCTGTTACCAGTGGCTGCTGCCAGTGGCGATAAGTCGTGTC TTACCGGGTTGGACTCAAGACGATAGTTACCGGATAAGGCGCAGCGGTCG GGCTGAACGGGGGGTTCGTGCACACAGCCCAGCTTGGAGCGAACGACCTA CACCGAACTGAGATACCTACAGCGTGAGCTATGAGAAAGCGCCACGCTTC CCGAAGGGAGAAAGGCGGACAGGTATCCGGTAAGCGGCAGGGTCGGAACA GGAGAGCGCACGAGGGAGCTTCCAGGGGGAAACGCCTGGTATCTTTATAG TCCTGTCGGGTTTCGCCACCTCTGACTTGAGCGTCGATTTTTGTGATGCT CGTCAGGGGGGCGGAGCCTATGGAAAAACGCCAGCAACGCGGCCTTTTTA CGGTTCCTGGCCTTTTGCTGGCCTTTTGCTCACATGTTCTTTCCTGCGTT ATCCCCTGATTCTGTGGATAACCGTATTACCGCCTTTGAGTGAGCTGATA CCGGTCGCCGCAGCCGAACGACCGAGCGCAGCGAGTCAGTGAGCGAGGAA GCGGAAGAGCGCCCAATACGCAAACCGCCTCTCCCCGCGCGTTGGCCGAT TCATTAATGCAGCTGGCACGACAGGTTTCCCGACTGGAAAGCGGGCAGTG AGCGCAACGCAATTAATGTGAGTTACCTCACTCATTAGGCACCCCAGGCT TTACACTTTATGCTTCCGGCTCCTATGTTGTGTGGAATTGTGAGCGGATA ACAATTTCACACAGGAAACAGCTATGACCATGATTACGCCAAGCTCGAAA TACGACTCACTATAGGGCGAATTGGGTACCGGGCCGGCCGTCGAGCTTGA TGGCATCGTGGTGTCACGCTCGTCGTTTGGTATGGCTTCATTCAGCTCCG GTTCCCAACGATCAAGGCGAGTTACATGATCCCCCATGTTGTGAAAAAAA GCGGTTAGCTCTTCGGTCCTCCGATCGTTGTCAGAAGTAAGTTGGCCGCA GTGTTATCACTCATGGTTATGGCAGGAACTGCATAATTCTCTTACTGTCA TGCCATCCGTAAGATGCTTTTCTGTGACTGGTGTACTCAACCAAGTCATT CTGAGAATAGTGTATGCGGCGACCGAGTTGCTCTTGCCCGGCGTCAACAC GGGATAATACCGCGCCACATAGCAGAACTTTAAAAGTGCTCATCATTGGA AAACGTTCTTCGGGGCGAAAACTCTCAAGGATCTTACCGCTGTTGAGATC CAGTTCGATGTAACCCACTCGTGCACCCAACTGATCTTCAGCATCTTTTA CTTTCACCAGCGTTTCTGGGTGAGCAAAAACAGGAAGGCAAAATGCCGCA AAAAAGGGAATAAGGGCGACACGGAAATGTTGAATACTCATACTCTTCCT TTTTCAATATTATTGAAGCATTTATCAGGGTTATTGTCTCATGAGCGATA CATATTTGAATGTATTTAGAAAAATAAACAAATAGGGGTTCCGCGCACAT TTCCCCGAAAAGTGCCACCTGACGTCTAAGAAACCATTATTATCATGACA TTAACCTATAAAAATAGGCGTATCACGAGGCCCTTTCGTCTTCAAGAATT GGGGATCTACGTATGGTCATTCTTCTTCAGATTCCCTCATGGAGAAGTGC GGCAGATGTATATGACAGAGTCGCCAGTTTCCAAGAGACTTTATTCAGGC ACTTCCATGATAGGCAAGAGAGAAGACCCAGAGATGTTGTTGTCCTAGTT ACACATGGTATTTATTCCAGAGTATTCCTGATGAAATGGTTTAGATGGAC ATACGAAGAGTTTGAATCGTTTACCAATGTTCCTAACGGGAGCGTAATGG TGATGGAACTGGACGAATCCATCAATAGATACGTCCTGAGGACCGTGCTA CCCAAATGGACTGATTGTGAGGGAGACCTAACTACATAGTGTTTAAAGAT TACGGATATTTAACTTACTTAGAATAATGCCATTTTTTTGAGTTATAATA ATCCTACGTTAGTGTGAGCGGGATTTAAACTGTGAGGACCTCAATACATT CAGACACTTCTGACGGTATCACCCTACTTATTCCCTTCGAGATTATATCT AGGAACCCATCAGGTTGGTGGAAGATTACCCGTTCTAAGACTTTTCAGCT TCCTCTATTGATGTTACACTCGGACACCCCTTTTCTGGCATCCAGTTTTT AATCTTCAGTGGCATGTGAGATTCTCCGAAATTAATTAAAGCAATCACAC AATTCTCTCGGATACCACCTCGGTTGAAACTGACAGGTGGTTTGTTACGC ATGCTAATGCAAAGGAGCCTATATACCTTTGGCTCGGCTGCTGTAACAGG GAATATAAAGGGCAGCATAATTTAGGAGTTTAGTGAACTTGCAACATTTA CTATTTTCCCTTCTTACGTAAATATTTTTCTTTTTAATTCTAAATCAATC TTTTTCAATTTTTTGTTTGTATTCTTTTCTTGCTTAAATCTATAACTACA AAAAACACATACAGG appended as SEQ ID NO: 3. Underlined sequences show sites for primers Bolded nucleotides represent the inserted PHO5
Underlined sequences show sites for primers Bolded nucleotides represent the inserted PHO5
[0070] The presence of PHO5 was verified by PCR using the same primers as described above as well as by cutting with EcoRV followed by gel electrophoresis, then transformed into yeast strains YS18 and YMR4 using a standard LiOAc S. cerevisiae transformation protocol. Yeasts containing the vector with insert were selected for on uracil negative YNB plates (DIFCO, USA) containing the appropriate amino acids. The resulting transformant strains were named YS-p5 and YM-p5, respectively.
[0000] Construction of Deletion Strains
[0071] The PHO10 deletions were generated by PCR-mediated gene replacement, Baudin et al. (1993) A simple and efficient for direct gene deletion in Saccharomyces cerevisiae. Nucleic Acids Res. 21, 3329-3330 using HIS5 from Saccharomyces pombe (corresponding to HIS3 in Saccharomyces cerevisiae ) as the selectable marker. As template DNA the plasmid pFA6a-HIS3MX6; Wach et al. (1994) New heterologous modules for classical or PCR-based gene disruptions in Saccharomyces cerevisiae. Yeast. 10, 1793-1808 was used.
Primers for deletion of PHO10 5′: CGATAGATTCAAGCTCAGTTTCGCCTTGGTTGTAAAGTAGG CAGCT GAAGCTTCGTACGC -3′, appended as SEQ ID NO:4 5′: GGTCTATTTACTGTTTTAATAAAGTGTCGTTGTAGTGCTTGG GGCA GATGATGTCGAGGCG -3′, appended as SEQ ID NO 5
[0072] These oligonucleotides were used as primers for construction of deletion cassettes. Underlined sequences are complementary to HIS5 in the template, and non-underlined parts to flanking regions of PHO10. The PHO10 deletions were generated by PCR-mediated gene replacement using HIS5 from Saccharomyces pombe (corresponding to HIS3 in S. cerevisiae ) as the selectable marker. As template DNA the plasmid pFA6a-HIS3MX6 was used.
[0073] Sequence of the Resulting PCR product used for deletion of PHO10 by homologous recombination:
CGATAGATTCAAGCTCAGTTTCGCCTTGGTTGTAAAGTAGC CAGCTGAAG CTTCGTACGC TGCAGGTCGACGGATCCCCGGGTTAATTAAGGCGCGCCAG ATCTGTTTAGCTTGCCTCGTCCCCGCCGGGTCACCCGGCCAGCGACATGG AGGCCCAGAATACCCTCCTTGACAGTCTTGACGTGCGCAGCTCAGGGGCA TGATGTGACTGTCGCCCGTACATTTAGCCCATACATCCCCATGTATAATC ATTTGCATCCATACATTTTGATGGCCGCACGGCGCGAAGCAAAAATTACG GCTCCTCGCTGCAGACCTGCGAGCAGGGAAACGCTCCCCTCACAGACGCG TTGAATTGTCCCCACGCCGCGCCCCTGTGAGAAATATAAAAGGTTAGGAT TTGCCACTGAGGTTCTTCTTTCATATACTTCCTTTTAAATCTTGCTAGGA TACAGTTCTCACATCACATCCGAACATAAACAACCATGGGTAGGAGGGCT TTTGTAGAAAGAAATACGAACGAAACGAAAATCAGCGTTGCCATCGCTTT GGACAAAGCTCCCTTACCTGAAGAGTCGAATTTTATTGATGAACTTATAA CTTCCAAGCATGCAAACCAAAAGGGAGAACAAGTAATCCAAGTAGACACG GGAATTGGATTCTTGGATCACATGTATCATGCACTGGCTAAACATGCAGG CTGGAGCTTACGACTTTACTCAAGAGGTGATTTAATCATCGATGATCATC ACACTGCAGAAGATACTGCTATTGCACTTGGTATTGCATTCAAGCAGGCT ATGGGTAACTTTGCCGGCGTTAAAAGATTTGGACATGCTTATTGTCCACT TGACGAAGCTCTTTCTAGAAGCGTAGTTGACTTGTCGGGACGGCCCTATG CTGTTATCGATTTGGGATTAAAGCGTGAAAAGGTTGGGGAATTGTCCTGT GAAATGATCCCTCACTTACTATATTCCTTTTCGGTAGCAGCTGGAATTAC TTTGCATGTTACCTGCTTATATGGTAGTAATGACCATCATCGTGCTGAAA GCGCTTTTAAATCTCTGGCTGTTGCCATGCGCGCGGCTACTAGTCTTACT GGAAGTTCTGAAGTCCCAAGCACGAAGGGAGTGTTGTAAAGAGTACTGAC AATAAAAAGATTCTTGTTTTCAAGAACTTGTCATTTGTATAGTTTTTTTA TATTGTAGTTGTTCTATTTTAATCAAATGTTAGCGTGATTTATATTTTTT TT CGCCTCGACATCATCTGCC CCAAGCACTACAACGACACTTTATTAAAA CAGTAAATAGACC appended as SEQ ID NO:6 Underlined sequences represent primers (or complementary strand to primer) used Italic shows sequence corresponding to PHO10 (SGD)
Underlined sequences represent primers (or complementary strand to primer) used Italic shows sequence corresponding to PHO10 (SGD)
[0074] The PCR reactions were performed in 100 μl using VENT polymerase, the crude PCR product was purified by cutting the appropriate band from a preparative agorase gel-electrophoresis and YMR4 and YS18 were transformed by the lithium acetate method resulting in strains named YM10 and YS10, respectively. The deletions were verified by PCR on whole yeast colonies as well as on extracted DNA.
[0075] Deletion of PHO80 was performed by PCR-based gene disruption, mainly according to Baudin et al., (1993) “A simple and efficient for direct gene deletion in Saccharomyces cerevisiaw. ” Nucleic Acids Res. 21, 3329-3330, and Goldstein and McCusker, (1999) “New heterologous modules for classical or PCR-based gene disruptions in Saccharomyces cerevisiae. ” Yeast, 10,1793-1808. A deletion fragment consisting of a selectable marker flanked by 5′ and 3′ flanking sequences of PHO80 was constructed. At transformation, the PHO80 ORF was exchanged for hygromycin B phosphotransferase (hph) by homologous recombination. The plasmid pAG32 Goldstein et al., containing the selectable marker hph (hygromycin B phosphotransferase) was used as template for the PCR based construction of the PHO80 deletion fragment. For the PHO80 region, primers were designed according to SGD and for the hph region according to Gritz and Davis (1983) “Plasmid encoded hygromycin B resistance: the sequence of hygromycin B phosphotransferase gene and its expression in Escherichia coli and Saccharomyces cerevisiae. ” Gene. 25, 178-188.
Deletion of PHO80 Forward primer: 5′: CAGCGTATATTGGCTTTCCTTTAATCTAATGCCCCAAGCC CACATA CGATTTAGGTGACAC -3′ APPENDED AS SEQ ID NO:10 Backwards primer: 5′-GGAGTTCTCAAGCTCATCTCGAAGTGTTTTCTGTCGCTTATG AATAC GACTCACTATAGGGTG -3′ APPENDED AS SEQ ID NO:11
[0076] Underlined sequences complement hph in pAG32 (Goldstein and McCusker, 1999, Yeast 15:1541-1553) The rest are deleting sequences that complement regions flanking PHO80 (SGD). The plasmid pAG32 (Goldstein and McCusker, 1999), containing the selectable marker hygromycin B phosphotransferase (hph), was used as template. FW primer complements to non-coding strain. Starting at ˜483 bp upstream hph start (ATG) in pAG32 and 315 bp upstream PHO80 start. BW primer complements to coding strand. Oligo. (63 bp.) starts 311 bp downstream hph end in pAG32, and 267 bp downstream PHO80 end in S. cerevisiae.
[0077] The PCR mix consisted of Thermopol buffer, 0.1 μg/pl acetylated BSA (Bovine Serum Albumin), 0.2 mM dNTPs, 0.5 μM of each primer and 2 units of VENT polymerase. To each reaction approximately 0.7 μg/ml template DNA was added. Following the PCR reaction, products were separated by agarose gel electrophoresis (0.7% agarose in TBE buffer. 100V) and purified by QIAquick Gel Extraction Kit (QIAGEN).
[0078] Resulting PCR product used for deletion of PHO80 by homologous recombination:
CAGCGTATATTGGCTTTCCTTTAATCTAATGCCCCAAGCCCACATACGAT TTAGGTGACAC TATAGAACGCGGCCGCCAGCTGAAGCTTCGTACGCTGCA GGTCGACGGATCCCCGGGTTAATTAAGGCGCGCCAGATCTGTTTAGCTTG CCTCGTCCCCGCCGGGTCACCCGGCCAGCGACATGGAGGCCCAGAATACC CTCCTTGACAGTCTTGACGTGCGCAGCTCAGGGGCATGATGTGACTGTCG CCCGTACATTTAGCCCATACATCCCCATGTATAATCATTTGCATCCATAC ATTTTGATGGCCGCACGGCGCGAAGCAAAAATTACGGCTCCTCGCTGCAG ACCTGCGAGCAGGGAAACGCTCCCCTCACAGACGCGTTGAATTGTCCCCA CGCCGCGCCCCTGTAGAGAAATATAAAAGGTTAGGATTTGCCACTGAGGT TCTTCTTTCATATACTTCCTTTTAAAATCTTGCTAGGATACAGTTCTCAC ATCACATCCGAACATAAACAACCATGGGTAA AAAGCCTGAACTCACCGCG ACGTCTGTCGAGAAGTTTCTGATCGAAAAGTTCGACAGCGTCTCCGACCT GATGCAGCTCTCGGAGGGCGAAGAATCTCGTGCTTTCAGCTTCGATGTAG GAGGGCGTGGATATGTCCTGCGGGTAAATAGCTGCGCCGATGGTTTCTAC AAAGATCGTTATGTTTATCGGCACTTTGCATCGGCCGCGCTCCCGATTCC GGAAGTGCTTGACATTGGGGAATTCAGCGAGAGCCTGACCTATTGCATCT CCCGCCGTGCACAGGGTGTCACGTTGCAAGACCTGCCTGAAACCGAACTG CCCGCTGTTCTGCAGCCGGTCGCGGAGGCCATGGATGCGATCGCTGCGGC CGATCTTAGCCAGACGAGCGGGTTCGGCCCATTCGGACCGCAAGGAATCG GTCAATACACTACATGGCGTGATTTCATATGCGCGATTGCTGATCCCCAT GTGTATCACTGGCAAACTGTGATGGACGACACCGTCAGTGCGTCCGTCGC GCAGGCTCTCGATGAGCTGATGCTTTGGGCCGAGGACTGCCCCGAAGTCC GGCACCTCGTGCACGCGGATTTCGGCTCCAACAATGTCCTGACGGACAAT GGCCGCATAACAGCGGTCATTGACTGGAGCGAGGCGATGTTCGGGGATTC CCAATACGAGGTCGCCAACATCTTCTTCTGGAGGCCGTGGTTGGCTTGTA TGGAGCAGCAGACGCGCTACTTCGAGCGGAGGCATCCGGAGCTTGCAGGA TCGCCGCGGCTCCGGGCGTATATGCTCCGCATTGGTCTTGACCAACTCTA TCAGAGCTTGGTTGACGGCAATTTCGATGATGCAGCTTGGGCGCAGGGTC GATGCGACGCAATCGTCCGATCCGGAGCCGGGACTGTCGGGCGTACACAA ATCGCCCGCAGAAGCGCGGCCGTCTGGACCGATGGCTGTGTAGAAGTACT CGCCGATAGTGGAAACCGACGCCCCAGCACTCGTCCGAGGGCAAAGGAA T AATCAGTACTGACAATAAAAAGATTCTTGTTTTCAAGAACTTGTCATTTG TATAGTTTTTTTATATTGTAGTTGTTCTATTTTAATCAAATGTTAGCGTG ATTTATATTTTTTTTCGCCTCGACATCATCTGCCCAGATGCGAAGTTAAG TGCGCAGAAAGTAATATCATGCGTCAATCGTATGTGAATGCTGGTCGCTA TACTGCTGTCGATTCGATACTAACGCCGCCATCCAGTGTCGAAAACGAGC TCGAATTCATCGATGATATCAGATCCACTAGTGGCCTATGCGGCCGCGGA TCTGCCGGT CTCCCTATAGTGAGTCGTATTCATAAGCGACAGAAAACACT TCGAGATGAGCTTGAGAACTCC , appended as SEQ ID NO:12 Nucleotides in bold show the ORF of the hgh gene. Underlined sequences shows the PCR primers, partly complementary to the PHO80 gene
Nucleotides in bold show the ORF of the hgh gene. Underlined sequences shows the PCR primers, partly complementary to the PHO80 gene
[0079] The purified deletion fragment was transformed into YS18 by electroporation. The protcol for transformation was mainly based on a protocol at Gottschling Lab website. Transformants were incubated in 30° C. in 1 ml 1M sorbitol+1 ml 2× YPD for 2 h to allow expression of the drug resistance marker, then spread onto selective growth medium (YPD, 0.9 mg/ml hygromycin B). Colonies appeared after a few days and putative transformants were tested for accuracy by PCR. The resulting strain was designated YD80 (MATα; his3-11, 3-15; leu2-3, 2-112; ura3Δ5; canR; pho80Δ::hph)
[0000] 2.5. Construction of Combined pho80Δ deletion and PHO4 and PHO5 overexpressing strains.
[0080] The plasmid pYX212 containing the insert PHO5 (described above) was transformed into strain YD80 using a standard LiOAc S. cerevisiae transformation protocol. Furthermore, PHO4 was PCR cloned as described above using the primers:
Primers for overexpression of PHO4 Forward primer (JP42) 5′-CG GAATTC ATGGGCCGTACAACTTCTGAGG-3′, APPENDED AS SEQ ID NO:7 Backwards primers (JT42) 5′-CG CTCGAG TCACGTGCTCACGTTCTGCAG-3′, APPENDED AS SEQ ID NO:8
[0081] Underlined sequences complement EcoRI and XhoI restriction sites in pYX212 and the rest are sequences that complement start and end regions in PHO4 (SGD).
[0082] Sequence of pYX212 containing the insert PHO4:
GAATTCATGGGCCGTACAACTTCTGAGG GAATACACGGTTTTGTGGACGA TCTAGAGCCCAAGAGCAGCATTCTTGATAAAGTCGGAGACTTTATCACCG TAAACACGAAACGGCATGATGGGCGCGAGGACTTCAACGAGCAAAACGAC GAGCTGAACAGTCAAGAGAACCACAACAGCAGTGAGAATGGGAACGAGAA TGAAAATGAACAAGACAGTCTCGCGTTGGACGACCTAGACCGCGCCTTTG AGCTGGTGGAAGGTATGGATATGGACTGGATGATGCCCTCGCATGCGCAC CACTCCCCAGCTACAACTGCTACAATCAAGCCGCGGCTATTATATTCGCC GCTAATACACACGCAAAGTGCGGTTCCCGTAACCATTTCGCCGAACTTGG TCGCTACTGCTACTTCCACCACATCCGCTAACAAAGTCACTAAAAACAAG AGTAATAGTAGTCCGTATTTGAACAAGCGCAGAGGTAAACCCGGGCCGGA TTCGGCCACTTCGCTGTTCGAATTGCCCGACAGCGTTATCCCAACTCCGA AACCGAAACCGAAACCAAAGCAATATCCGAAAGTTATTCTGCCGTCGAAC AGCACAAGACGCGTATCACCGGTCACGGCCAAGACCAGCAGCAGCGCAGA AGGCGTGGTCGTAGCAAGTGAGTCTCCTGTAATCGCGCCGCACGGATCGA GCCATTCGCGGTCGCTGAGTAAGCGACGGTCATCGGGCGCGCTCGTGGAC GATGACAAGCGCGAATCACACAAGCATGCAGAGCAAGCACGGCGTAATCG ATTAGCGGTCGCGCTGCACGAACTGGCGTCTTTAATCCCCGCGGAGTGGA AACAGCAAAATGTGTCGGCCGCGCCGTCCAAAGCGACCACCGTGGAGGCG GCCTGCCGGTACATCCGTCACCTA CAGCAGAACGTGAGCACGTGA CTCGA G CTCAGCTAGCTAACTGAATAAGGAACAATGAACGTTTT TCCTTTCTCTTGTTCCTAGTATTAATGACTGACCGATACATCCCTTTTTT TTTTTGTCTTTGTCTAGCTCCAGCTTTTGTTCCCTTTAGTGAGGGTTAAT TCAATTCACTGGCCGTCGTTTTACAACGTCGTGACTGGGAAAACCCTGGC GTTACCCAACTTAATCGCCTTGCAGCACATCCCCCTTTCGCCAGCTGGCG TAATAGCGAAGAGGCCCGCACCGATCGCCCTTCCCAACAGTTGCGCAGCC TGAATGGCGAATGGCGCGACGCGCCCTGTAGCGGCGCATTAAGCGCGGCG GGTGTGGTGGTTACGCGCAGCGTGACCGCTACACTTGCCAGCGCCCTAGC GCCCGCTCCTTTCGCTTTCTTCCCTTCCTTTCTCGCCACGTTCGCCGGCT TTCCCCGTCAAGCTCTAAATCGGGGGCTCCCTTTAGGGTTCCGATTTAGT GGTTTACGGCACCTCGACCCCAAAAAACTTGATTAGGGTGATGGTTCACG TAGTGGGCCATCGCCCTGATAGACGGTTTTTCGCCCTTTGACGTTGGAGT CCACGTTCTTTAATAGTGGACTCTTGTTCCAAACTGGAACAACACTCAAC CCTATCTCGGTCTATTCTTTTGATTTATAAGGGATTTTGCCGATTTCGGC CTATTGGTTAAAAAATGAGCTGATTTAACAAAAATTTAACGCGAATTTTA ACAAAATATTAACGTTTACAATTTCCTGATGCGGTATTTTCTCCTTACGC ATCTGTGCGGTATTTCACACCGCATAGGGTAATAACTGATATAATTAAAT TGAAGCTCTAATTTGTGAGTTTAGTATACATGCATTTACTTATAATACAG TTTTTTAGTTTTGCTGGCCGCATCTTCTCAAATATGCTTCCCAGCCTGCT TTTCTGTAACGTTCACCCTGTACCTTAGCATCCCTTCCCTTTGCAAATAG TCCTCTTCCAACAATAATAATGTCAGATCCTGTAGAGACCACATCATCCA CGGTTCTATACTGTTGACCCAATGCGTCTCCCTTGTCATCTAAACCCACA CCGGGTGTCATAATCAACCAATCGTAACCTTCATCTCTTCCACCCATGTC TCTTTGAGCAATAAAGCCGATAACAAAATCTTTGTCGCTCTTCGCAATGT CAACAGTACCCTTAGTATATTCTCCAGTAGATAGGGAGCCCTTGCATGAC AATTCTGCTAACATCAAAAGGCCTCTAGGTTCCTTTGTTACTTCTTCTGC CGCCTGCTTCAAACCGCTAACAATACCTGGCCCCAGCACACCGTGTGCAT TCGTAATGTCTGCCCATTCTGCTATTCTGTATACACCCGCAGAGTACTGC AATTTGACTGTATTACCAATGTCAGCAAATTTTCTGTCTTCGAAGAGTAA AAAATTGTACTTGGCGGATAATGCCTTTAGCGGCTTAACTGTGCCCTCCA TCGAAAAATCAGTCAATATATCCACATGTGTTTTTAGTAAACAAATTTTG GGACCTAATGCTTCAACTAACTCCAGTAATTCCTTGGTGGTACGAACATC CAATGAAGCACACAAGTTTGTTTGCTTTTCGTGCATGATATTAAATAGCT TGGCAGCAACAGGACTAGGATGAGTAGCAGCACGTTCCTTATATGTAGCT TTCGACATGATTTATCTTCGTTTCCTGCAGGTTTTTGTTCTGTGCAGTTG GGTTAAGAATACTGGGCAATTTCATGTTTCTTCAACACTACATATGCGTA TATATACCAATCTAAGTCTGTGCTCCTTCCTTCGTTCTTCCTTCTGTTCG GAGATTACCGAATCAAAAAAATTTCAAAGAAACCGAAATCAAAAAAAAGA ATAAAAAAAAAATGATGAATTGAATTGAAAAGCTGTGGTATGGTGCACTC TCAGTACAATCTGCTCTGATGCCGCATAGTTAAGCCAGCCCCGACACCCG CCAACACCCGCTGACGCGCCCTGACGGGCTTGTCTGCTCCCGGCATCCGC TTACAGACAAGCTGTGACCGTCTCCGGGAGCTGCATGTGTCAGAGGTTTT CACCGTCATCACCGAAACGCGCGAGACGAAAGGGCCTCGTGATACGCCTA TTTTTATAGGTTAATGTCATGATAATAATGGTTTCTTAGACGTGCGGCCG CTCTAGAACTAGTGGATCAATTCCACGGACTATAGACTATACTAGTATAC TCCGTCTACTGTACGATACACTTCCGCTCAGGTCCTTGTCCTTTAACGAG GCCTTACCACTCTTTTGTTACTCTATTGATCCAGCTCAGCAAAGGCAGTG TGATCTAAGATTCTATCTTCGCGATGTAGTAAAACTAGCTAGACCGAGAA AGAGACTAGAAATGCAAAAGGCACTTCTACAATGGCTGCCATCATTATTA TCCGATGTGACGCTGCAGCTTCTCAATGATATTCGAATACGCTTTGAGGA GATACAGCCTAATATCCGACAAACTGTTTTACAGATTTACGATCGTACTT GTTACCCATCATTGAATTTTGAACATCCGAACCTGGGAGTTTTCCCTGAA ACAGATAGTATATTTGAACCTGTATAATAATATATAGTCTAGCGCTTTAC GGAAGACAATGTATGTATTTCGGTTCCTGGAGAAACTATTGCATCTATTG CATAGGTAATCTTGCACGTCGCATCCCCGGTTCATTTTCTGCGTTTCCAT CTTGCACTTCAATAGCATATCTTTGTTAACGAAGCATCTGTGCTTCATTT TGTAGAACAAAAATGCAACGCGAGAGCGCTAATTTTTCAAACAAAGAATC TGAGCTGCATTTTTACAGAACAGAAATGCAACGCGAAAGCGCTATTTTAC CAACGAAGAATCTGTGCTTCATTTTTGTAAAACAAAAATGCAACGCGAGA GCGCTAATTTTTCAAACAAAGAATCTGAGCTGCATTTTTACAGAACAGAA ATGCAACGCGAGAGCGCTATTTTACCAACAAAGAATCTATACTTCTTTTT TGTTCTACAAAAATGCATCCCGAGAGCGCTATTTTTCTAACAAAGCATCT TAGATTACTTTTTTTCTCCTTTGTGCGCTCTATAATGCAGTCTCTTGATA ACTTTTTGCACTGTAGGTCCGTTAAGGTTAGAAGAAGGCTACTTTGGTGT CTATTTTCTCTTCCATAAAAAAAGCCTGACTCCACTTCCCGCGTTTACTG ATTACTAGCGAAGCTGCGGGTGCATTTTTTCAAGATAAAGGCATCCCCGA TTATATTCTATACCGATGTGGATTGCGCATACTTTGTGAACAGAAAGTGA TAGCGTTGATGATTCTTCATTGGTCAGAAAATTATGAACGGTTTCTTCTA TTTTGTCTCTATATACTACGTATAGGAAATGTTTACATTTTCGTATTGTT TTCGATTCACTCTATGAATAGTTCTTACTACAATTTTTTTGTCTAAAGAG TAATACTAGAGATAAACATAAAAAATGTAGAGGTCGAGTTTAGATGCAAG TTCAAGGAGCGAAAGGTGGATGGGTAGGTTATATAGGGATATAGCACAGA GATATATAGCAAAGAGATACTTTTGAGCAATGTTTGTGGAAGCGGTATTC GCAATATTTTAGTAGCTCGTTACAGTCCGGTGCGTTTTTGGTTTTTTGAA AGTGCGTCTTCAGAGCGCTTTTGGTTTTCAAAAGCGCTCTGAAGTTCCTA TACTTTCTAGAGAATAGGAACTTCGGAATAGGAACTTCAAAGCGTTTCCG AAAACGAGCGCTTCCGAAAATGCAACGCGAGCTGCGCACATACAGCTCAC TGTTCACGTCGCACCTATATCTGCGTGTTGCCTGTATATATATATACATG AGAAGAACGGCATAGTGCGTGTTTATGCTTAAATGCGTACTTATATGCGT CTATTTATGTAGGATGAAAGGTAGTCTAGTACCTCCTGTGATATTATCCC ATTCCATGCGGGGTATCGTATGCTTCCTTCAGCACTACCCTTTAGCTGTT CTATATGCTGCCACTCCTCAATTGGATTAGTCTCATCCTTCAATGCTATC ATTTCCTTTGATATTGGATCATATGCATAGTACCGAGAAACTAGTGCGAA GTAGTGATCAGGTATTGCTGTTATCTGATGAGTATACGTTGTCCTGGCCA CGGCAGAAGCACGCTTATCGCTCCAATTTCCCACAACATTAGTCAACTCC GTTAGGCCCTTCATTGAAAGAAATGAGGTCATCAAATGTCTTCCAATGTG AGATTTTGGGCCATTTTTTATAGCAAAGATTGAATAAGGCGCATTTTTCT TCAAAGCTGCGGCCGCACTCTCACTAGTACGTCAGGTGGCACTTTTCGGG GAAATGTGCGCGGAACCCCTATTTGTTTATTTTTCTAAATACATTCAAAT ATGTATCCGCTCATGAGACAATAACCGTGATAAATGCTTCAATAATATTG AAAAAGGAAGAGTATGAGTATTCAACATTTCCGTGTCGCCCTTATTCCCT TTTTTGCGGCATTTTGCCTTCCTGTTTTTGCTCACCCAGAAACGCTGGTG AAAGTAAAAGATGCTGAAGATCAGTTGGGTGCACGAGTGGGTTACATCGA ACTGGATCTCAACAGCGGTAAGATCCTTGAGAGTTTTCGCCCCGAAGAAC GTTTTCCAATGATGAGCACTTTTAAAGTTCTGCTATGTGGCGCGGTATTA TCCCGTATTGACGCCGGGCAAGAGCAACTCGCTCGCCGCATACACTATTC TCAGAATGACTTGGTTGAGTACTCACCAGTCACAGAAAAGCATCTTACGG ATGGCATGACAGTAAGAGAATTATGCAGTGCTGCCATAACCATGAGTGAT AACACTGCGGCCAACTTACTTCTGACAACGATCGGAGGACCGAAGGAGCT AACCGCTTTTTTGGACAACATGGGGGATCATGTAACTCGCCTTGATCGTT GGGAACCGGAGCTGAATGAAGCCATACCAAACGACGAGCGTGACACCACG ATGCCTGTAGCAATGGCAACAACGTTGCGCAAACTATTAACTGGCGAACT ACTTACTCTAGCTTCCCGGCAACAATTAATAGACTGGATGGAGGCGGATA AAGTTGCAGGACCACTTCTGCGCTCGGCCCTTCCGGCTGGCTGGTTTATT GCTGATAAATCTGGAGCCGGTGAGCGTGGGTCTCGCGGTATCATTGCAGC ACTGGGGCCAGATGGTAAGCCCTCCCGTATCGTAGTTATCTACACGACGG GGAGTCAGGCAACTATGGATGAACGAAATAGACAGATCGCTGAGATAGGT GCCTCACTGATTAAGCATTGGTAACTGTCAGACCAAGTTTACTCATATAT ACTTTAGATTGATTTAAAACTTCATTTTTAATTTAAAAGGATCTAGGTGA AGATCCTTTTTGATAATCTCATGACCAAAATCCCTTAACGTGAGTTTTCG TTCCACTGAGCGTCAGACCCCGTAGAAAAGATCAAAGGATCTTCTTGAGA TCCTTTTTTTCTGCGCGTAATCTGCTGCTTGCAAACAAAAAAACCACCGC TACCAGCGGTGGTTTGTTTGCCGGATCAAGAGCTACCAACTCTTTTTCCG AAGGTAACTGGCTTCAGCAGAGCGCAGATACCAAATACTGTCCTTCTAGT GTAGCCGTAGTTAGGCCACCACTTCAAGAACTCTGTAGCACCGCCTACAT ACCTCGCTCTGCTAATCCTGTTACCAGTGGCTGCTGCCAGTGGCGATAAG TCGTGTCTTACCGGGTTGGACTCAAGACGATAGTTACCGGATAAGGCGCA GCGGTCGGGCTGAACGGGGGGTTCGTGCACACAGCCCAGCTTGGAGCGAA CGACCTACACCGAACTGAGATACCTACAGCGTGAGCTATGAGAAAGCGCC ACGCTTCCCGAAGGGAGAAAGGCGGACAGGTATCCGGTAAGCGGCAGGGT CGGAACAGGAGAGCGCACGAGGGAGCTTCCAGGGGGAAACGCCTGGTATC TTTATAGTCCTGTCGGGTTTCGCCACCTCTGACTTGAGCGTCGATTTTTG TGATGCTCGTCAGGGGGGCGGAGCCTATGGAAAAACGCCAGCAACGCGGC CTTTTTACGGTTCCTGGCCTTTTGCTGGCCTTTTGCTCACATGTTCTTTC CTGCGTTATCCCCTGATTCTGTGGATAACCGTATTACCGCCTTTGAGTGA GCTGATACCGGTCGCCGCAGCCGAACGACCGAGCGCAGCGAGTCAGTGAG CGAGGAAGCGGAAGAGCGCCCAATACGCAAACCGCCTCTCCCCGCGCGTT GGCCGATTCATTAATGCAGCTGGCACGACAGGTTTCCCGACTGGAAAGCG GGCAGTGAGCGCAACGCAATTAATGTGAGTTACCTCACTCATTAGGCACC CCAGGCTTTACACTTTATGCTTCCGGCTCCTATGTTGTGTGGAATTGTGA GCGGATAACAATTTCACACAGGAAACAGCTATGACCATGATTACGCCAAG CTCGAAATACGACTCACTATAGGGCGAATTGGGTACCGGGCCGGCCGTCG AGCTTGATGGCATCGTGGTGTCACGCTCGTCGTTTGGTATGGCTTCATTC AGCTCCGGTTCCCAACGATCAAGGCGAGTTACATGATCCCCCATGTTGTG AAAAAAAGCGGTTAGCTCTTCGGTCCTCCGATCGTTGTCAGAAGTAAGTT GGCCGCAGTGTTATCACTCATGGTTATGGCAGGAACTGCATAATTCTCTT ACTGTCATGCCATCCGTAAGATGCTTTTCTGTGACTGGTGTACTCAACCA AGTCATTCTGAGAATAGTGTATGCGGCGACCGAGTTGCTCTTGCCCGGCG TCAACACGGGATAATACCGCGCCACATAGCAGAACTTTAAAAGTGCTCAT CATTGGAAAACGTTCTTCGGGGCGAAAACTCTCAAGGATCTTACCGCTGT TGAGATCCAGTTCGATGTAACCCACTCGTGCACCCAACTGATCTTCAGCA TCTTTTACTTTCACCAGCGTTTCTGGGTGAGCAAAAACAGGAAGGCAAAA TGCCGCAAAAAAGGGAATAAGGGCGACACGGAAATGTTGAATACTCATAC TCTTCCTTTTTCAATATTATTGAAGCATTTATCAGGGTTATTGTCTCATG AGCGATACATATTTGAATGTATTTAGAAAAATAAACAAATAGGGGTTCCG CGCACATTTCCCCGAAAAGTGCCACCTGACGTCTAAGAAACCATTATTAT CATGACATTAACCTATAAAAATAGGCGTATCACGAGGCCCTTTCGTCTTC AAGAATTGGGGATCTACGTATGGTCATTCTTCTTCAGATTCCCTCATGGA GAAGTGCGGCAGATGTATATGACAGAGTCGCCAGTTTCCAAGAGACTTTA TTCAGGCACTTCCATGATAGGCAAGAGAGAAGACCCAGAGATGTTGTTGT CCTAGTTACACATGGTATTTATTCCAGAGTATTCCTGATGAAATGGTTTA GATGGACATACGAAGAGTTTGAATCGTTTACCAATGTTCCTAACGGGAGC GTAATGGTGATGGAACTGGACGAATCCATCAATAGATACGTCCTGAGGAC CGTGCTACCCAAATGGACTGATTGTGAGGGAGACCTAACTACATAGTGTT TAAAGATTACGGATATTTAACTTACTTAGAATAATGCCATTTTTTTGAGT TATAATAATCCTACGTTAGTGTGAGCGGGATTTAAACTGTGAGGACCTCA ATACATTCAGACACTTCTGACGGTATCACCCTACTTATTCCCTTCGAGAT TATATCTAGGAACCCATCAGGTTGGTGGAAGATTACCCGTTCTAAGACTT TTCAGCTTCCTCTATTGATGTTACACTCGGACACCCCTTTTCTGGCATCC AGTTTTTAATCTTCAGTGGCATGTGAGATTCTCCGAAATTAATTAAAGCA ATCACACAATTCTCTCGGATACCACCTCGGTTGAAACTGACAGGTGGTTT GTTACGCATGCTAATGCAAAGGAGCCTATATACCTTTGGCTCGGCTGCTG TAACAGGGAATATAAAGGGCAGCATAATTTAGGAGTTTAGTGAACTTGCA ACATTTACTATTTTCCCTTCTTACGTAAATATTTTTCTTTTTAATTCTAA ATCAATCTTTTTCAATTTTTTGTTTGTATTCTTTTCTTGCTTAAATCTAT AACTACAAAAAACACATACAG Appended as Seq ID:9 Bolded sequence shows PHO4 Underlined sequences represent sites for primers.
[0083] Also pYX212 with PHO4 was transformed into YD80 using the methods already described.
[0000] Sample Preparation, Inositol Phosphates and pNPP
[0084] 1.5 ml of cell suspension was withdrawn at intervals during the growth and centrifuged for 3 minutes at 13000 rpm to pellet the cells. One ml of the supernatant was transferred to a new micro-tube and acidified by adding 150 μl of 4 M HCl. This yields approximately 0.5 M HCl, which is enough to inactivate all enzymatic activity potentially left in the supernatant. Chemical acid hydrolysis of inositol phosphates does not take place in such solutions without strong heating. These samples were stored in freezer until use for analysis of IP:s and pNPP. A reference sample for identification of peaks was prepared by chemically hydrolyzing 1 mM sodium phytate (Na-IP6) in 2 ml of 0.5 M HCl. The solution was heated to 110° C. for 15 h yielding a mixture of isomers of IP:s that was stored in freezer until used as reference sample.
[0000] Bread Dough Making, Phosphate Extraction and Analysis
[0085] To analyze the P i and IP6 content in a typical environment, baker's yeast are exposed to during bread leavening two simple doughs were mixed, in which two types of flour were used: whole meal wheat flour (100% extraction rate; i.e. the proportion of the whole wheat grain obtained as finished flour), and normal wheat flour (extraction rate 60%). The dough mixture contained: 300 g flour, log sucrose, 3 g NaCl, 20 g commercial baker's yeast (Swedish Yeast Company) and 200 g tap-water. At time zero and thereafter every 15 min, 20 g of dough was withdrawn and mixed with 40 ml 0.5 M HCl (at room temperature this HCl concentration will not hydrolyze IP6, but is sufficient to inactivate enzymatic activity). Inorganic phosphate (P i ) and IP6 were extracted by magnetically stirring the mixture for three hours at room temperature. The extracts were centrifuged, the supernatant collected and frozen until use. For analysis, the samples were thawed and 1 ml was centrifuged in a micro-tube for 5 min at 13000×g. The resulting supernatants were appropriately diluted with mQ-water and inositol phosphates were analyzed by HPIC chromatography as described in previous paragraph. The ion chromatographic analysis of P i were performed using a Dionex (Sunnyvale, Calif., USA) model 4500i equipped with a 50 μl loop injector, PAX-100 guard and analytical column, Anion Micro Membrane Supressor and a conductivity detector. The samples were eluted with a linear gradient of water and increasing portion of 200 mM NaOH, starting with 6% NaOH and ending after 35 min at 50% NaOH
[0000] Results
[0000] Expression and Eepression of Phytase Activity in Wild-Type Yeasts
[0086] IP6 is efficiently degraded by yeast in a synthetic medium with IP6 as the sole phosphorous source. Türk et al. (2000) Inositol hexaphosphate hydrolysis by baker's yeast. Capacity, kinetics, and degradation products. J. Agric. Food Chem. 48, 100-104 In order to test whether extracellular IP6 hydrolysis by S. cerevisiae was repressed by inorganic phosphate (P i ), synthetic yeast minimal medium containing P i (26 mM) was supplemented with IP6 (CBSIP6+P i ). For all S. cerevisiae tested, that is SKQ2n, CBS 7764, CBS 7765, YS18, BY4741 and YMR4 virtually no breakdown of IP6 was detected in the IP6+P i cultures, showing an efficient repression of phytase activity by high levels of extracellular P i . Referring to FIG. 1 , growth of S. cerevisiae SKQ2n (squares) and extracellular concentration of inositol hexaphosphate (IP6; triangles), measured by HPIC, as a function of time is shown. Growth was performed in synthetic CBS medium with 2% (wt/vol) glucose as carbon and energy source. Filled symbols: Inositol hexaphosphate (IP6) as the sole phosphorous source; open symbols: inositol hexaphosphate plus inorganic phosphate (P i ) as combined phosphorous sources. Data are from a representative experiment performed many times. Error bars on IP6 data show maximum variation between repeated HPIC analysis. The typical pattern for the IP6 concentration in the medium during growth in the absence and presence of P i is depicted for strain SKQ2n in FIG. 1 .
[0087] In this experiment, all the IP6 was depleted before 20 h of growth in the CBSIP6 culture, while in the CBSIP6+P i culture no IP6 was degraded at that time. For all strains, the growth rates, as calculated by regression in the exponential respiro-fermentative phase (glucose growth), were as rapid in CBSIP6 medium as compared with CBSIP6+P i or CBSP i media, showing efficient utilization of IP6 as P-source for growth by S. cerevisiae.
[0088] The same type of experiments were performed also in complex and rich YPD medium, either with the addition of only IP6 (YPDIP6) or with the addition of IP6 and Pi (YPDIP6+P i ). The YPD experiments yielded data consistent with the CBS cultures, that is IP6 degradation without loss in growth rate in YPDIP6 medium and repression of phytase activity in YPDIP6+P i medium (data not shown). However, the P i induced repression was for some strains (e.g. YS18) less pronounced in YPD as compared with CBS medium, that is a certain constitutive, not negligible, phytase activity was detected.
[0000] Inositol Phosphates Formed During IP6 Degradation
[0089] IP6 and the breakdown products formed as a result of IP6 hydrolysis by the yeast were identified and quantified by HPIC. Referring to FIG. 2 , chromatographic profiles (HPIC) of chemical acid hydrolysate of sodium phytate (first line), and supernatant from S. cerevisiae cultures (second and third lines) after 15 h of growth is shown. S. cerevisiae was cultured in CBS medium containing either IP6 as the sole P-source (second line, thick) demonstrating yeast phytase activity, or in CBS medium with IP6 and P i as combined P-sources (third line) showing P i -induced repression of phytase activity. Numbered peaks: 1: SO 4 −2 ; 2: Ins(1,2,6)P 3 ; 3: Ins(1,2,5,6)P 4 ; 4: Ins(1,2,4,5,6)P 5 ; 5: IP6.
[0090] The chromatographic profile showed that the enzymes exerting the yeast phytase activity are very specific with respect to position on the inositol ring. Only one isomer of each IP 5 , IP 4 and IP 3 was detected for samples withdrawn during growth of S. cerevisiae in CBSIP6 medium ( FIG. 2 , second line). These isomers aligned with an acid chemical hydrolysate ( FIG. 2 , first line, in which all peaks previously have been identified) proved to be I(1,2,4,5,6)P 5 , I(1,2,5,6)P 4 , I(1,2,6)P 3 , respectively. It is known that peak 2 in the hydrolysate may contain a mixture of I(1,2,6)P 3 and I(1,2,3)P 3 . However, the 1(1,2,3)P 3 isomer can be excluded in the yeast samples since position 3 was already missing. The same pattern of IP isomers was obtained for all strains tested in our collection, including laboratory strains and several wild-types. The lower, third line in FIG. 2 shows the extracellular composition of IP:s from a S. cerevisiae CBSIP6+Pi culture at 15 hrs of growth. In such cultures no lower inositol phosphates were detectable and the concentration of IP6 (peak 5) remained high through out the experiment proving the P i induced repression of extracellular phytase activity.
[0000] PHO Deletion Mutants
[0091] The major secretory acid phosphatase, encoded by PHO5, may be involved in phytate hydrolysis. A PHO5 deletion mutant may be less efficient in degrading extracellular IP6 as compared with the corresponding parent strain. For this purpose the pho3Δpho5Δ double mutant YMR4 was used. By using this mutant the effect of missing PHO3, in addition to PHO5, was assessed. However, this gene may be less important since it has been shown to be repressed by thiamine, (which is present in the CBS medium) and its product is mainly a thiamine phosphatase, Praekelt et al. (1994) Regulation of TH14 (MOL1), a thiamine-biosynthetic gene of Saccharomyces cerevisiae. Yeast. 10, 481-490. Contrary to expectation, the mutant was not affected.
[0092] Referring to FIGS. 3A and 3B , growth (squares) of S. cerevisiae parent strain YS18 (open symbols) and S. cerevisiae YMR4 pho5Δpho3Δ double deletion mutant (filled symbols) and extracellular concentration of IP6 (circles) as determined by HPIC. FIG. 3A shows synthetic CBS medium with glucose as carbon and energy source and IP6 plus P i as phosphorous sources (repressing conditions). FIG. B shows synthetic CBS medium with glucose as carbon and energy source and IP6 as the sole phosphorous source (de-repressing conditions). Represented data are means of double samples from a representative experiment run twice.
[0093] In repeated experiments strain YMR4 hydrolyzed extracellular IP6 at a rate equal to its parent strain YS18 ( FIG. 3B ). In addition, FIG. 3A shows that in CBSIP6+P i medium (repressing conditions), the pattern of growth and the P i induced repression was unaffected in the mutant strain YMR4, which closely follows the pattern for YS18. For both strains at time 24 h after inoculation, 94% of the initial amount of IP6 was still present in the CBSIP6+P i cultures ( FIG. 3A ). At this time, neither IP6 nor any other lower IP:s were detectable in the medium of the parallel CBSIP6 culture ( FIG. 3B ). Additional evidence for independence of PHO5 in this context was provided by the rate of growth for the mutant in CBSIP6 medium. The calculated growth rate in the exponential respiro-fermentative phase (growth on glucose, CBSIP6 medium) was 0.33 h −1 (generation time of 2.1 h) for both YMR4 and its parent strain YS18. This is not evidence that Pho5p and Pho3p are unable to hydrolyze IP6, it is only evidence that shows that they are not needed by the yeast for intact phytase activity.
[0094] By PCR and homologous recombination PHO10 was deleted in YMR4 and YS18 thereby obtaining a pho5Δpho3Δpho10Δ triple mutant and pho10Δ single mutant labeled YM10 and YS10, respectively. Referring to FIG. 4 , concentration of inositol hexaphosphate (IP6) in yeast culture supernatant as a function of growth in CBS medium with IP6 as the sole phosphorous source is shown. Grey circles: YS18 parent strain with all PHO genes intact; filled squares: YMR4 pho3Δpho5Δ double mutant; filled triangles: YM10 pho3Δpho5Δpho10Δ triple mutant; and open diamonds: YS10 pho10Δ single deletion mutant. Data are means of double samples from separate cultures and error bars show the variation between those. These strains were cultured in CBSIP6 and YPDIP6 medium, and the medium concentration of IP6 was monitored by HPIC during growth. In CBS, the rate of IP6 degradation was unaffected in YS10 showing that also PHO10 was superfluous ( FIG. 4 ) for intact phytase activity.
[0095] Even in YM10, in which the only remaining secretory phosphatase is Pho11p, the net extracellular phytase activity was unaffected as compared with YS18 and YMR4. Only a slight, but significant, decrease in the rate of IP6 degradation was in CBS detected in this mutant ( FIG. 4 ). However, in the complex medium YPD, the triple mutant showed a strong reduction in rate of extracellular IP6 ( FIG. 5 ) with maintained growth rate, suggesting phytase activity for Pho10p and at least one more enzyme.
[0096] Referring to FIG. 5 , concentration of inositol hexaphosphate (IP6) in yeast culture supernatant as a function of growth in complex YPD medium with IP6 as the added phosphorous source is shown. Grey circles: YS18 parent strain with all PHO genes intact; filled squares: YMR4 pho3,Δpho5Δ double mutant; filled triangles: YM10 pho3Δpho5Δpho10Δ triple mutant; and open diamonds: YS10 pho10Δ single deletion mutant. Data are means of double samples from separate cultures and error bars show the variation between those.
[0000] Overexpression of PHO5
[0097] Referring to FIG. 6 , a vector construct consisting of plasmid pYX212 containing the insert PHO5 used for transformation of YS18 and YMR4. The glycolytic promoter triose phosphate isomerase (TPI1) controlling expression of PHO5, the yeast selection marker URA3 and the Amp R gene are depicted.
[0098] In order to assess the impact of exclusively PHO5 expression on the extracellular IP6 degradation YMR4 and YS18 were both transformed with pYX212 containing the insert PHO5 controlled by the constitutive glycolytic promoter TPI1 ( FIG. 6 ).
[0099] The resulting strains were designated YM-p5 and YS-p5, respectively (Table 1). The experiments with these mutants were performed in YPD medium with the addition of the appropriate phosphorous source. Growth and extracellular IP6 concentration were assessed as a function of time. Referring to FIGS. 7A and 7B , extracellular concentration of IP6 as a function of growth time of S. cerevisiae YMR4 (A) and YS18 (B), with and without the PHO5 containing plasmid pYX212. Open symbols: strains without plasmid; solid symbols: strains containing the plasmid pYX212-PHO5. The experiment was performed in YPD medium with 2% glucose supplemented with either only IP6 (circles) or with both IP6 and P i (triangles). Represented data are means from two to three independent experiments with a standard deviation never exceeding 5%. From both YM-p5 and YS-p5 data it is evident that PHO5 encodes an enzyme with phytase activity ( FIGS. 7A and B).
[0100] Under normally repressing conditions (YPDIP6+Pi) IP6 was by YM-p5 and YS-p5 degraded at a fairly high rate (filled triangles in FIGS. 7A and 7B ), demonstrating that phytase activity was in these mutants constitutively expressed. The corresponding parent strains lacking the plasmid are shown as controls (open triangles). These controls were in YPD somewhat lesser repressed as compared with CBS medium, however, much more repressed than the cells with plasmid. After 24 h of growth strain YM-p5 had degraded 63% of the initial IP6 whereas in the YMR4 control strain the corresponding value at 24 h was only 22.5% ( FIG. 6 ). The rate of IP6 degradation in YPDIP6 non-repressing medium was also analyzed. During these conditions PHO10 and PHO11 plus the introduced PHO5 would be expressed in YM-p5, and PHO5, PHO10 and PHO11 plus the introduced PHO5 in the YS-p5 strain. The data show that the plasmid located PHO5 indeed increased the net rate of IP6 degradation ( FIGS. 7A and 7B ) in both strains. The effect was more pronounced in YS-p5, in which the PHO5 gene is present both in the genome and on the plasmid. The combined data from the PHO5 overexpression experiments and the experiments with deletion strains compared with their parent strains ( FIGS. 3 and 4 ) shows that Pho5p, Pho10p and at least one more enzyme, believed to be Pho11p, are by definition all phytases.
[0000] Deletion of the Regulator Genes PHO80, PHO85 and PHO2
[0101] The PHO system is involved in the yeast phytase activity. Accordingly, deletions in the regulatory genes PHO80 and PHO85 yield constitutive phytase activity.
[0102] Referring to FIG. 8 , a direct comparison of phytate degrading capacity between PHO5 overexpressing strains, and pho80Δ and pho85Δ deletions mutants. Extracellular concentration of IP6 is plotted as a function of growth time of S. cerevisiae YS18-p5 (triangles) with the PHO5 containing plasmid pYX212, S. cerevisiae pho80Δ deletion mutant (squares) and pho85Δ deletion mutant (circles) is shown. The experiment was performed in YPD medium with 2% glucose supplemented with either only IP6 (solid symbols) or with both IP6 and P i (open symbols). Data are means from two independent experiments with a standard deviation never exceeding 5%.
[0103] As shown in FIG. 8 these mutants were highly effective in degrading IP6, and completely constitutive demonstrating that the PHO system indeed is involved in S. cerevisiae phytase activity. Since the net rate of IP6 degradation was very rapid, these strains were compared with the YS18-p5 (PHO5 overexpressing) strain. Both strain pho80Δ and pho85Δ showed a higher net rate in IP6 degradation as compared with the YS18-p5 ( FIG. 8 ). The growth rate was unchanged in strain pho80Δ, however significantly reduced in strain pho85Δ. In addition to the pho80Δ and pho85Δ strains retrieved from BY4741 (EUROSCARF collection), another pho80Δ, referring to FIG. 12 , mutant was constructed by deletion in YS18, yielding strain YD80. The highly efficient extracellular phytase activity was reconfirmed in this strain.
[0104] Referring to FIG. 9 , phytate degrading capacity of pho2Δ deletion mutant is shown. For comparison, pho80Δ deletion strain and BY4741 with all PHO genes intact are also shown. Extracellular concentration of IP6 is plotted as a function of growth time in YPD. For explanation of symbols see Figure. The P-source used is shown within parenthesis. In addition to IP6 data, growth data as OD610, are shown for the pho2Δ deletion mutant and for its parent strain BY4741. Data are means from two independent experiments with a standard deviation never exceeding 5%.
[0105] PHO2 is together with PHO4 known to positively regulate the expression of the secretory phosphatases PHO5, PHO10 and PHO11. In a direct comparison the pho2 deletion mutant was demonstrated to lack virtually all phytase activity, demonstrating that yeast phytase activity is largely a matter of its PHO system. The phytase activity may therefore be further increased by overexpressing PHO2 and/or PHO4.
[0000] Expression of PHO3
[0106] The expression of PHO3, in addition to expression of PHO5, PHO10 and PHO11 may increase the rate of extracellular IP6 degradation. For this purpose the parent strain YS18 was used in a CBS medium excluding thiamine, which is known to repress PHO3 expression, Nosaka et al. (1989) A possible role for acid phosphatase with thiamin - binding activity encoded by PHO 3 in yeast. FEMS Microbiol. Lett. 51, 55-59; Nosaka (1990) High affinity of acid phosphatase encoded by PHO 3 gene in Saccharomyces cerevisiae for thiamin phosphates. Biochim. Biophys. Acta. 1037, 147-154. As controls normal CBSIP6 medium (with thiamine) was used, with and without thiamine phosphate to ensure that the yeast was not negatively affected by the missing thiamine. Growth rates and IP6 degradation were by YS18 not different between the three media used, indicating that PHO3 is of no or minor significance for yeast phytase activity (data not shown).
[0000] Competitive Degradation of IP6 and pNPP
[0107] The PHO system in S. cerevisiae has frequently been studied using phenyl phosphate and para-nitrophenyl phosphate (pNPP) as substrates. Monod et al. (1989) Functional analysis of the signal - sequence processing site of yeast acid phosphatase. Eur. J. Biochem. 182, 213 -221; Shnyreva et al. (1 996) Biochemical properties and excretion behavior of repressible acid phosphatases with altered subunit composition. Microbiol. Res. 151, 291-300; Martinez et al. (1998) Identification, cloning and characterization of a derepressible Na + - coupled phosphate transporter in Saccharomyces cerevisiae. Mol. Gen. Genet. 258, 628-638. These compounds are used as model organic phosphorous source. Yeasts are often exposed to several organic phosphorous sources.
[0108] Accordingly, the impact of adding a second organic phosphorous compound (PNPP) on the rate of IP6 degradation was studied. Both compounds are readily degraded by S. cerevisiae and since the PHO system is involved in both cases a competitive situation arose.
[0109] Referring to FIG. 10 , extracellular concentration of para-nitrophenyl phosphate (PNPP, squares) and IP6 (triangles) as a function of growth of S. cerevisiae SKQ2n in CBS medium with 2% glucose as carbon and energy source is shown. The CBS medium was supplemented either with IP6 as the sole P-source (open triangles), with pNPP as the sole P-source (open squares) or with both IP6 and pNPP as combined P-sources (Solid symbols).
[0110] In the experiment, with both IP6 and pNPP present and P i absent, the rate of IP6 degradation was completely unchanged as compared with IP6 alone ( FIG. 10 ). However, the rate of pNPP was delayed by presence of IP6 compared to pNPP alone. Most of the degradation of pNPP occurred after IP6 was depleted from the medium. At 12 h of growth, IP6 was depleted in both cultures, whereas only 17% of the initial pNPP was used in the mixed culture, and 49% in the sole pNPP culture. The experiment was also performed with the pNPP concentration set to 6 times the concentration of IP6 (2.25 mM) to obtain equal stoichiometry in number of available phosphate groups. Six times more frequently pNPP randomly met the enzymes. The experiment yielded similar data, that is no change in rate of IP6 hydrolysis in the presence of pNPP and delayed pNPP degradation as compared with pNPP alone was observed (data not shown).
[0000] Content of Inorganic Phosphate and IP6 in Bread Dough
[0111] To understand the yeast environment during bread making, relative to the PHO system, the P i and IP6 content were analyzed in two types of wheat based bread doughs. In both doughs the level of P i increased and the level of IP6 decreased as a function of leavening time ( FIG. 11 ).
[0112] Referring to FIG. 11 , the content of inositol hexaphosphate (IP6, triangles) and inorganic phosphate (P i ; squares), expressed as μmol per gram wet dough, as a function of leavening time in two types of wheat based doughs is shown. Solid symbols: whole meal wheat flour (100% extraction rate; i.e. the proportion of the whole wheat grain obtained as finished flour), and open symbols: white wheat flour (extraction rate 60%). Error bars indicate the maximum variation between double samples.
[0113] The concentration of P i was higher in the whole wheat flour dough starting at 4 μmol/g wet dough (approximately equal to mM), and ending after 60 min of leavening at 11.8 μmol/g dough, while in the white wheat flour the start and end concentrations were 1.7 μmol/g and 5.8 μmol/g, respectively. The initial concentrations of IP6 were 9 μmol/g and 3 μmol/g for whole-wheat flour and white wheat flour, respectively, decreasing to 4.8 and 0.4 μmol/g after 60 minutes of leavening. This demonstrates that phytases are active in the dough.
[0114] Most previous investigations in the context of yeast degrading IP6 refer to a “yeast phytase”, frequently distinguishing it from phosphatases, without identifying genes and enzymes. Nayini et al. (1984) The phytase of yeast. Lebensm. Wiss. u-Technol. 17, 24-26; Harland et al. (1989) Effects of phytase from three yeasts on phytate reduction in Norwegian whole wheat flour. Cereal Chem. 4, 357-358; Nair et al. (1991) Phytic acid content reduction in canola meal by various microorganisms in a solid state fermentation process. Acta Biotechnologica. 11, 211-218. Lambrechts et al. (1992) Utilization of phytate by some yeasts. Biotechnol. Lett. 14, 61-66 Attempts to assess the yeast contribution to the observed phytase activity during bread leavening has sometimes been performed in conditions such as starvation in combination with 50° C., Harland et al. (1989) Effects of phytase from three yeasts on phytate reduction in Norwegian whole wheat flour. Cereal Chem. 4, 357-358.
[0115] The yeast phytase activity in conditions suitable for yeast growth were studied and it was observed that, provided absence of P i , S. cerevisiae is well adapted to utilize extracellular IP6 as a phosphorous source. The rate of IP6 degradation was rapid and supplied the yeast metabolic machinery with phosphorous without a decrease in growth rate, that arose from the increased energy cost of synthesizing the degrading enzymes. The phosphate-induced repression of phytase activity indicated that the PHO gene family in S. cerevisiae is involved.
[0116] In low concentrations of inorganic phosphate S. cerevisiae is known to induce the synthesis of at least three phosphatases that are exported out through the cellular membrane. It appears that the enzymes work best in oligomeric organization, as studied by Shnyreva et al. Shnyreva et al. (1996) Biochemical properties and excretion behavior of repressible acid phosphatases with altered subunit composition. Microbiol. Res. 151, 291-300, composed of a specific ratio between Pho5p (86%), Pho10p and Pho11p (14% together). The so-called “yeast phytase” may be the concerted action of the components in this oligomeric enzyme.
[0117] However, when using pNPP as substrate Shnyreva et al., Shnyreva et al. (1996) Biochemical properties and excretion behavior of repressible acid phosphatases with altered subunit composition. Microbiol. Res. 151, 291-300 have shown that also homopolymers of the individual secretory acid phosphatases have significant and different activities. In addition to being present in the largest amount, Pho5p was found to exert the highest specific activity. Fifteen times higher activity was obtained for Pho5p expressed alone as compared with Pho10p and Pho11p, respectively.
[0118] The PHO5 deletion did not yield a less efficient strain with respect to IP6 degradation. Several explanations could fit the data: (i) PHO5 was not important for phytase activity or (ii) the remaining level of Pho10p and Pho11p, organized without Pho5p, was sufficient for unchanged phytase activity. It may be that (iii) PHO10 and PHO11 became unregulated in the absence of PHO5. In fact, the absence of PHO10 or PHO11 has been shown to increase the Pho5p level Shnyreva et al. (1996) Biochemical properties and excretion behavior of repressible acid phosphatases with altered subunit composition. Microbiol. Res. 151, 291-300 and hence, the opposite may also be true. A (iv) different as yet unidentified phytase enzyme may exist. The S. cerevisiae gene DIA3 for instance, encodes a protein largely related to Pho3, Pho5, Pho10 and Pho11 (see e.g. the YPD database). Dia3p may be extracellular.
[0119] Since the significance of the different secretory phosphatases in IP6 specific degradation is not known a strain was created lacking only PHO10 (YS10). Using strain YS10 it was demonstrated that PHO10 was also dispensable for yeast phytase activity, shown by intact growth- and IP6 degradation rate. Thus, neither of PHO3, PHO5 or PHO10 was essential for high phytase activity. However, in a triple mutant (YM10), a very small, but significant decrease in rate of IP6 degradation was observed in CBS and a pronounced decrease in YPD, demonstrating two things. First, Pho10p is an enzyme with phytase activity since a change was observed when PHO10 was the only difference and second, a strain with only Pho11p alone (or an unknown phytase) still has a remarkable phytase activity in defined medium. For all these deletion strains the growth rate remained unchanged, so the net phytase activity is comparable also if expressed as biomass specific phytase activity. This further means that phosphorous never became limiting, even in a strain lacking three secretory phosphatases during growth on IP6. It is interesting that the main secretory phosphatase (Pho5p) is dispensable and that a strain encoding only one of two so-called minor secretory phosphatases, (Pho11p), is alone able to keep almost unchanged phytase activity.
[0120] To assess the phytase potential of solely Pho5p, two strains were constructed which expressed almost exclusively PHO5 during growth in repressing medium. The data obtained using these strains show that PHO5 by itself encodes a protein with phytase activity and is therefore likely to participate when a wildtype strain degrades IP6. When growing YM-p5 and YS-p5 in de-repressing media, additional phytase activity was observed as compared with the corresponding strains lacking the plasmids ( FIG. 6 ). This was not necessarily expected since the increased rate of IP6 degradation leads to increase in P i concentration which in turn have a repressing impact on the genomic phytase encoding genes. The data reveals that yeast phytase activity is not the action of one gene product. However, simply by overexpressing one single gene strains were obtained with improved net phytase activity under both repressing and de-repressing conditions.
[0121] Furthermore, the regulatory components pho80p and pho85p are known to phosphorylate pho4p in conditions of high medium Pi levels. The phosphorylated pho4p retrieves affinity for a transporter and leaves the nucleus instead of acting as a transcription activator for several PHO genes, including the secretory phosphatases. If one or both of pho8Op and pho85p is missing its kinase activity on pho4p is lost and pho4p will together with pho2p remain active as transcriptional activators for the sectretory phosphatases. The resulting mutant constitutively expresses PHO5, PHO10 and PHO11. Since deletions of PHO80 or PHO85 both yielded very strong constitutive phytase activity the involvement of the PHO system was again demonstrated.
[0122] It has previously been shown that the contribution of yeast to the phytase activity observed during bread leavening is very small, and not sufficient for a significant increase in iron and zinc absorption, Harland et al. (1989) Effects of phytase from three yeasts on phytate reduction in Norwegian whole wheat flour. Cereal Chem. 4, 357-358; Türk et al. (1992) Phytate degradation during bread making: effect of phytase addition. J. Cereal Science. 15, 281-294; Türk et al. (1996) Reduction in the levels of phytate during wholemeal bread making; Effect of yeast and wheat phytases. J. Cereal Science. 23, 257-264. The IP6 level and mineral uptake in human intestine was, however, improved when adding commercial Aspergillus phytase to dough or wheat rolls, respectively, Türk et al. (1992) Phytate degradation during bread making: effect of phytase addition. J. Cereal Science. 15, 281-294; Türk et al. (1996) Reduction in the levels of phytate during wholemeal bread making; Effect of yeast and wheat phytases. J. Cereal Science. 23, 257-264. It has been shown that the phytase activity is P i repressed. The concentration of P i was shown to be in the millimolar range which is above the level known to induce repression, Yoshida et al. (1989) Function of the PHO regulatory genes for repressible acid phosphatase synthesis in Saccharomyces cerevisiae. Mol. Gen. Genet. 217, 40-46. (10 mM P i is often used as “high” and 0.2 mM as “low”; Ogawa et al. (2000) New components of a system for phosphate accumulation and polyphosphate metabolism in Saccharomyces cerevisiae revealed by genomic expression analysis. Mol. Biol. Cell. 11, 4309-4321). Hence, in the typical bread making situation the PHO genes encoding Pho5p, Pho10p and Pho11p are not very active and, as shown, phytase activity is not substantially expressed. Furthermore, it has been shown that the IP6 degradation in cereals must be extensive to improve the iron absorption, Brune et al. (1992) Human iron absorption from bread: Inhibiting effects of cereal fibre, phytate and inositol phosphates with different numbers of phosphate groups. J. Nutr. 122, 442-449. As little as 0.5 μmol/g dry sample of IP6 and IP5 is inhibitory, Sandberg et al. (1999) Inositol phosphates with different number of phosphate groups influence iron absorption in humans. Am. J. Clin. Nutr. 70, 240-246. The data on the content of IP6 in dough were expressed per wet weight (i.e. the dry content is higher), and even at the end of the fermentation it exceeds iron inhibitory levels. The reduction in IP6 taking place during dough fermentation with commercial baker's strains has been shown to be almost exclusively due to plant phytases present in the flour. A constitutively expressing yeast strain is desirable.
[0123] It has further been demonstrated herein an apparent preference for IP6 over pNPP when these were given together. In Nayaini et al., Nayini et al. (1984) The phytase of yeast. Lebensm. Wiss. u-Technol. 17, 24-26. yeast phytase and phosphatase were purified from a total biomass extraction of a Baker's yeast cake. The distinction between phytase (which is a phosphatase, for which one of the substrates is phytate) and phosphatase activity was that a phosphatase was able to hydrolyze alpha-glycerophosphate but unable to hydrolyze IP6. The purified phytase was assessed for substrate specific activity using 11 different phosphorous sources. Phenyl-phosphate was one of these and the specific activity with this substrate was 40 times higher than for IP6. The data set forth above, shows virtually no degradation of pNPP until IP6 is depleted. Even at six times higher pNPP concentration the data indicate an inhibition of pNPP hydrolysis by IP6. Although the yeast phytase is not one single enzyme the activity was shown to be very precise in regard to the position on the inositol ring to be hydrolyzed, consistent with previous data on one commercial baker's strain, Türk et al. (2000) Inositol hexaphosphate hydrolysis by baker's yeast. Capacity, kinetics, and degradation products. J. Agric. Food Chem. 48, 100-104. This specificity, the so-called 3-phytase activity, was true for all yeasts tested, including such different wild isolates of S. cerevisiae including those from fish intestine and clinical isolates of human pathogens, as well as for all deletion strains. Accordingly, the modified strains can be used to efficiently produce highly specific isomers of lower inositol phosphates.
[0124] In addition to the Saccharomyces phytase work we are screening non- Saccharomyces yeasts for the possibility of finding novel enzymes with desirable properties. Tested species are primarily from tropical- and cactus origin. Desired properties are high temperature optimum and/or a specificity yielding different isomers as compared with S. cerevisiae. So far, all tested species and strains have shown phytase activity. However, biochemical properties of the different enzymes have not yet been examined.
[0125] In addition to S. cerevisiae, other yeast species that are capable of expressing phytase can be transformed to exhibit increased phytase activity.
[0126] Although the present invention has been shown and described with respect to several preferred embodiments thereof, various changes, omissions and additions to the form and detail thereof, may be made therein, without departing from the spirit and scope of the invention. | The present invention relates to a method for producing a modified Saccaromyces cerevisiea having improved phytase activity, such a Saccaromyces cerevisiae, use of such a modified strain, as well as phytase production, and inositol isomers derived from use of such a modified strain. | 0 |
[0001] This continuation-in-part patent application is based on and claims priority to U.S. patent application Ser. No. 10/975,272, filed Oct. 28, 2004, entitled, Nitrogen-Modified Titanium and Method of Producing Same, and is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention relates in general to forming metal alloys and, in particular, to a method for gas-phase alloying of metallic materials.
[0004] 2. Description of the Related Art
[0005] Many metal objects are produced by thermomechanical processes including casting, rolling, stamping, forging, extrusion, machining, and joining operations. Multiple steps are required to produce a finished article. These conventional operations often require the use of heavy equipment, molds, tools, dies, etc. For example, a typical process sequence required to form a small cylindrical pressure vessel might include casting an ingot, heat treating and working the casting to homogenize it by forging, extrusion, or both, machining a hollow cylinder and separate end caps from the worked ingot and, finally, welding the end caps to the cylinder.
[0006] Conventional production methods are subtractive in nature in that material is removed from a starting block of material to produce a more complex shape. Subtractive machining methods are deficient in many respects. Large portions of the starting material are reduced to waste in the form of metal cuttings and the like. These methods also produce waste materials such as oils and solvents that must be further processed for purposes of reuse or disposal. Even the articles produced are contaminated with cutting fluids and metal chips. The production of such articles also requires cutting tools, which wear and must be periodically reconditioned and ultimately replaced. Moreover, fixtures for use in manufacturing must be designed, fabricated, and manipulated during production.
[0007] Machining is even more difficult when a part has an unusual shape or has internal features. Choosing the most appropriate machining operations and the sequence of such operations requires a high degree of experience. A number of different machines are needed to provide capability to perform the variety of operations, which are often required to produce a single article. In addition, sophisticated machine tools require a significant capital investment and occupy a large amount of space. In contrast, using the present invention instead of subtractive machining provides improved solutions to these issues and overcomes many disadvantages.
[0008] Another difficulty with conventional machining techniques is that many objects must be produced by machining a number of parts and then joining them together. Separately producing parts and then joining them requires close-tolerance machining of the complementary parts, provision of fastening means (e.g., threaded connections) and welding components together. These operations involve a significant portion of the cost of producing an article as they require time for design and production as well as apparatus for performing them.
[0009] Titanium has been used extensively in aerospace and other manufacturing applications due to its high strength-to-weight ratio. To increase the usefulness of titanium, various titanium alloys have been produced, many being tailored to provide desired characteristics. However, the equilibrium solute levels (as measured in weight-percent) in conventionally processed titanium alloys are below that which maximizes the beneficial effect of the solute.
[0010] For example, in concentrations over 500 ppm, nitrogen is typically considered a contaminant in titanium alloys. At levels higher than 500 ppm, the tensile strength increases greatly with a corresponding drop in tensile ductility. Additionally, solidification cracking can be a serious problem at high nitrogen levels. It is this embrittling effect that prohibits the use of nitrogen as a significant alloying agent.
[0011] Titanium alloys typically exhibit low wear resistance due to their low hardness. Under certain circumstances, titanium also can be subject to chemical corrosion and/or thermal oxidation. Prior art methods for increasing the hardness of titanium alloys have been limited to surface modification techniques. For example, a hard face coating is a discrete surface layer applied to a substrate and is subject to delamination. Current methods are also subject to macro and micro cracking of the surface-hardened layer. For example, U.S. Pat. Nos. 5,252,150 and 5,152,960 disclose titanium-aluminum-nitrogen alloys. These patents disclose an alloy that is formed through a solid-state reaction of titanium in a heated nitrogen atmosphere. The alloy is formed in a melt with aluminum to create the final alloy product.
[0012] Rapid solidification processes (RSP) also can be used to increase the amount of solute levels in alloys. In these processes, a rapid quenching is used in freezing the alloy from a molten state so that the solutes remain in desired phases. After quenching, diffusion may allow for dispersion throughout the material and agglomeration at nucleation sites, which further improves the desired characteristics of the alloy. While this type of process is widely used, the resulting product is typically in powder, flake, or ribbon forms, which are unsuitable for manufacturing applications requiring material in bulk form. Thus, an improved metal alloy and process for producing the same would be desirable for many practical applications.
SUMMARY OF THE INVENTION
[0013] The present invention comprises a system and method that uses a liquid-state reaction between a metallic molten pool and an atmosphere having a small fraction of reactive gas. For example, the invention can increase the mechanical strength and hardness of a metallic material through gaseous alloying. A direct manufacturing technique involving rapid solidification processing is used rather than conventional casting techniques that require bulk melting of solid-state materials.
[0014] By utilizing rapid solidification techniques, solubility levels of metallic materials can be increased resulting in alloys with unique mechanical and physical properties that are unattainable through conventional processing methods. For example, laser deposition techniques may be used on commercially pure metals in atmospheres having various amounts of inert and reactive gases. In one embodiment, the resultant alloys are significantly strengthened without cracking in atmospheres having concentrations of reactive gases of approximately 10%. Very high hardness values indicate that these types of materials have valuable applications as hard face coatings and in functionally graded materials.
[0015] The foregoing and other objects and advantages of the present invention will be apparent to those skilled in the art, in view of the following detailed description of the present invention, taken in conjunction with the appended claims and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] So that the manner in which the features and advantages of the invention, as well as others which will become apparent, are attained and can be understood in more detail, more particular description of the invention briefly summarized above may be had by reference to the embodiment thereof which is illustrated in the appended drawings, which drawings form a part of this specification. It is to be noted, however, that the drawings illustrate only an embodiment of the invention and therefore are not to be considered limiting of its scope as the invention may admit to other equally effective embodiments.
[0017] FIG. 1 is a schematic perspective view of one embodiment of a portion of a solid freeform fabrication device constructed in accordance with the present invention;
[0018] FIG. 2 is a schematic front view of the device of FIG. 1 during fabrication of a part, and is constructed in accordance with the present invention;
[0019] FIG. 3 is a high level flow diagram of one embodiment of a method constructed in accordance with the present invention;
[0020] FIG. 4 is a series of optical and electron micrographs depicting various structures of one embodiment of a composition of matter constructed in accordance with the present invention;
[0021] FIG. 5 is a plot of atmospheric nitrogen versus nitrogen absorbed and hardness in one embodiment of a composition of matter constructed in accordance with the present invention;
[0022] FIG. 6 is a series of optical micrographs depicting various structures of one embodiment of a composition of matter constructed in accordance with the present invention;
[0023] FIG. 7 is a series of optical micrographs depicting various structures of one embodiment of a composition of matter constructed in accordance with the present invention; and
[0024] FIG. 8 is a high level flow diagram of another embodiment of a method constructed in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention is directed to a method for producing the novel compositions of matter comprising metal alloys. In one embodiment, the new alloys are well suited for use in aerospace applications that require a combination of high strength and low density. To enable formation of these new compositions of matter, one method of producing the alloys utilizes a solid freeform fabrication (SFF), or direct deposition, device to achieve rapid cooling and solidification while forming a bulk part.
[0026] The alloys of the present invention utilize a rapid solidification process (RSP) to retain the desired metastable phases, and a method of direct manufacturing that results in rapid solidification is shown in the figures. FIG. 1 is a schematic, perspective view of a portion of a SFF device 11 , such as is available from Optomec Design Company, Albuquerque, N. Mex., and sold under the trademark LENS™ (Laser Engineered Net Shaping).
[0027] Device 11 comprises a high energy density heat source, such as a laser beam 13 . Other forms of heat sources may include, for example, electron beams and arcs, as illustrated at step 301 in FIG. 3 . The laser beam 13 may be formed by various laser types and delivered to the desired location by fixed or fiber optics. Beam 13 acts as the heat source for melting a feedstock, such as a metallic powder or wire, for example. The feedstock may be simply positioned for alloying (e.g., on a platform), or delivered through one or more guide nozzle(s) 15 (four shown), as depicted at step 305 in FIG. 3 . If nozzles are used, the feedstock exits the nozzles through an outlet 17 at the lower end of each nozzle.
[0028] In one embodiment, the controls for the heat source and nozzles are mounted to a movable platform, as depicted in step 303 in FIG. 3 . In the laser embodiment, the controls may utilize optics to direct the laser beam 13 . The platform also is computer-controlled to position the beam 13 and nozzles 15 in a desired location for each section or layer of the part being formed. These portions of the method are illustrated at step 307 in FIG. 3 . In the illustrated embodiment, device 11 is shown as having four nozzles 15 located at 90° increments in an array having a selected radius from, and being centered on, beam 13 . Though shown with four nozzles 15 , device 11 may have more or fewer nozzles 15 , and the nozzles 15 may be arranged in various orientations.
[0029] To form a part using the device 11 , the metal or metallic alloy feedstock is presented, such as by delivery into and through the nozzles 15 . As shown in FIG. 2 , when e.g., the powdered metal 19 is used as the feedstock, the metallic powder is entrained in an inert gas, typically argon, for delivery via the nozzles (step 305 , FIG. 3 ). The feedstock is carried out of the exit 17 of each nozzle 15 and directed at a point where the stream(s) of the metal 19 converge with the heat source. In one embodiment, the laser beam 13 melts the metal 19 (step 309 , FIG. 3 ), forming a molten pool on the platform or substrate 21 . The metal 19 is simultaneously exposed to a gaseous alloying element (e.g., nitrogen, oxygen, carbon dioxide, etc.). As one of or both the platform for the beam 13 and the nozzles 15 is/are moved (step 311 , FIG. 3 ), the pool rapidly cools and solidifies as an alloy. When the heat source or beam 13 is moved away, a continuous line of deposited alloy 19 forms a portion of part 23 . Device 11 is used to form adjacent, side-by-side layers to form the width of the part, and is used to form adjacent, stacked layers to create the height of part 23 .
[0030] In another embodiment ( FIG. 8 ), one embodiment of the method starts as indicated at step 801 , and comprises providing a heat source and a metallic feedstock in a gaseous atmosphere (step 803 ); delivering a gaseous alloying element proximate to the metallic feedstock (step 805 ); converging the heat source on the metallic feedstock and the gaseous alloying element (step 807 ); melting the metallic feedstock with the heat source to form a molten pool such that the metallic feedstock alloys with the gaseous alloying element to form a composition (step 809 ); cooling and solidifying the composition (step 811 ); before ending as indicated at step 813 .
[0031] In one experiment, five different argon/nitrogen atmospheric combinations were evaluated in addition to a baseline 100% Ar CP—Ti. Custom mixed bottles of argon and nitrogen were mixed with the following ratios (Ar/N 2 ): 96/4, 93/7, 90/10, 85/15, and 70/30. Cp-Ti specimens were then laser deposited in each gas composition. Prior to deposition, an amount of the desired composition was purged through the system to ensure a homogeneous mixture at the target concentration. Another amount of the desired composition was used to keep the chamber at operating pressure and as a carrier gas for the powder delivery system.
[0032] In this embodiment, heat treatments were performed on some test samples in order to examine microstructural stability and thermal effects. Microstructural characterization was carried out using optical and scanning electron microscopy. Under equilibrium conditions, the solidification sequence for compositions under 1.2% N, which corresponds to about 7% atmospheric nitrogen, is:
L→L+β→β→β+α→α+Ti 2 N
[0033] And for equilibrium solidification at compositions greater than 1.9% N:
L→L+α→α+β→α→α+Ti 2 N
[0034] This solidification behavior is likely valid under equilibrium conditions and therefore not necessarily valid for laser deposited structures (i.e., due to rapid solidification characteristics). Rapid solidification tends to increase solid solubilities, which effectively shifts the phase diagram towards the solute end, thus favoring metastable phase formation. However, microstructural analysis is consistent with the above solidification sequences, though the composition limits may be uncertain. In one embodiment, the Ti alloy contains a weight percentage of N of approximately 0.05% to 3.0%.
[0035] FIG. 4 shows a micrograph series for the 90/10 and 70/30 mixtures of Ar/N 2 for one embodiment. For the 90/10 mixture ( FIGS. 4A, 4B , 4 C), the macrostructure ( FIG. 4A ) is typical of what is seen in conventional Ti alloys (i.e., large prior β grain boundaries with a martensitic α′ lath basket weave structure). FIG. 4B shows a backscattered electron SEM image (BSEM) that reveals compositional contrast and indicates that Ti x N y compounds might exist in the interlath regions. FIG. 4C shows the 90/10 composition after heat treatment for 1-hour at 1000° C. Here, the Ti x N y particles are clearly seen pinning α grain boundaries in a recrystallized microstructure. The particle composition was verified using energy dispersive spectroscopy (EDS) to be Ti 2 N.
[0036] The 70/30 mixture ( FIGS. 4D, 4E , 4 F) has a macrostructure that is quite different from the 90/10 composition. FIG. 4D shows an optical micrograph of the as-deposited structure clearly showing dendritic formation of primary α. Closer look via BSEM ( FIG. 4E ) shows that the interdendritic region likely contains the Ti 2 N compound. FIG. 4F shows the 70/30 mixture after 1-hour heat treatment at 1150° C. Here again, the Ti 2 N particles are clearly seen pinning the α grain boundaries though the size of the particles is much larger when compared to those seen in the 90/10 sample (note the micron bars).
[0037] The chemistry results are shown in Table 1. Of interest here is the nearly linear relationship between atmospheric nitrogen and dissolved nitrogen in the as-deposited samples. This relationship is more clearly seen in FIG. 5 , as are the plotted superficial hardness values. Here the relationship seems to follow a power-law relationship indicating that significant hardening benefits can be obtained at low concentrations while the effect diminishes at higher concentrations.
TABLE 1 Element CP-Ti 4% N 7% N 10% N 15% N 30% N Nominal ASTM B348 C 0.0880% 0.0980% 0.0670% 0.0870% 0.0640% 0.0910% 0.0910% 0.0800% H 0.0050% 0.0018% 0.0020% 0.0012% 0.0037% 0.0038% — 0.0150% N 0.0200% 0.6700% 1.7300% 1.3300% 1.9400% 3.4500% 0.0080% 0.0300% O 0.1700% 0.1500% 0.1440% 0.1400% 0.1470% 0.1400% 0.1250% 0.1800%
[0038] Table 2 shows results from mechanical testing of the control CP—Ti specimens and the 96/4 and 90/10 compositions. The samples above 10% suffered cracking that prevented them from being tested. A small amount of nitrogen (as little as 0.1%) may result in gains in ultimate tensile strength on the order of 60% (i.e., as high as 140 ksi), and gains in hardness on the order of 100% (up to 55 HRC). Essentially no ductility was found in any of the nitrogen-modified samples.
TABLE 2 Comp. ID Test Log Temp. UTS 0.2% YS % E % RA Mod. Hard. 10% N4 — — — — — — — 55 10% N5 980791 RT 33.3 — — — 18.6 55 10% N6 980792 RT 28.4 — — — 18.5 55 AVG 30.9 18.6 55.0 4% N26 980796 RT 137.9 — — — 17.2 46 4% N27 980797 RT 155.5 — — — 17.3 48 4% N28 980789 RT 139 — — — 17 47 AVG 144.1 17.2 47.0 CP N21 980793 RT 88 76.7 6.5 9.5 16.7 100 (23) CP N23 980794 RT 88 74.6 23 31 16.7 97 (18) CP N24 980795 RT 81 73.2 5.5 13 16.7 98 (19) AVG 85.7 74.8 11.7 17.8 16.7 98.3 (20.0)
[0039] FIGS. 6 and 7 show the effect of heat treatment on the 90/10 composition. FIGS. 6A-6D show a series of optical micrographs of the sample in the as-deposited condition. Here the layered deposition structure is clearly seen. This structure is likely due to local thermal variation resulting in small differences in the scale of the microstructural features. This inhomogeneity is detrimental to mechanical properties as it provides a path of least resistance for defects to propagate. The series of optical micrographs in FIGS. 7A-7D show the same sample after a β anneal heat treatment at 1000° C. Here the microstructure has recrystallized and eliminated the layered structure seen in the non-heat treated condition. This microstructure might lead to mechanical property improvement, namely ductility.
[0040] While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention. For example, other compositions of materials (e.g., aluminum-oxygen, carbon dioxide, etc.) may be utilized. Moreover, other alloys having a mixture range of 0.1 to 30% may be more suitable for other combinations of materials. | A direct manufacturing technique involving rapid solidification processing uses a reaction between a metallic molten pool and a reactant gas in an inert atmosphere to form alloys with improved desired properties. By utilizing rapid solidification techniques, solubility levels can be increased resulting in alloys with unique mechanical and physical properties. Laser deposition of alloys in atmospheres of varying reactant content produce significant strengthening without cracking. In addition, these materials have very high hardness values for hard face coating and functionally graded materials applications. | 2 |
RELATED APPLICATIONS
The present invention is also related to U.S. patent application Ser. No. 09/634,411 entitled “Liquid-Cooled Electrical Machine With Integral Bypass” incorporated by reference herein.
BACKGROUND OF THE INVENTION
The present invention relates generally to electrical machines, and more particularly to cooling of electrical machines.
DESCRIPTION OF THE RELATED ART
Ways are continually sought to increase the electrical output of automotive alternators. With increased electrical output comes additional heat generated in the various electrical components of the alternator. In addition, friction in the bearings which support the rotor shaft of the alternator also generates heat. Because heat generated in an alternator is frequently the factor which limits the electrical output of the alternator, effective cooling of the alternator is very important.
Circulating liquid within an alternator has been recognized as one means for providing cooling. A liquid cooling design which provides effective cooling and which can support demands for ever-reducing package size of the alternator can be particularly advantageous.
SUMMARY OF THE INVENTION
The present invention provides an electrical machine comprising a rotor mounted on a shaft for rotation therewith and defining an axis of rotation, and a stator disposed coaxially with and in opposition to the rotor. The electrical machine further comprises a housing enclosing the stator and the rotor, the housing having a first axial end with a wall with an inner surface and an outer surface and a second axial end with a wall with an inner surface and an outer surface. The electrical machine also includes a first cooling tube having a first end and a second end and an embedded portion thereof embedded between the first inner surface and the first outer surface. A second cooling tube having a first end and a second end and an embedded portion thereof embedded between said inner surface and said outer surface of the wall of the second axial end. The first end of the first cooling tube and the first end of the second cooling tube are fluidically coupled together to permit fluid flow in parallel between the first cooling tube and the second cooling tube.
Designs according to the present invention are advantageous in that they can provide effective cooling of an electrical machine while also supporting packaging-efficient electrical machine designs.
Other objects and features of the present invention will become apparent when viewed in light of the detailed description of the preferred embodiment when taken in conjunction with the attached drawings and appended claims.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an alternator 20 according to one embodiment of the present invention.
FIG. 2 is a cross-sectional view of alternator 20 taken along a plane parallel to the axis of rotation of alternator 20 .
FIG. 3 is a perspective view of rotor 26 of alternator 20 .
FIG. 4 is a cross-sectional view of alternator 20 taken along line 4 — 4 of FIG. 2 .
FIG. 5 is a cross-sectional view of alternator 20 taken along line 5 — 5 of FIG. 2 .
FIG. 6 is a perspective view of a second embodiment of the invention.
FIG. 7 is a rotated perspective view of the second embodiment shown in FIG. 6 .
FIG. 8 is a partially exploded view of the second embodiment shown in FIG. 6 .
FIG. 9 is a perspective of one housing portion having an inlet according to the present invention.
FIG. 10 is a partially cutaway perspective view of a portion of the housing of FIG. 10 .
FIG. 11 is a perspective view of second embodiment of an inlet according to the present invention.
FIG. 12 is a partial cross-sectional view through the inlet of FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Refer first to FIGS. 1-3, an alternator 20 includes a front housing portion 22 and a rear housing portion 24 which are suitably bolted or otherwise attached together. Front housing portion 22 and rear housing portion 24 are preferably metallic. Included within front housing portion 22 and rear housing portion 24 is a rotor 26 . Those skilled in the art will recognize rotor 26 as being generally of the “claw-pole” variety. A plurality of permanent magnets 28 are disposed within rotor 26 in order to enhance the electrical output of alternator 20 .
Rotor 26 includes a shaft 29 having two slip rings 30 and 32 which are means for providing electrical power from a voltage regulator (not shown in the particular sectioning employed in FIG. 2) to a field coil 34 disposed within rotor 26 . Also coupled to shaft 29 is a pulley 36 , or other means for rotating rotor 26 . Shaft 29 is rotatably supported by a front bearing 50 , itself supported by front housing portion 22 , and a rear bearing 52 , rotatably supported by rear housing portion 24 .
A stator 54 is disposed in opposition to rotor 26 . Stator 54 includes a ferromagnetic stator core 56 , on which stator windings 58 are wound. The end turns 60 of stator windings 58 on one axial side of stator core 56 are substantially enclosed in a groove 62 in front housing 22 . The end turns 64 of stator winding 58 on the other axial side of stator core 56 are substantially enclosed in a groove 66 in rear housing 24 . Preferably, end turns 60 and 64 are encapsulated in a highly thermally conductive compound in order to facilitate heat transfer away from stator windings 58 .
A rectifier 70 , coupled to stator windings 58 in order to rectify the alternating current output generated in stator windings 58 by the operation of alternator 20 , is mounted to rear housing 24 . Rectifier 70 includes a negative rectifier plate 72 , which forms the common connection for the cathodes of the “negative” diodes 72 A. Rectifier 70 also includes a positive rectifier plate 74 , which forms the common connection for the anodes of the “positive” diodes 74 A. Negative rectifier plate 72 and positive rectifier plate 74 are electrically insulated from one another. A plastic cover 76 covers the rear of alternator 20 , including rectifier 70 . Electrical connectors 77 and 78 provide the required electrical connections to and from alternator 20 . As those connections are conventional, they are not described in detail here.
Front housing portion 22 also includes cooling tube 80 , and rear housing portion 24 includes cooling tube 82 . Cooling tubes 80 and 82 are preferably metallic, in order to assure good heat transfer from housing portions 22 and 24 to cooling tubes 80 and 82 , respectively. Cooling tubes 80 and 82 are preferably die-cast into their respective axial end walls 81 , 83 of housing portions 22 and 24 . Of course, if cooling tubes 80 and 82 are included within housing portions 22 and 24 by die casting, the material comprising cooling tubes 80 and 82 must have a higher melting temperature than the material comprising housing portions 22 and 24 , in order to allow cooling tubes 80 and 82 to be die-cast therein.
The ends of cooling tube 80 emerge from front housing portion 22 , and the ends of cooling tube 82 emerge from rear housing 24 . End 84 of cooling tube 80 forms an inlet into which cooling fluid can be introduced into alternator 20 . End 86 of cooling tube 82 forms an outlet from which cooling fluid exits from alternator 20 . The remaining two ends of cooling tube 80 and cooling tube 82 are coupled together by a “cross-over” formed by flexible tube 88 and two clamps 90 and 92 . Cooling fluid can thus flow into inlet end 84 of cooling tube 80 , through the length of cooling tube 80 , through the “cross-over” into cooling tube 82 , through the length of cooling tube 82 , and out the outlet end 86 of cooling tube 82 . Inlet end 84 and outlet end 86 are coupled to a source of cooling fluid such as the cooling system of a motor vehicle engine.
Referring now to FIG. 4, it can be seen that cooling tube 80 is formed substantially as a circular loop until points 100 and 102 , where cooling tube 80 begins to emerge from front housing portion 22 .
Referring now additionally to FIG. 5, it can be seen that cooling tube 82 is also formed in a substantially circular loop until points 104 and 106 , where cooling tube 82 begins to emerge from rear housing portion 22 .
The design disclosed herein is particularly effective for cooling alternator 20 , for a number of reasons. First, end turns 60 and 64 of stator 54 are substantially enclosed by grooves 62 and 66 in the housing of alternator 20 . Because the housing is cooled by cooling tubes 80 and 82 , heat generated in stator windings 58 is effectively conducted away from those windings. Second, front housing portion 22 presents a large, substantially flat surface 108 to rotor 26 across a small air gap 110 . Air gap 110 is preferably about 0.5 millimeters wide. Because front housing portion 22 is cooled by cooling tube 80 , the large, flat surface 108 across small air gap 110 provides for substantial heat transfer away from rotor 26 , including heat generated in field coil 34 . Rear housing portion 24 presents a similar large, substantially flat surface 112 to rotor 26 across a small air gap 114 . Air gap 114 is preferably about 0.5 millimeters wide. Third, with bearings 50 and 52 mounted in housing portions 22 and 24 and in proximity with cooling tubes 80 and 82 , heat generated in bearings 50 and 52 due to rotation of shaft 29 is effectively conducted away.
The design disclosed herein provides the cooling advantages described immediately above, while also contributing to alternator 20 having a short axial length. It can be seen that the axial alignment of cooling tube 80 , end turns 60 and bearing 50 , as well as the axial alignment of cooling tube 82 , end turns 64 and bearing 52 cause alternator 20 to have the short axial length. This is very much an advantage in packaging alternator 20 in a vehicle.
Referring now to FIGS. 6 and 7, a second embodiment having parallel flow as opposed to the serial flow described above is illustrated. In the following description the same reference numerals that are used above in the first embodiment are primed for the same components in FIG. 6 . In this embodiment, a fluid interface 220 is used for coupling fluids to alternator 20 ′. When fluid enters alternator 20 ′ through fluid interface 220 , fluid travels through cooling tube 80 ′ and cooling tube 82 ′ simultaneously. The fluid then exits fluid interface 220 from both cooling tube 80 ′ and cooling tube 82 ′. Fluid interface 220 has an inlet 222 and an outlet 224 . In the preferred embodiment, inlet 222 and outlet 224 are coupled to the cooling system of an automotive vehicle. As will be further described below, it is preferred to have a minimal pressure drop across the alternator. Therefore, providing a parallel flow as in FIGS. 6 and 7 versus a series flow reduces the pressure drop by as much as 70 percent. In the preferred embodiment, inlet 222 and outlet 224 are located on the same housing 22 ′. However, those skilled in the art would recognize that inlet 222 and outlet 224 may also be located on housing 24 ′.
To achieve the parallel flow the cooling tube 80 ′ has a first end 226 fluidically and mechanically coupled to first end 228 of second cooling tube 82 ′. First end 226 and first end 228 are fluidically coupled to inlet 222 . Second end 230 of first cooling tube 80 ′ is fluidically and mechanically coupled to second end 232 of second cooling tube 82 ′. Second end 230 and second end 232 are fluidically coupled to outlet 224 .
An inlet hose interface 234 may be coupled to inlet 222 . An outlet hose interface 236 is preferably coupled to outlet 224 . Both inlet hose interface 234 and outlet hose interface 236 are mechanically coupled to the respective inlet 222 and outlet 224 . The mechanical coupling may be fixed or may be rotatable to provide convenient assembly. Also, by locating the inlet 222 and the outlet 224 on the same housing, the ease of assembly during manufacture of the vehicle is increased in the ever shrinking underhood environment.
Referring now to FIG. 8, a partial exploded view of alternator 20 ′ is illustrated. As can be seen, fluid interface 220 has a first flange 238 coupled adjacent to first end 226 and second end 230 . A second flange 240 is positioned adjacent first end 228 and second end 232 of second cooling tube 82 ′. As is illustrated, each flange 238 , 240 has nearly a “figure 8” shape. At least one of the flanges 238 and 240 preferably have a seal channel 242 formed therein. Seal channel 242 is sized to receive a seal 244 at least partially therein. Seal 244 provides a seal between first flange 238 and second flange 240 to prevent fluid leakage therebetween. These skilled in the art will recognize various types of seals and gaskets may be used.
To conserve material a common wall 246 is preferably located between first end 226 and second end 230 of first cooling tube 80 ′.
Referring now to FIGS. 9 and 10, a third embodiment of the present invention is illustrated. In this embodiment the same reference numerals used in the second embodiment will be used for the same components. In this embodiment, the common wall 246 between inlet 222 and outlet 224 has a port 248 formed therethrough. Port 248 is sized to allow fluid to pass directly through common wall 246 from inlet 222 and outlet 224 . By allowing fluid to pass directly between inlet 222 and outlet 224 , the fluid resistance of the alternator is reduced. Moreoever, the amount of fluid traveling through first cooling tube 80 ′ and second cooling tube 82 ′ is sufficient to cool the alternator. Thus, because the pressure drop across the alternator is reduced, a bypass manifold with its associated hoses and connection is not required.
Preferably, inlet 222 , outlet 224 and port 248 are colinear along line 250 . However, those skilled in the art will recognize that a non-colinear alignment may be used with the risk of increasing the pressure drop across the alternator.
The diameter D of port 248 may be varied to increase or decrease the pressure drop across the alternator. The amount of pressure increase or decrease across the alternator will vary depending on the particular vehicle configuration and cooling system flow requirements.
Referring now to FIGS. 11 and 12, a second embodiment of an alternative fluid interface 220 ′ is illustrated. Fluid interface 220 ′ in this embodiment includes an inlet T-shaped portion 260 and an outlet T-shaped portion 262 . Inlet T-shaped portion 260 is coupled to first end 226 ′ of first cooling tube 80 ″ and first end 228 ′ of second cooling tube 82 ″. Outlet T-shaped portion 262 is coupled to second end 230 ′ of first cooling tube 80 ″ and second end 232 ′ of second cooling tube 82 ″. Preferably, a flange 264 extends between first end 226 ′ and second end 230 ′ of first cooling tube 80 ″. A second flange 266 preferably extends between first end 228 ′ and second end 232 ′ of second cooling tube 82 ″.
As is best illustrated in FIG. 12, first cooling tube 80 ″ has a receiving portion 268 that extends into inlet T 260 that inlet T-shaped portion 260 may be received thereon. Also, second cooling tube 82 ″ has a receiving portion 270 extending therefrom. Receiving portion 270 also extends inward into inlet T 260 so that inlet T is receiving thereon. A plurality of fields 272 such as O-rings are positioned between inlet T-shaped portion 260 and receiving portions 268 , 270 . Seals 272 prevent fluid leakage between the T-shaped portion 260 out of the fluid path.
Although FIG. 12 only illustrates a cross-sectional view through first T-shaped portion 260 , second T-shaped portion 262 is also configured in a similar manner.
Inlet T-shaped portion 260 has an inlet end 261 for receiving fluid from the coolant path of the automotive vehicle. Outlet T-shaped portion 262 has an outlet end 263 for returning coolant to the coolant path of the automotive vehicle. In this embodiment similar to the prior embodiment, coolant enters inlet end 261 and travels through first coolant tube 80 ″ and second coolant tube 82 ″ in parallel so that coolant circulates therethrough and exits simultaneously through outlet end 263 .
Other embodiments may be formed as would be evident to those skilled in the art. For example, the inlet 222 and outlet 224 may be located on alternate housing portions. Further, port 248 may be located in a different housing portion than inlet 222 and outlet 224 .
Various other modifications and variations will no doubt occur to those skilled in the arts to which this invention pertains. Such variations which generally rely on the teachings through which this disclosure has advanced the art are properly considered within the scope of this invention. This disclosure should thus be considered illustrative, not limiting; the scope of the invention is instead defined by the following claims. | An electrical machine comprising a rotor ( 26 ) mounted on a shaft ( 29 ) for rotation therewith and defining an axis of rotation, and a stator ( 54 ) disposed coaxially with and in opposition to the rotor ( 26 ). The electrical machine further comprises a housing ( 22, 24 ) enclosing the stator ( 54 ) and the rotor ( 26 ), the housing ( 22, 24 ) having a first axial end with a wall with an inner surface and an outer surface and a second axial end with a wall with an inner surface and an outer surface. The electrical machine also includes a first cooling tube ( 80 ′) having a first end and a second end and an embedded portion thereof embedded between the first inner surface and the first outer surface of end wall ( 81 ). A second cooling tube ( 82 ′) has a first end and a second end and an embedded portion thereof embedded between said inner surface and said outer surface of the wall ( 83 ) of the second axial end. The first end ( 226 ) of the first cooling tube and the first end ( 228 ) of the second cooling tube ( 82 ′) are fluidically coupled together to permit fluid flow in parallel between the first cooling tube ( 80 ′) and the second cooling tube ( 82 ′). | 7 |
FIELD OF THE INVENTION
The present invention generally relates to software.
BACKGROUND
A file is a complete, named collection of information, such as program, a set of data used by a program, or a user-created document. Files are typically structured into folders residing on computer disk drives. Files and folders are generally organized in a hierarchical namespace and provide users and applications with a consistent and efficient way to access and manage these files and folders. A namespace can be viewed as a single tree-structured hierarchy. To access a namespace file, the file must first be identified. One way to identify a file is to use a path, which is a route followed by the operating system through the directories in finding, sorting, and retrieving files on a disk. For example, an object may have a name, such as “MyFile.htm.” Because there might be other files with that name elsewhere in the namespace, the file can be uniquely identified by using an address, such as “C./MyDocs/MyFile.htm” or “http://MyDocs/MyFile.htm”.
Suppose a source file “MyFile.htm” at the address “http://MyDocs/” needs to also appear at another address, such as “http://HisDocs/” Conventionally, the source file “MyFile.htm” would be copied from the address “http://MyDocs/” and pasted to the address “http://HisDocs/” The copied file then has no further relationship to the source file. If changes were to be made to the source file, the copied file cannot be updated because of the lack of ongoing relationship between the source file and the copied file. Conventional copying works fine if all that is wanted is a static file. The problem arises when a static file is not desired, but instead, a dynamic file that can be updated or can inform appropriate users of the copied file of changes.
One conventional technique to add dynamism to copied files is the use of symbolic links, which are area directory entries that take the place of directory entries of a copied file but are actually references to source files in different directories. Thus, using a symbolic link, the copied file “MyFile.htm” at the address “http://HisDocs/” actually references the file “MyFile.htm” at the address “http://MyDocs/” This works very well if a single namespace exists containing the addresses to both the source file and the copied file. But in cases where the source file may reside in a namespace that is different from the namespace containing the copied file, the use of symbolic links will not work.
SUMMARY
In accordance with this invention, a computer-readable medium, system, and method for copying and updating files is provided. The system form of the invention includes a networked system that comprises a first server with a first security policy containing a file at a first address. The networked system further comprises a browser that displays options selectable to reproduce the file at the first address as a copy of the file at a second address within the server with the first security policy. The options includes an option to update the copy of the file automatically when the file has been changed. The networked system further comprises a second server with a second security policy different from the first security policy of the first server. The networked system further comprises a control that facilitates the reproduction of the file as another copy on the second server.
In accordance with further aspects of this invention, a computer-readable medium form of the invention includes a computer-readable medium having one or more data structures stored thereon for tracking copies of a file. The computer-readable medium comprises a destinations field that stores a pointer to a destination data structure that contains addresses of the copies of the file, a version field that stores a version of the file, and a source field that contains an address of another file from which the file was copied. The destination data structure includes one or more copy destination tags that contain addresses of copies of the file. The addresses include Web addresses. The destination data structure includes an attribute that specifies whether a copy is to be updated when the file has been changed and another attribute that specifies an alias of a user who creates the copy.
In accordance with further aspects of this invention, a method form of the invention includes a computer-implemented method for copying files. The method comprises receiving events that indicate an act of hovering a pointer over a file to invoke a context menu, which displays an option to send a copy of the file to an address and another option to go to the source of the file. The method further comprises displaying a fly-out menu when the option to send the copy of the file to an address is selected, the fly-out menu displaying three categories of menu items that are selected from a group consisting of copying to suggested destinations, upgrading copies, and specifying new locations.
The method comprises presenting a first window when the menu item for specifying new locations is selected. The first window provides a first text box adapted to receive an address, a second text box adapted to receive a name for the copy, an indication of whether the copy is to receive updates, and another indication of whether an alert is sent when an update is available. The method comprises presenting a second window when the menu item for upgrading copies is selected. The second window provides click boxes for each copy of the file for a particular address, the click boxes being selectable to indicate that an upgrade is to be sent. The method comprises. presenting a third window that lists namespaces and addresses under the namespaces where copies of the file will be reproduced. The third window includes a button that is selectable to indicate that copying shall proceed and another button that is selectable to terminate the copying. The method comprises presenting a fourth window that lists namespaces and addresses under the namespaces where attempts have been tried to reproduce the copies of the file, the window indicating whether the copying at each address terminates successfully or terminates in failure. The fourth window includes a button that is selectable to indicate that copying shall be attempted again for copying that terminates in failure. The method comprises presenting a text box that indicates that a file is a copy of another file. The text box further indicates an address of the another file. The text box further presents an upgrade link that is selectable to upgrade copies of the another file. The method comprises presenting a window that displays copies that requested updates and copies that did not request updates.
DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a block diagram illustrating an exemplary system for copying files and creating relationships between source files and copied files;
FIG. 2A is a pictorial diagram illustrating an exemplary user interface in which a copy operation is specified;
FIG. 2B is a pictorial diagram illustrating an exemplary user interface by which a user specifies a destination to deposit a copy of a source file and whether the copied file can be updated;
FIG. 2C is a pictorial diagram illustrating an exemplary user interface for indicating copied files to be updated;
FIG. 2D is a pictorial diagram illustrating a an exemplary user interface showing the progress of copying;
FIG. 2E is a pictorial diagram illustrating an exemplary user interface for reporting copying errors;
FIG. 2F is a pictorial diagram illustrating an exemplary user interface for reporting copying errors;
FIG. 3A is a pictorial diagram illustrating an exemplary user interface for indicating the source file from which the copied file was copied;
FIG. 3B is a pictorial diagram illustrating an exemplary user interface for managing copied files;
FIG. 4A is a pictorial diagram illustrating a metadata matrix storing information about copied files or the source file;
FIG. 4B is a textural diagram illustrating a schema for storing addresses of copied files;
FIGS. 5A-5E are process diagrams illustrating a method for copying files.
DETAILED DESCRIPTION
FIG. 1 illustrates a system 100 that includes servers 100 - 114 . On the Internet or other network, these servers 100 - 114 are computers or programs that respond to commands from clients. For example, a file server may contain an archive of data or program files; when a client submits a request for a file, the server transfers a copy of the file to the client.
The server 100 is located at address “http://ServerA”. The server 110 is located at address “http://ServerB”. The server 112 is located at address “http://ServerC”. The server 114 is located at address “http://ServerD”. SOAP layers 100 A- 114 A are coupled to servers 100 - 114 , respectively. These SOAP layers 110 A- 114 A use a simple; customizable, tag-based protocol for exchanging structured and typed information on the Web. A Web browser 104 is a piece of software that lets a user view tagged documents and gain access to files and software related to those documents. Originally developed to allow users to view browsable documents on the World Wide Web, Web browsers can blur the distinction between local and remote resources for the user by also providing access to documents on a network, the Internet, or a local hard drive. The Web browser 104 is built on the concept of hyperlinks, which allow users to point and click with a mouse in order to jump from document to document in whatever order they desire. Most Web browsers are also capable of downloading and transferring files, displaying graphics embedded in the document, playing audio and video files associated with a document, and executing small programs, such as Java applets or ActiveX controls included by programmers in the documents.
The system 100 also includes means 106 to add interactivity to a Web page (“a control 106 ”). Many suitable implementations of the control 106 are possible. One suitable implementation includes an ActiveX control. Various embodiments of the present invention use the Web browser 104 or the control 106 to facilitate copying a file from one address to another address. These addresses can be under one namespace, such as the namespace of the server 100 , or multiple namespaces, such as those namespaces organized under servers 100 - 114 . If a copy operation were to be performed in a single namespace, such as the namespace of the server 100 , either the Web browser 104 or the control 106 can be used to make desired copies. If a copy operation were to be performed to reproduce a file from one namespace to one or more other namespaces, it is preferred that the control 106 be used to perform such a transfer and avoid security problems. The control 106 can mediate between two servers that may have differing security policies. The control 106 can authenticate itself with one server and with another server so as to faciliate the copying and updating processes of a file on one server and a copy of the file on another server.
A GetItem() function 102 is used either by the Web browser 104 or the control 106 to obtain a desired file. CopyItems() functions 108 A- 108 C can be used to reproduce the file obtained by the GetItem() function 102 to other namespaces. Both the GetItem() function 102 and the CopyItems() functions 108 A- 108 C use the SOAP layers 100 A- 114 A to write and read to various namespaces on servers 100 - 114 . Both the Web browser 104 and the control 106 are preferably executed on a client, such as a personal computer, that communicates and intermediates between the server 100 and servers 110 - 114 .
FIG. 2A illustrates a collection of user interface elements 202 . The collection of user interface elements 202 includes another collection of user interface elements 204 that includes an icon and a textual element “purple”. Another collection of user interface elements 208 includes an icon and a textual element “Show Desktop”. A collection of user interface elements 266 includes an icon and a textual element “Schedule” from which a context menu 210 is invoked. The menu 210 includes menu item 212 “View Properties” which can be selected to view the properties of a file named by the textual element “Schedule”. A menu item 214 “Edit Properties” can be selected to edit the properties of the file named by the textual element “Schedule”. The file named by the textual element “Schedule” can be deleted by selecting menu item 216 “Delete”. If the file named by the textual element “Schedule” is a copy of another file, menu item 220 “Go to the source item” can be selected so that the source file from which the copied file named by the textual element “Schedule” can be found.
If a copy operation or an update operation were to be performed on the file named by the textual element “Schedule”, menu item 218 “Send To” is selected to cause a menu 222 to fly out. Menu item 224 A “Local Hard Drive”; menu item 224 B “E-mail”; menu item 224 C “Listing”; menu item 224 D “Knowledge Store”; and menu item 224 E “My Site” are suggestions of locations where a user may copy the file named by the textual element “Schedule”. Menu item 226 can be selected so as to allow a user to specify copies of the file named by the textual element “Schedule” to be updated. Menu item 228 “Other Location” can be selected to bring forth a window 230 ( FIG. 2B ) to specify an address at which a copy of the file named by the textual element “Schedule” is stored.
As illustrated at FIG. 2B , the window 230 is presented when the user selects menu item 228 “Other Location”. The window 230 includes a textual element 232 “Copy:bebop.doc” indicating that the file named “bebop.doc” is to be copied to a destination specified in panel 234 . Within panel 234 , a text box 234 A appears to allow the user to enter a destination address at which a copy of the file “bebop.doc” will be reproduced. Another text box 234 B allows the user to change the name of the copy of the file “bebop.doc”. Panel 236 allows the user to select one of two radio buttons 236 A (YES/NO) indicating whether the copied file should be updated automatically when a new major version is created. Line 236 B contains a click box, which can be selected for an alert to be issued such as a piece of e-mail, when a major version is created, allowing the user to decide whether to update one or more copies of a particular file. An alert can be suitably used when automatic updating is not desired and the user wants to gain control of when the updating should occur after receiving the alert. For example, a person who is responsible for a file and its copies may want to review the update before the update is migrated to all copies of the file. If the user decides to terminate the copy operation, a cancel button 240 can be selected. Otherwise, if the user wishes to proceed with the copy operation, an OK button 238 can be selected.
FIG. 2C illustrates a window 242 which is invoked when the user selects menu item 226 “Multiple Copies”. The window 242 includes the textual element 244 “Update Copies:bebop.doc”, indicating that an update operation can be specified to commence to update various copies of the file “bebop.doc”. Panel 246 indicates the destination address of various copies of the file “bebop.doc”. Addresses 246 A- 246 D have click boxes adjacent to them which the user may select so as to indicate that a particular copy is to be updated.
FIG. 2D illustrates a window 248 , which informs the user of the progress of the copying operation. A text box 250 indicates various namespaces or servers in bold letters, such as “http://office” or “http://windows”. The address under each namespace is then specified to indicate various locations at which the copy of the file will be reproduced. For example, at the following addresses a reproduction of the file “bebop.doc” will occur: “. . . /docs/bebop.doc”; “. . . /teams/wss/expenses/bebop rpt.doc”; and “. . . /specs/specs2/bebop.doc”. A scroll bar 252 appears when additional text is available for scrolling so as to allow the user to view the additional text. If the user decides to terminate the copy operation, a cancel button 256 can be selected. Otherwise, if the copy operation is to proceed, the user may select an OK button 254 .
FIG. 2E illustrates a window 258 for reporting on the progress of the copy operation. A text box 260 shows the statuses of the success or failure of the copy operation at various namespaces or servers. For example, a copy attempt to the address “. . . /teams/wss/expenses/bebop rpt.doc” under the namespace “http://office” terminated in failure because write access was denied. A click box 262 is selectable by the user so as to indicate destination addresses for the copy operation to retry. Note that the copy operation to the namespace “http://windows” successfully terminated. If the user wishes to retry a failed copy operation, a “Retry Selected” button 264 can be clicked to begin the copy operation process again. The user, alternatively, may also select a Done button 266 to acknowledge the presentation of the window 258 and the statuses of copy operations.
FIG. 2F illustrates a window 268 that includes a textual element 270 “Copy Results:Bebop.doc” indicating various results in copying the file “bebop.doc”. Namespaces 272 - 276 are presented in bold, such as “http://office”; “http://arsenal”; and “http://bebop”. Check boxes 272 A, 272 B can be selected to indicate that the copy operation should be repeated or retried at those destination addresses. Line 272 C indicates that the copy operation to destination address “. . . docs/orange/bebop.doc” terminated successfully. Various errors can be reported, such as that write access is denied; the file has been checked out and made unavailable; or that the control 106 must be present in order to copy files from one namespace or server to another namespace or another server.
FIG. 3A illustrates a collection of user interface elements 302 which includes a text element 302 A that indicates whether a file is a copy of another file. The textual element 302 A indicates the address at which the source file can be found, such as “http://office/personal/jmorrill/docs/bebop.doc”. Additionally, contained within the textual element 302 A are hyperlinks “Update” and “Unlink” to enable a user to update the copied file or unlink the relationship between the copied file and the source file. Line 302 B indicates a date and a time and by whom the copied file was created. Line 302 C indicates the date, the time, and the person who last modified the copied file.
FIG. 3B illustrates a window 304 that allows a user to manage copies of a file. A text element 306 “Manage Copies:Bebop.doc” indicates that various copied files in various destination addresses can be managed by the window 304 . A panel 308 indicates copies of “bebop.doc” which have requested that whenever changes to the orignal “bebop.doc” are made, the copies be updated. Panel 310 lists copied files or copies of the file “bebop.doc” that have requested not to receive updates. A hyperlink 312 can be selected by the user to cause an update of the file “bebop.doc” to migrate to those copied files that have requested updates.
FIG. 4A illustrates a metadata matrix 400 that contains pieces of metadata connected with various files. When a file is copied, its metadata as described by the matrix 400 is copied and reproduced at the desire destination. The file is represented by a bit stream referenced by stream field 404 . An ID field 402 contains identification information connected with various source and copied files. A stream field 404 is the binary content of a file itself. Each file typically has a title and that is described by the title field 406 . Each file also has an author and that is described by the author field 408 . A destinations field 410 is a pointer to a data structure which is suitably formed by a customizable, tag-based language. The schema of this data structure is described by FIG. 4B . The version field 412 prevents users from overriding a file. Each time a file is updated, the version field 412 is checked to ensure that the version being updated is appropriate. The version field 412 can suitably contain an integer which is incremented whenever an appropriate version has been updated. Suppose that the first user obtains the file with version 1 . A second user also obtains the file with version 1 . The second user saves the file, hence incrementing the version to version 2 . The first user now saves the file, but because the version being saved is an older version (version 1 ) than the present version of the file (version 2 ), the save operation terminates unsuccessfully. The matrix 400 also includes a source field 414 for containing an address of the source file from which copied files were made. Any addressing scheme can be used. One suitable addressing scheme includes uniform resource locators.
FIG. 4B illustrates a schema 416 that contains destination addresses at which copies of a file were made. The schema 416 can be formed from any suitable language. One suitable language includes a customizable, tag-based language, such as XML. A tag <copy destinations> 418 indicates the beginning of one or more tags that specify one or more tags that specify the destination addresses of various copies of a file. A tag <copydest> 420 includes an attribute URL that contains an address where a copy of the file bebop.doc may be found, such as “http://office.bebop.doc”. The tag 420 also includes an attribute update as defined on line 422 . The attribute update can either be false or true depending on whether automatic update is to be migrated to the copy of the file. Line 424 describes another attribute ModifiedBy, which contains the name or e-mail address of the person who created the copy of the file. The attribute ModifiedBy reveals who made a copy of the file.
FIGS. 5A-5E illustrate a method 500 for copying files. From a start block, the method 500 proceeds to block 502 where a cursor is hovered over a file to be copied and a-context menu is invoked. Next, at block 504 , the Send-To menu item is selected causing another menu to fly out from the Send-To menu item. The fly-out menu displays menu items that can be classified into three categories: suggested destinations, multiple copies, and other locations. See block 506 . Next, the method 500 proceeds to decision block 508 where a test is performed to determine whether the suggested destinations menu item was selected. If the answer to the test at decision block 508 is no, the method 500 proceeds to a continuation terminal (“Terminal A 1 ”). If the answer to the test at decision block 508 is yes, the rest of the file, such as a uniform resource locator, is memorized. See block 510 . The method 500 then continues to another continuation terminal (“Terminal A 4 ”).
From Terminal A 1 ( FIG. 5B ), the method 500 proceeds to decision block 512 where a test is performed to determine whether the multiple copies menu item was selected. If the answer to the test at decision block 512 is no, the method 500 continues to another continuation terminal (“Terminal A 2 ”). Otherwise, if the answer to the test at decision block 512 is yes, the method 500 proceeds to block 514 where a user interface screen displays check boxes next to locations of copies of the file. Next, at block 516 , check boxes next to locations of the copy of the file that have to be updated are selected. The addresses, such as the URLs of the locations of copies of the file that have to be updated, are memorized. See block 518 . The method 500 then continues to Terminal A 4 .
From Terminal A 2 ( FIG. 5C ), the method 500 proceeds to decision block 520 where a test is performed to determine whether another locations menu item was selected. If the answer to the test at decision block 520 is no, the method 500 continues to another continuation terminal (“Terminal A 3 ”). If the answer to the test at decision block 520 is yes, the method 500 proceeds to block 522 where a user interface screen displays a text box for receiving a destination address and another text box for receiving a file name. The user interface screen also displays radio buttons (Yes/No) selectable to indicate whether the copied item is to be updated. See block 524 . At block 526 , the destination address, such as a URL, and the name of the copy of the file are memorized. The method 500 then continues to Terminal A 4 .
From Terminal A 4 ( FIG. 5D ), the method 500 proceeds to decision block 528 where a test is performed to determine whether a control is installed to facilitate copying. If the answer to the test at decision block 528 is yes, the method 500 proceeds to another continuation terminal (“Terminal A 5 ”). If the answer to the test at decision block 528 is no, another test is performed at decision block 530 to determine whether the destination address is on the same server or namespace as the source file. If the answer to the test at decision block 530 is no, the method 500 displays an error indicating lack of a control to copy the file. See block 532 . The method 500 then terminates execution. If the answer to the test at decision block 530 is yes, the method continues to another continuation terminal (“Terminal A 6 ”).
From Terminal A 5 ( FIG. 5E ), the method 500 proceeds to block 534 where the control invokes a GetItem function specifying the address (i.e., source URL) at which the file to be copied resides. At block 536 , the GetItem function obtains the binary stream of the file and returns the properties of the file. The control invokes a CopyItems function specifying the source URL, the binary stream, the properties, and a list of destination addresses to be copied. See block 538 . Next at block 540 , the CopyItems function copies the file to the destination addresses. The destination's metadata connected with the file is refreshed to include the address of its copy and whether updating should occur. See block 542 . The source metadata connected with the copy of the file is modified to include the address of the file from which it was copied. See block 544 . The method 500 then terminates execution. From Terminal A 6 ( FIG. 5E ), the method 500 proceeds to block 546 where blocks 534 - 544 are executed by the browser instead of by the control and the CopyIntoItemsLocal function is invoked in lieu of the CopyItems function. Block 546 is executed when a file is to be copied into the same namespace containing the file. In such a situation, it is inefficient to transfer bits and so instead, a reference is used to obtain the binary stream of the file without having to duplicate the entire binary stream and then reproduce it at another location.
While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention. | Copied and source files are tracked so that authors of these documents can selectively update these files. Stale copied files can be eliminated. A control is provided to mediate copying of files among servers that have differing security policies. Metadata of a file being copied is downloaded from a server to the control and the control uploads the metadata of the file to one or more servers. A relationship between copied files and source files are memorialized whether or not copied files reside in different namespaces from the namespace of the source files. | 6 |
BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates to backup, or secondary, sump pumps which are battery powered and used to evacuate the water from the sump in the event of an emergency caused by failure of a primary sump pump. In particular, the invention relates to a protection device or column which maintains the backup sump pump free of debris and dry until the backup sump pump is needed to evacuate water from the sump.
A primary sump pump normally is powered from an electrical line bringing power from a remote power station. Often, especially in more rural areas, due to failure of power in the electrical lines during a storm, the primary pump will not be operative. At that time, the battery powered backup pump takes over the task of removing water from the sump.
Obviously, due to their nature, such backup pumps operate only infrequently. Yet, normally they will be located in the sump where they are alternately submerged in water and then free of water as the water level in the sump goes up and down as a result of the action of the primary pump. This constant bathing of the pump components and then exposing them to air can be particularly hard on the pump components and the mechanical operating condition of the pump, especially when the pump is normally standing idle, corrosively impairing pump operation and dramatically shortening its useful life. Furthermore, the water moving into and out of the backup sump pump is likely to carry with it contaminates and debris which are deposited on and in that pump or its pump screen, further impairing its operating condition. Since it is not uncommon for a power failure to occur as the result of a storm, the backup pump may become inoperative at just the very time it is needed most.
Therefore, the principal purpose of the present invention is to provide a protection device for a backup sump pump apparatus to exclude water, and any contaminates that it may carry, from the operating components of the pump during its period of inaction. There therefore will be less opportunity for those operating components to be so deleteriously affected that the pump will fail to operate when it is needed.
In accordance with the invention, the protection device for the backup sump pump apparatus is composed of an elongated, hollow guard column which surrounds the pump unit of the sump pump apparatus. The bottom portion of the guard column is closed to form a buoyant vessel, permitting the column to float as the liquid level rises in the sump. A series of openings in the form of vertical slots are located in the guard column extending upwardly from a short distance above the water line to a short distance from the top of the column. This upper part of the column fits about the pump unit to thereby guide the guard for aligned vertical movement. When liquid rises to an abnormal elevation in the sump, the bottom of the guard column strikes the bottom of the pump unit, preventing the guard column from rising any further within the sump. As the liquid level then continues to rise in the sump, liquid enters the guard column through the openings, causing the guard column to sink to the bottom of the sump and allowing the pump to be primed for subsequent pumping operation.
BRIEF DESCRIPTION OF THE DRAWING
The drawing illustrates an embodiment in elevation, which embodiment is located in a sump, depicted in section.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following disclosure is offered for public dissemination in return for the grant of a patent. Although it is detailed to ensure adequacy and aid understanding, this is not intended to prejudice that purpose of a patent which is to cover each new inventive concept therein no matter how others may later disguise it by variations in form or additions or further improvements.
A conventional sump pump, shown generally at 10, is employed in a sump 11 to remove liquid, e.g., water, which may collect therein. For example, the basements of homes or commercial establishments may have such sumps to collect water for removal and thereby keep the basements dry. A discharge pipe 12 is connected to the pump so that the water to be removed can be conducted to an appropriate location for discharge. Such pump has controls (not illustrated) so that, for example, the pump is energized when the level of the water in the sump reaches that indicated by line 13 and the pump is turned off after it has extracted sufficient liquid from the sump to lower the liquid level to the line 14. The sump is formed by fixed components, such as bottom 8 and side walls 9.
As a result of the fact that the primary sump pump may occasionally fail to operate, many users of sump pumps will also employ a secondary or backup sump pump unit, especially when vital records and other documents and materials are located in the vicinity of the sump, such as those records in a basement bank vault. The backup sump pump unit is designated at 15 and includes a housing 15a within which a battery powered electric motor is connected to an impeller (neither the motor nor impeller being illustrated) positioned to pump water upwardly from the sump 11. The bottom 15b of the housing is open to permit water to enter to reach the impeller and this is the only opening other than that at the top for the connection to a discharge conduit 18. The sump pump 15 is connected by means of a flexible hose 16 and hose clamps 17 to the discharge conduit 18. Mounting means, not shown, fixedly position the pump unit in the sump. The arrangement of the backup sump pump 15 is such that when the motor of the pump is energized, the pump draws liquid out of the sump and discharges it from the sump through the conduit 18. Further details of such a pump are illustrated and described in my copending U.S. Pat. application Ser. No. 793,402, filed May 3, 1977, and entitled "Through Flow Sump Pump", now Pat. No. 4,177,021, the disclosure of which is incorporated herein by reference.
Such a secondary pump is not intended to operate constantly, but only in the event that the primary pump 10 fails to keep the liquid level in the sump down to the lower portion thereof. Thus, for example, the controls of the secondary pump unit 15 will be set so that the pump unit will be energized when the liquid level in the sump reaches that indicated by the line 19 and will turn the pump unit off when the liquid level drops to that indicated by the line 20.
One such control for providing a differential in the liquid level between the point at which the motor of the pump unit 15 turns on and turns off is described in my copending U.S. Pat. application Ser. No. 891,213, filed Mar. 29, 1978, and entitled "Air Pressure Switch Signaling Two Different Pressure Conditions", now abandoned, the disclosure of which is incorporated herein by reference. As shown in part in the drawing of the present invention, it comprises a bell 21 which is suspended with its open end down and which communicates through a hose or tube 22 to a fluid pressure actuator (not illustrated) located in an electrical control device 23. As water rises above the open end of the bell 21, air pressure builds up in the bell, which pressure is transmitted through the hose 22 to the actuator in the electrical control device 23, energizing the backup sump pump 15. The same differential water level/switch actuation can be achieved with float switches, as for example that described in my U.S. Pat. No. 4,086,457, issued Apr. 25, 1978, the disclosure of which is also incorporated herein by reference.
With an arrangement as thus far described, it will be noted that as the liquid level in the sump varies between the liquid level limits defined by the lines 13 and 14 (resulting from operation of the primary pump 10) the liquid will correspondingly go up and down in the pump 15, unless excluded therefrom. This repeated bathing of the parts within the secondary pump 15 and then exposing them to air as the water level rises and falls can have a deleterious effect upon the backup pump unit. Also, debris such as that indicated at 24 may get past the screen of the pump and work into the pump where it can have a further deleterious effect. Obviously, the backup pump unit 15 was put into the sump to provide protection in the event of an emergency and should the pump 15 fail to operate when required, its purpose has not been fulfilled. Therefore, included as a part of the invention is a protection device, generally designated at 25, to protect the backup pump 15 to provide additional assurance that it will operate when necessary.
As shown in the drawing, the protection device 25 consists of an elongated guard column or cylinder 26 which is hollow and which surrounds the pump unit 15. The top of the column 26 is open, while the bottom 27 of the column is sealed. The closed bottom portion of the guard, i.e., that below the bottom of slots 28, is a vessel and displaces more than enough water to offset the weight of the guard so that the guard is buoyant. Thus the column floats and protects the backup pump 15 by keeping it dry as the liquid level rises in the sump 11 under normal conditions between level limits defined by the lines 13 and 14. The column 26 is sufficiently tall so that even when the bottom 27 rests on the bottom of the sump, as shown in phantom, a portion of the column will surround part of the backup pump 15, thus preventing the column from inadvertently being removed from the pump when the sump is low or empty. The upper part of the column, i.e., that part above the bottom of slots 28, primarily serves as a guide about the fixedly mounted pump unit 15 and maintains the vessel portion in alignment with the pump unit.
The column 26 also includes a series of passages, shown as slots 28, intermediate the top and bottom thereof for providing an inlet through which liquid can flow from the exterior into the interior of the column. The slots 28 extend vertically in the column 26 from a short distance above the water line, shown at 29, to prevent the column 26 from sinking under normal conditions. With the use of relatively narrow slots, the column will serve also as a screen to prevent debris from getting to the pump after the column has moved to the position illustrated in dashed lines. If such debris causes a lower portion of the slot to plug up, the rising water in the sump will flow into the guard through the part of the slot below or above the location at which that obstruction exists. Obviously, apertures of shapes other than slots, e.g., a large number of variously placed round openings may be employed. A petcock 30 may be located at the bottom of the column 26 to permit draining of the interior of the column in that area below the bottom of the slots 28 after the column has become filled with liquid.
As indicated above, normally the primary pump 10 will be operational and the water level 29 will vary between limits depicted by the lines 13 and 14. The protection device 25 will float up and down about the backup pump 15 as the water level varies between its high and low limits. If the primary pump 10 fails to operate, adverse conditions may cause the liquid level to rise above that indicated by the line 13, and the protection device 25 correspondingly continues to float with the liquid level as it rises. When the liquid level has risen to a sufficient height, the bottom 27 of the column 26 strikes the bottom of the pump housing 15a. Thus the bottom 27 serves as a stop on the column. Therefore, the protection device is prevented from rising further with respect to the pump unit 15. The lowermost portion of the slots form passages between the exterior and interior of the column and as the liquid level then rises even further, liquid begins to pour into the column 26 through those passages. This occurs before the liquid reaches the level 19 at which the pump turns on. When a sufficient quantity of liquid has entered the bottom vessel portion of column 26 to overcome its buoyancy, it sinks to the bottom of the sump 11 to the position indicated in dashed lines in the drawing. Now the liquid can enter the pump through the slots 28 and the open bottom 15b of the pump unit to rise within the pump unit 15 to a level corresponding to that of the then-existing liquid level in the sump. This will prime the pump. As the liquid continues to rise in the sump and reaches the level indicated by the line 19, the electrical control device 23 actuates the pump unit 15 to begin discharge of liquid from the sump 11. When the liquid level in the sump drops to that indicated by the line 20, the electrical control device 23 deenergizes the backup sump 15, allowing the liquid level to again rise to the line 19 for the pumping procedure to be repeated.
Preferably, and as described in greater detail in my copending U.S. Pat. application Ser. No. 969,065, filed Dec. 13, 1978, and entitled "Sump Pump With Air Column Therein When Pump Is Not Operating", a light or audible alarm is connected to the electrical control device 23 and placed at a strategic location within the building in which the sump 11 is located so that when the backup pump 15 is actuated, the light or other alarm is also actuated to apprise the occupants of the building that the primary pump 10 has failed and that the secondary pump 15 has assumed the protective role of eliminating water from the sump 11. Presumably the occupants of the building will now take action to remedy the failure of the primary pump 10.
After the primary pump 10 is put back into operation, it will commence withdrawing liquid from the sump. As the liquid level drops below that indicated by the line 20, the backup pump 15 will no longer be needed. The building occupant may then grasp the protection device 25 and raise it above the water level 29, and open the petcock 30 to drain any surplus liquid contained within the column 26. The petcock 30 is then closed and the protection device returned into the liquid to again float with the liquid level and protect the backup pump 15 until the primary pump 10 has again failed. Alternatively, the petcock 30 can be omitted, and the column 26 may be evacuated when elevated about the pump 15 by energizing the pump 15 for a short burst sufficient to clear the interior of the column 26 below the slots 28. Also it is possible to remove the water from the guard by raising the pump unit 15 sufficiently to permit the guard 25 to fall away from the pump unit, then emptying the guard before replacing it on the pump unit in the sump as illustrated.
In the drawing, the secondary pump unit 15 has been illustrated at a particular elevation above the bottom of the sump 11. While the particular location of the backup pump 15 is unimportant so long as in an emergency it is operated to prevent liquid from flowing from the sump 11, the height of the column 26 must be always maintained greater than that of the elevation of the bottom of the pump 15 above the bottom of the sump 11 or above a support (e.g., a cement block) resting on the bottom of the sump. As an alternative, the protection device 25 could be suspended from an overhead support by chains or flexible cords in a manner such that it could not fall away from the pump unit 15 when there was little or no water in the sump, yet could move up and down with higher water elevations. Also, the maximum water level attained when the primary pump 10 is operating normally must be below the level of the bottom of the slots 28 when the guard 25 is abutting the bottom of the pump unit 15. Various parameters, including sump size and configuration, will dictate where the backup pump 15 is to be located within the sump 11, and therefore the necessary minimum height of the column 26. | A protection column is employed about a sump pump to exclude liquid and foreign matter in the sump from entering the pump interior until a time just prior to priming and activation of the pump. The column has a closed bottom portion serving as a vessel and permitting the column to float as the liquid level rises in the sump. The upper part of the column fits about the pump to act as a guide and has a series of vertical slots. The column floats until the bottom of the column strikes the bottom of the sump pump, which prevents the column from rising further. As the water level continues to rise in the sump, water enters the column through the slots, causing the column to sink to the bottom of the sump and permitting the liquid to rise to a level in the pump commensurate with the level elsewhere in the sump, thereby priming the pump. | 5 |
BACKGROUND OF THE INVENTION
[0001] (a) Field of the Invention
[0002] The invention relates to polymer production and in particular to a process for microbiologically producing poly-3-hydroxyalkanoate (PHAs) and derivatives thereof.
[0003] (b) Description of Prior Art
[0004] There has been considerable interest in recent years in the use of biodegradable polymers to address concerns over plastic waste accumulation. The potential worldwide market for biodegradable polymers is enormous. Some of the markets and applications most amenable to the use of such biopolymers involve those having single, short use applications, including packaging, personal hygiene, garbage bags, and others. These applications are ideally suited for biodegradation through composting.
[0005] Also, polymers find uses in a variety of plastic articles including films, sheets, fibers, foams, molded articles, adhesives and many other specialty products. For applications in the areas of packaging, agriculture, household goods and personal care products, polymers usually have a short (less than 12 months) use cycle. For example, in food packaging, polymers play the role of a protective agent and are quickly disposed of after the contents are consumed. Hygiene products like sanitary or diapers are immediately discarded once the product is used.
[0006] The majority of this plastic material ends up in the solid waste stream, headed for rapidly vanishing and increasingly expensive landfill space. While some efforts at recycling have been made, the nature of polymers and the way they are produced and convened to products limits the number of possible recycling applications. Repeated processing of even pure polymer results in degradation of material and consequently poor mechanical properties. Different grades of chemically similar plastics (e.g., polyethylene of different molecular weights, as used in milk jugs and grocery bags) mixed upon collection can cause processing problems that make the reclaimed material inferior or unusable.
[0007] Polyhydroxyalkanoates (PHAs) and more specifically poly-3-hydroxybutyrate (P3HB), a short side chain length polymer, have been known for years as being naturally synthesized biodegradable, biocompatible thermoplastics. These are bacterial polyesters used as energy storage when microorganisms are submitted to adverse growth conditions. The polymers are then formed as intracellular granules that can accumulate to 80 percent of the cell mass. The various monomers formulae are commonly reduced to:
—OCHR(CH 2 ) n —CO—
[0008] wherein n is an integer ranging from 1 to 5 and R consists either of a hydrogen or an alkyl group. The physical properties of P3HB (and mostly the copolymer P3Hn-co-3HV) have shown to compare those of polypropylene (PP) such that conventional processing techniques like melting, extrusion and blow forming may be used. Other polymers known as medium side chain length (mcl) behave like elastomers and therefore aim at different applications.
[0009] So far, PHAs have been produced through fermentation processes followed by extraction and purification methods. Although research is undergoing toward production in transgenic plants, it is expected that robustness and versatility of bioprocesses will claim to make fermentation the preferred technique for potential medium to large-scale production.
[0010] Until recently the limitations to viable commercial production of these bioplastics were mainly due to production costs as compared to synthetic petroleum based polymers. At present, it becomes well recognized that the properties of the PHAs are sought for specific applications and high value-added products in the fields of specialty packaging, cosmetics and biomedicals. Nevertheless, the production costs are still considered to be a major constraint to the development of a profitable industry. In order to address this drawback, it is necessary to make use of cheap carbon sources that are also abundant.
[0011] It would be highly desirable to be provided with method for producing a biologically degradable and biocompatible polyhydroxyalkanoate and derivatives thereof.
SUMMARY OF THE INVENTION
[0012] One aim of the present invention is to provide a process for production of polyhydroxyalkanoate (PHA) which comprises the step of incubating a PHA-producing microorganism in a medium comprising crude, isolated or treated starch and recovering PHA from the microorganism.
[0013] In accordance to the present invention, is provided a biomass containing starch which is processed to render the starch available sufficiently in a soluble form and/or in the form of an extract to be chemically biochemically, enzymatically and/or biologically treated.
[0014] In accordance with the present invention there is provided the starch is further hydrolyzed before incubation of PHA producing microorganisms.
[0015] Another aim of the present invention is to provide a process for producing polyhydroxyalkanoate selected from the group consisting of polymer of hydroxyalkanoic acid, hydroxybutyric acid, hydroxyvaleric acid, and copolymers thereof, wherein the copolymers may be poly(hydroxybutyrate-co-hydroxyvalerate) (PHBHV) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB), polymers and/or copolymers of hydroxyterminated polyhydroxybutyrate (PHB-OH), heteropolmers thereof, and any other polymers having a chemical structure consistent with the general formula previously described.
[0016] In accordance with the present invention another object is to provide a A polyhydroxyalkanoate (PHA) produced by incubation of at least one strain of PHA-producing microorganism in a culture medium comprising starch and/or a derivative thereof.
[0017] The biomass of the present invention may be selected from the group consisting of plants, wastewater, washed waters, potatoes, and by-products or derivatives thereof.
[0018] The biomass may also be processed by homogenization, grinding, crushing, shredding, cutting up, carving, breaking, lyophilizing, digesting, fermenting, incubating, dessicating, and microbiologically, thermally, chemically, biochemically and/or biologically treating, and combination thereof, before solubilisation.
[0019] In accordance with the present invention there is provided a biomass under the form of a powder, an homogenate, a grinded, crushed, cutted up, carved, or broken biomass, a piece, and/or a part of biomass.
[0020] Another aim of the present invention is to provide microorganisms selected from the group consisting of bacteria, mould, yeast, Azotobacter, Peudomonas, Nocardia, Coliform, Alcaligenes, Bacillus, Lactobacillus, Burkholderia, Rhodococcum, Methylobacterium, and genetically modified form thereof.
[0021] More specifically, microorganisms may be Azotobacter chroococcum, Azotobacter vinelandii, Escherichia coli, Pseudomonas cepacia, Alcaligenes lipolytica, Pseudomonas oleovorans and Azotobacter salinestris.
[0022] This summary of the invention does not necessarily describe all variations of the invention, but that the invention may also reside in a sub-combination of these features described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] [0023]FIG. 1 illustrates the evolution of glucose concentration (g/l), cell dry weight (g/l) and PHA accumulation when conditions of example 1 are applied
DETAILED DESCRIPTION OF THE INVENTION
[0024] The following description is of a preferred embodiment by way of example only and without limitation to the combination of features necessary for carrying the invention into effect.
[0025] In accordance with the present invention, there is provided a process comprising fermentation conditions in which at least one PEA producing microorganism at high yields and/or output rates from starch or hydrolysable derivatives thereof as carbon source. Among derivatives that can be included, limiting the invention: chemically, biochemically, biologically and/or enzymatically modified starch and/or byproducts of starch.
[0026] One embodiment of the invention is to provide a process for producing PHAs, which comprises culturing at least one strain of PHA producing bacteria. The strains of PHA producing bacteria can be selected from the group of species consisting of Azotobacter, Pseudomonas, Nocardia, Alcaligenes, Bacillus, Lactobacillus, Methylobacterium, Rhodoccus, Burkholderia, Escherichia coli, and recombinant forms thereof. Other PHA producing microorganisms that can be considered, but without any limitation, in the present invention are yeasts, fungi and moulds.
[0027] A preferred embodiment of the invention is the use of bacteria Azotobacter salinestris, Azotobacter vinelandii, recombinant Escherichia coli, Pseudomonas cepacia, Pseudomonas oleovorans, Methylobacterium extorquens, Azotobacter chroococcum, and/or Alcaligenes eutrophus, or a mixture thereof, to perform the fermentation step in production of PHAs from starch.
[0028] The process of the present invention is applicable to recover PHA polymers produced by microorganisms either naturally or through genetic engineering, or PHAs that are synthetically produced. PHA is a polymer having the following general structure:
H—[O—CHR—(CH 2 )p—CO] n —OH
[0029] wherein R is preferably an H, alkyl, or alkenyl; p is 0, 1, 2, 3, 4, or 5; and n is an integer.
[0030] In another embodiment of the invention PHA may consist entirely of a single monomeric repeating unit, in which case it is referred to as a homopolymer. For example, polyhydroxybutyrate (PHB) homopolymer has repeating monomeric units where R is a methyl group and p=1. Copolymers, in contrast, contain two different types of monomeric units. PHBHV, for example, is a copolymer containing both polyhydroxybutyrate and hydroxyvalerate where R is an ethyl group, and p=1) units in variable ratios and incorporation order. Another copolymer of interest contains 3-hydroxybutyrate and 4-hydroxybutyrate units (P3HB4HB). When three different types of repeating units are present the polymer is referred to as a terpolymer.
[0031] Alternatively, biological synthesis of the biodegradable PHAs useful in the present invention may be carried out by fermentation with the proper organism (natural or genetically engineered) with the proper carbon source (single or multicomponent).
[0032] The PHA compositions produced according to one embodiment of the present invention can be recovered from the PHA-producing microorganism by conventional methods. Typically, a solvent-based approach is utilized, wherein the cells are harvested, dried, and the PHA is extracted with a solvent capable of dissolving PHA from other bacterial components. However, methods suitable for the recovery of PHAs from microbial and other biomass sources are also expected to be suitable for the recovery of analogs or modified forms of PHA made in accordance with the present invention.
[0033] In another embodiment of the present invention, there is provided a method of using the PHA of the present invention to produce a polymer or copolymer, wherein the PHA may be reacted with a coupling agent. The polymer or copolymer to produced could be, for example, a block, a random or graft polymer or copolymer thereof. Also provided are the polymer and copolymer compositions produced therefrom. Suitable coupling agents may include, for example, alkyl or aryl diisocyanate or triisocyanate, phosgene, alkyl or diaryl carbonate, a monomeric organic diacid, a monomeric organic diacid chloride, a monomeric organic diacid anhydride or a monomeric organic tetraacid dianhydride. Alternatively, the coupling agent can be an oligomer with end-groups that are reactive with chemically modified PHA, such as carboxy-terminated oligomeric polyesters or an isocyanate-terminated oligomeric polyol or polyester. This approach can be used, for example, to produce polyesters, copolyesters, polyester-carbonates, and polyester urethanes.
[0034] The most preferred PHA polymers for use in this invention are poly(hydroxybutyrate-co-hydroxyvalerate) polymers (PHBHPV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers (P3HS4HB), and hydroxyterminated polymers and copolymers of polyhydroxybutyrate (PHB-OH) and polyhydroxyalkanoate (PHA-OH).
[0035] According to a further embodiment of the present invention, there is provided a method of using the analogs and/or modified PHA of the present invention to produce a polymer of copolymer, wherein the PHA is reacted with a coupling agent and with a different modified moiety. The polymer so produced could be, for example, a block or random block polymer or copolymer. Also provided are the polymer and copolymer compositions produced therefrom. Suitable coupling agents may include, for example, alkyl or aryl diisocyanate or triisocyanate, phosgene, alkyl or diaryl carbonate, a monomeric organic diacid, a monomeric organic diacid chloride, a monomeric organic diacid anhydride or a monomeric organic tetraacid dianhydride. Alternatively, the coupling agent can be an oligomer with end-groups that are reactive with modified PHA, such as carboxy-terminated oligomeric polyester or polyamide, or a isocyanate-terminated oligomeric polyol, polyester or polyamide. A chemically modified moiety for use in this embodiment can include polyester diols such as polycaprolactone diol, polybutylene succinate diol, polybutylene succinate co-butylene adipate diol, polyethylene succinate diol, and similar aliphatic polymeric and copolymeric diols. Alternatively, the chemically modified moiety can be a polyesther diol such as a polyethylene oxide-diol, polypropylene oxide-diol, or polyethylene oxide-propylene oxide diol. This approach can be used, for example, to produce polyesters, copolyesters, polyester carbonates, polyester urethanes, polyester ethers, polyester amides, copolyester ethers, polyester ether carbonates, and polyester ether urethanes.
[0036] In a further embodiment of the present invention, there is provided a method of using the PHA or analogs thereof to produce a block polymer or copolymer, comprising the steps of reacting the PHA with a reactive monomer. Also provided are the PHA-containing copolymer compositions produced therefrom. Where needed, catalysts and other reactants known in the art to facilitate the reaction are used. The reactive monomer used in this embodiment can include, for example, alkyl epoxides such as ethylene oxide and propylene oxide, lactones such as caprolactone, butyrolactone, propiolactone, valerolactone, lactams such as caprolactam, and formaldehyde. This approach can be used to produce polyesters, copolyesters, polyester ethers, polyester amides, and polyester acetals.
[0037] According to one embodiment of the invention, all strains of microorganisms are cultured in a medium that may contain the following mineral salts: 0.6-3.0 mM magnesium sulfate, 10-200 μM ferrous sulfate, 1.0-6.0 mM potassium phosphate monobasic or 2-5 mM potassium phosphate dibasic, 0.7-32 μM sodium molybdate, 10-25 mM sodium chloride, and 0.4-1 mM calcium sulfate or calcium chloride.
[0038] In a particular embodiment, the salts medium contained may be 40-60 μM ferric citrate and 15-300 mM ammonium acetate. In one other case, the salts medium contained 1.5-2.5 mM sodium citrate and 30-300 mM ammonium nitrate.
[0039] According to another embodiment of the invention, 2-5% w/v of glucose from hydrolyzed starch solution having a DE (dextrose equivalent on a scale of 100) of 80 to 95 may he added to the medium.
[0040] On particular embodiment of the present invention is the biocompatibility of the PHA produced according to the process of the present invention. The commercial potential for PHAs of the invention opens up to important industries such as cosmeceutical, pharmaceutical and biomedical, and is derived primarily from a most advantageous property that distinguish PHA polymers from most petrochemical-derived polymers, namely biocompatibility. Biocompatibility may be defined as the quality of not having toxicological effects on biological systems and/or the ability of a material to perform a specific application with this same quality. This quality allows for numerous applications such as drug delivery, orthopedic implant, tissue engineering and cardiovascular uses.
Material and Methods
[0041] Microorganism and Culture Media
[0042] The strain used for the production of PHA is Azotobacter salinestris (ATCC 49674). Azotobacter salinestris is a gram-negative bacteria related to Azotobacter chroococcum and is cultured in a medium as described above.
[0043] The fermentor inoculum consists in a pre-grown (18-24) culture with a corresponding cell dry weight of 1-5 g/l. Samples of quickly halted log growth phase are mixed with an equal volume of glycerol 30% (v/v) and stored in vials (1-2 ml) at −80° C. to constitute a working cells bank.
[0044] Potato Starch Hydrolysis
[0045] Potato tubers or peels are first washed and shredded. Water is then added to form 500-2000 g/l potato slurry depending on final glucose concentration desired. The resulting mixture may then be subjected to starch hydrolysis, which is a two steps process. In the first one, called liquefaction, the starch slurry is heat treated (65-95° C. at 350 rpm for 30 min-1 h), before being hydrolyzed to a maltodextrines solution with a heat-stable α-amylase enzyme preparation (Termamyl®120L, Novo Nordisk) in presence of calcium ions. This step is carried out directly in a steamed tank reactor vessel equipped with temperature, stirrer speed and pH adjustments all of which set at the following operating parameters. 90-100° C.; 200-350 rpm; pH=6.0-6.5 for a period of up to 60-120 min. The pH may be adjusted with calcium hydroxide to provide the necessary calcium ions. The second step, called saccharification, allows for further hydrolysis of the dextrines into glucose. It is performed with a 1,4-alpha-D-glucohydrolase (AMG 300, Novo Nordisk) after setting the operating parameters as: 55-60° C.; 200-250 rpm; pH=4.2-4.8 for a period of 24-60 h. The degree of enzymatic hydrolysis may be determined with the use of a rapid analysis system for the glucose concentration (Biolyzer by Kodak, New Haven, Conn.).
[0046] Fed-Batch Culture
[0047] Fermentation is performed in a conventional controlled stirred tank reactor (STR) at 25-30° C. and pH=7.0. The fermentation media is the same as the one described above for the cultivation of the microorganism. The fermentor is seeded with a 2-10% (v/v) fresh inoculum in active growth phase. The agitation and airflow rate are varied during course of fermentation to maintain the dissolved oxygen level (DO) above 3-5% saturation and preferably around 5-10% saturation. Following a log phase of 4-10 h, it is necessary to maintain the glucose level by feeding with a hydrolyzed starch stock solution at a concentration of 20-80% w/v glucose at a variable feed rate in the range of 5-10 ml/l/h. Fish peptone, modified meat peptone, or yeast extract may be also supplied to the growth medium to enhance PHB synthesis. Peptones are thought to act as a PHA yield promotion factor at concentration of 0.05 to 0.2% w/v. For best results, the peptone solution should be added at a rate proportional to the glucose supplement. It is also required to maintain a continuous supply of broth nutrient by feeding a concentrate of the fermentation medium throughout the growth phase. A typical feedstock may consist of a 4-20 times the initial broth concentration and should be supplied at a rate proportional to glucose feed solution. At the end of fermentation, cells are separated from the spent medium by centrifugation or filtration.
[0048] Polymer Extraction Method
[0049] PHA isolation consists in a step procedure in which cells are sequently separated, washed and then submitted to polymer extraction as described. Cells are washed once or twice in distilled water and membranes are broken by using hot mixture of NaOH and NH 4 OH or NaOH, NH 4 OH and SS or NaOH, NH 4 OH and Triton™, or mechanically by glass beads or other shear forces or by heat treatment. PHA is then isolated using different approaches such as solvent extraction using chloroform or methylene dichloride or by digesting NPCM (non polymer cell material) using enzyme cocktail of protease, lipase and nuclease. PHA is finally recovered by centrifugation, differential centrifugation or filtration, and dried avoiding direct light exposure. Physical determination such as average molecular weight and polydispersivity index may be carried out using standard procedures known in the art.
EXAMPLE I
Growth of A. salinestris and Production of PRA Following a Fedbatch Fermentation Strategy
[0050] An inoculum of A. salinestris (strain ATCC 49674) was grown aerobically in a 2 liters Fernback™ flask containing 500 ml of previously described culture medium. The flask was incubated at 30° C. for 24 h with rotating agitation set at 250 rpm.
[0051] The resulting inoculum was then added to a 14 liters bioreactor (CHEMAP) containing 8 liters of the previously described fermentation medium. The fermentation was carried out at 30° C. in a fed-batch mode at the following conditions: 1) the pH was maintained at 7 using concentrated solution of sodium hydroxyde or sulfuric acid; 2) the aeration rate and the agitation speed were adjusted manually during course of fermentation to maintain the level of oxygen above 5% and below 30% saturation. The maximum agitation speed reached was 610 rpm; 3) foam formation was controlled with addition of MAZU™ (PPG Industries); 4) glucose was fed throughout growth phase from 20-80% w/v stock solution as obtained by starch hydrolysis, at a rate of approximately 5-10 ml/l/h; 5) spent nutrients were provided throughout growth phase by feeding a 4-20 times concentrated fermentation medium. Feed rate was approximately 5-10 m/l/h. The fermentation was stopped after 30 hours.
[0052] The PHA was recovered using modified method of Berger (Berger et al. (1989) Biotechnology Techniques, 3:227-232). Cells were centrifuged 15 minutes at 3000×g and then washed twice in distilled water. 50 ml of methanol were added to an equivalent of 5 g (dry weight) of cells and vigorously mixed. The mixture was incubated 48 h at 40° C. and the cells were harvested by centrifugation at 3000×g for 15 minutes. The supernatant was discarded and 100 ml of chloroform was added to the pellet. The mixture was gently agitated and incubated at 40° C. for 24 h. 100 ml of distilled water was added to the chloroform mixture, carefully agitated and centrifuged at 3000×g for 15 minutes. The lower phase was recuperated and the soluble polymer precipitated with the addition of cold ethanol 95% under continuous agitation. The precipitated PHA obtained was recovered by filtration and dried at room temperature avoiding light exposure.
[0053] At the end of the fermentation, the cell biomass concentration was 30-40 g/l (dry weight), containing approximately 15-20 g/l of PHB/HV (92% HB and 8% HV) with a molecular weight of 1 million and a polydispersity index of 1.2.
EXAMPLE II
Production of Copolymer PHB/HV Following a Co-Substrate Fedbatch Fermentation Strategy
[0054] A inoculum of A. salinestris (ATCC 49674) was grown aerobically in a 2 liters flask containing 500 ml of previously described culture medium supplemented with 30 mM sodium valerate. The culture was incubated at 30° C. for 24-30 h rotating agitation set at 250 rpm.
[0055] The fermentation parameters were similar to those described in Example 1 for the aeration rate, pH and dissolved oxygen level. Sodium valerate as well as glucose were added during course of fermentation from a concentrate of 500 mM sodium valerate and 50% glucose in order to obtain a random copolymer of 3HB-3HV or a block copolymer. Depending on the feed strategy, copolymers were composed of 65 to 90% of HB and 10 to 35% of HV, with a MW of 1 million and P.I. of 1.2.
[0056] While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims. | The present invention relates to a process of production of polyhydroxyalkanoate (PHA) by incubating PHA producing microorganisms in a medium containing starch, starch extracts, or derivatives as sources of carbon. The process comprises also the synthesis of derived compounds belonging to the chemical family of PHA. | 2 |
[0001] This is a continuation of Parent application Ser. No. 11/001,283 filed on Dec. 1, 2004 and entitled “Method for isolating and modifying DNA from blood and body fluids”
CROSS-REFERENCE TO RELATED APPLICATIONS
[0002] Not applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] Not applicable
REFERENCE TO A MICROFICHE APPENDIX
[0004] Not applicable
BACKGROUND OF THE INVENTION
[0005] 1. Field of the Invention
[0006] This invention is related to a method for rapidly isolating and modifying DNA from blood and body fluids. This invention provides a procedure and composition to obtain a high yield of modified DNA for methylation-specific PCR assay by coupling DNA isolation and modification courses.
[0007] 2. Description of the Related Art
[0008] Epigenetic inactivation of the genes plays a critical role in many important human diseases, especially in cancer. The core mechanism for epigenetic inactivation of the genes is methylation of CpG islands in genome DNA. Methylation of CpG islands involves the course in which DNA methyltransferases (Dnmts) transfer a methyl group from S-adenosyl-L-methionine to the fifth carbon position of the cytosines. It was well demonstrated that methylation patterns of DNA from cancer cells are significantly different from those of normal cells. DNA of cancer cells is generally hypomethylated compared to that of normal cells. However DNA of cancer cells could be more methylated than that of normal cells in the selected regions such as in the promoter regions of tumor suppressor genes. Thus, detection of methylation patterns or ratio in the selected genes of cancer cells could lead to discrimination of cancer cells from normal cells, thereby providing an approach to early detection of cancer.
[0009] There have been many methods for detection of DNA methylation. The most widely used method among these is methylation-specific PCR (MS-PCR). This assay through chemical modification of DNA, selectively amplifies methylated sequences with primers specific for methylation (Herman et al., Proc. Natl. Acad. Sci. USA 93: 9821-9826, 1996). After PCR a gel-based detection is processed. MS-PCR was recently improved significantly by using the real-time probe system. These improved methods such as MethyLight, Q-MSP (Eads C A et al: Cancer Res, 59: 2302-2306, 1999), and HM-MethyLight (Cottrell SE et al: Nucleic Acids Res. 32: e10, 2004) proved to be more sensitive, specific and quantitative than MS-PCR. However, all existing DNA methylation-based technologies are still not enough to apply to clinical cancer detection, even including MethyLight, a method considered to have potential for clinical application. A critical weakness of these existing methods is that their clinical sensitivity is still too low when a sample from a non-invasive approach is used, such as from plasma/serum or other remote media. It was demonstrated that a cancer at its early stage may release its cells or free DNA into blood through apoptosis, necrosis or local angiogenesis, which establishes a basis for cancer detection using DNA methylation-based technology. The quantity of free circulating DNA from tumor, however, varies from tens of pictogram (pg) to hundreds of nanograms (ng) per ml plasma/serum. Most of them (>90%) range from several hundreds of pg to tens of ng per ml of plasma/serum. The collected DNA will be greatly reduced further by isolation and modification procedures. In general, only 5%-10% of the collected DNA is available as a modified DNA for PCR assay, which may be as low as several pgs (per ml plasma/serum). Based on the limitation level of methylated modified DNA detection (30 pg) in current quantitative MS-PCR technology (i.e.: HM-MethyLight), a complete cancer detection assay (at least 8 target genes) required at least 250 pg of completely methylated modified DNA, that is, 3-5 ng circulating tumor DNA. If considering the condition of that some target genes are only partly methylated (i.e.: 30%), the amount as high as 10-15 ng of circulating tumor DNA is required. It means that 20 ml of plasma/serum or 40 ml of blood must be collected for an assay in order to ensure the correct results available from 90% or greater of the samples. Obviously, low clinical sensitivity of the existing methylation-based cancer detection methods is mainly due to insufficient modified DNA available for PCR assay. To achieve sufficient modified DNA for Q-PCR assay, either a sufficient amount of blood or efficient isolation and modification of DNA must be needed. However, it should be difficult to collect 40 ml of blood for every routine assay for cancer detection. Therefore feasible approach to achieve sufficient modified DNA is only through highly efficient isolation and modification of DNA
[0010] Various methods used for DNA isolation from blood or body fluids are available commercially. A standard technique is digestion of the sample with proteinase K followed by phenol/chloroform extraction or more conveniently followed by column purification. Column methods mainly include the High Pure PCR Template Preparation Kit (Roche Diagnostics), QiAamp DNA Mini Kit (Qiagen) and NucleoSpin Blood Kit (Macherey-Nagel Duren). However, DNA recovery by using these methods is about only 40-50% of the original DNA amount because of loss in the handling process. There are also various methods of DNA modification all characterized by bisulfite-treatment. The bisulfite-based DNA modification is used to discriminate between cytosine and methylated cytosine, in which DNA is treated with bisulfite salt to convert cytosine residues to uracil in single-stranded DNA, while methylated cytosine remains same. The bisulfite-based DNA modification basically consists of three processing steps: 1) sulphonation, 2) hydrolytic deamination, and 3) alkali desulphonation. This process involves relatively complex chemistry conditions and it results in serious problems in all of the current bisulfite conversion methods: Time-consuming (usually 16 h) and more critically, severe DNA degradation (84-96%), which results in a low level recovery of modified DNA (Grunau C et al: Nucl Acids Res, 2001). Considering all the problems existing in both currently used DNA isolation and modification method, and furthermore, considering a separated use of existing DNA isolation and modification methods in generating modified DNA, it is impossible to obtain sufficient modified DNA available for a routine methylation-based cancer detection assay. Therefore a more efficient method of DNA isolation and modification is still needed for overcoming problems of existing method to improve methylation-based cancer detection.
BRIEF SUMMARY OF THE INVENTION
[0011] The highly efficient isolation and modification of DNA from blood or body fluids become a critical approach for improving methylation-based cancer detection technology. The present invention provides a method and kit to achieve this approach by a coupled DNA isolation and modification process, comprising the steps of: (1) Isolating genomic DNA, which comprises the interest DNA and background DNA, from plasma, serum, or other body fluids of an individual by using non-chaotropic reagents; (2) Chemically treating DNA in the same tube with a bisulfite salt and the DNA degradation-blocking agents as an essential component, which allows all of unmethylated cytosine bases to be completely converted to uracil in a short time, whereas methylated cytosine bases remain unchanged; (3) Binding chemically modified DNA to a solid phase followed by desulphonation and cleaning; and (4) Eluting the modified DNA with a low salt buffer or water.
[0012] Thus the invention allows a highly efficient and fast isolation and modification of genomic DNA from various body fluids, particularly from plasma/serum. This invention is based on the finding that genomic DNA from body fluids can be easily and quickly isolated by using a high concentration of non-chaotropic salt buffer. The invention is also based on the finding that isolated DNA can be directly used for chemical modification with a novel composition provided by this invention. The invention is further based on the finding that a complete modification of genomic DNA can be quickly finished with a high yield of modified DNA by using a novel composition presented in this invention. Therefore the method presented in this invention significantly overcomes the weaknesses existing in the prior technologies and enables a sufficient modified DNA available for a routine cancer detection assay using methylation-based technology.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 shows a diagram of the coupled DNA isolation and modification. The process involves the extraction of genomic DNA from plasma/serum and other body fluids and chemical modification of DNA in the same tube. Modified DNA is then captured with a solid carrier surface, purified and eluted.
[0014] FIG. 2 shows the recovery of DNA from the serum by using the method of this invention. The experiment was carried out as described in Example 1.
[0015] FIG. 3 shows an experiment that showed the DNA degradation rate and DNA modification efficiency by using the method of this invention. The experiment was carried out as described in Example 2.
[0016] FIG. 4 shows an experiment that showed the required amount of DNA contained in the serum sample for chemical modification using the method of this invention. The experiment was carried out as described in Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The object of the present invention is to provide a novel method for efficiently isolating and modifying genomic DNA from plasma/serum and other body fluids so that sufficient modified DNA can be available for a routine cancer detection assay using DNA methylation-based technologies. This method is particularly useful for gaining a high yield of modified DNA from a small quantity of starting materials. This method is also particularly useful for fast isolation and modification of DNA in a short time.
[0018] In contrast to previous methods for chemically modified DNA preparation (which required a separate process in that genomic DNA is first isolated and purified, and purified DNA is then modified), the method of the present invention, as illustrated in the Example section, generates modified DNA by coupling DNA isolation and modification in a single tube. This coupled process greatly reduces DNA loss, degradation and drastically shortens the process for preparing modified DNA.
[0019] The method of the present invention uses the high concentrations of non-chaotropic salts in association with protein enzyme inhibitors to isolate DNA from plasma, serum and other body fluids that include cerebro-spinal fluid, saliva, nasal swab or nasal aspirate, sputum, bronchoalveolar lavage, breast aspirate, cervical swab or vaginal fluid, semen, prostate fluid, and urine. The non-chaotropic salts include, but are not limited to sodium chloride, calcium chloride, lithium chloride, potassium chloride, magnesium chloride, sodium acetate, calcium acetate, lithium acetate, potassium acetate, magnesium acetate, sodium phosphate, calcium phosphate, lithium phosphate, potassium phosphate and magnesium phosphate. A high concentration of non-chaotropic salts is able to cause the dissociation of proteins from DNA and protein molecules precipitation from solution, and further enables DNA to precipitate out of an alcohol solution. It is preferred according to this invention that a sodium salt such as sodium chloride or sodium acetate or their mixture is used in a concentration of 0.1 M to 5 M. It is also preferred according to this invention that the salt solution is an alkalized solution with a pH ranged from 8 to 11. It is more preferred according to this invention that isopropnol or alcohol is used to precipitate DNA.
[0020] The DNA isolated in this manner is able to be used for chemical modification after DNA denaturing by heating or alkalized solution such as 0.2 M NaOH. According to this invention the composition of chemical modifying reagents comprise a bisulfite, a potassium salt, or a magnesium salt and an EDTA. The composition of chemical modifying reagents is made in a solution form. According to this invention that bisulfite is selected from sodium bisulfite, potassium bisulfite, ammonium bisulfite, magnesium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and magnesium metabisulfite, preferred a sodium metabisulfite from above in the concentrations of 0.5 M to 5 M. According to this invention a potassium salt is selected from potassium chloride, potassium phosphate, and preferred a potassium chloride in the concentrations ranged from 0.1 M to 1 M. According to this invention that an EDTA or an EDTA salt is also selected, preferred EDTA in the concentrations of 1 mM to 100 mM.
[0021] An advantage of the composition according to this invention is that unmethylated cytosine residues can be maximally converted to uracil in a single-stranded DNA, while methylated cytosine remains unchanged. Another advantage of the composition according to this invention is that degradation of DNA resulted from chemical, biochemical and thermophilic action in modification is efficiently prevented or reduced. A further advantage of the composition according to this invention is that the DNA modification process is much shorter without interrupting a completed conversion of unmethylated cytosine to uracil and without a significant thermodegradation of DNA resulted from depurination.
[0022] In this invention, the temperature for the chemical modification ranges between 50° C. and 80° C., and preferably between 60° C. and 69° C. and more preferably at 65° C. The reaction time set up for chemical modification ranges from 15 min to 4 h, preferably from 30 min to 2 h, more preferably for 1 h.
[0023] Once DNA modification is complete, DNA is captured, desulphonated and cleaned. The modified DNA can be captured by a solid matrix selected from silica salt, silica dioxide, silica polymers, glass fiber, celite diatoms and nitrocellulose in the presence of high concentrations of non-chaotropic salts. It is preferred according to this invention that modified DNA is captured with an apparatus comprising a column pre-inserted with a silica gel, or a silica membrane or a silica filter. It is more preferred according to this invention that a silica matrix is pre-treated with alkalized sodium salt solution at a high concentration to enhance the binding of modified DNA. It is further preferred according to this invention that a column is a micro-spin column which fits a 1.5 or 2.0 ml micro-centrifuge tube, and the combination of the column and the micro-centrifuge tube further fits inside a table-top microcentrifuge. After the modified DNA is applied to the column, a binding buffer consisting of non-chaotropic salts at concentrations from 1 M to 5 M can be added to further enhance the binding of the modified DNA to silica matrix. The DNA-bound silica matrix is washed by adding a washing buffer preferably comprising a buffered solution containing 50-90% of ethanol. The modified DNA is further desulphonated on the column with an alkalized solution, preferably sodium hydroxide at concentrations from 10 mM to 300 mM, more preferably at a concentration of 50 mM. Once desulphonation of modified DNA bound to silica matrix has been completed, the column is further washed with the washing buffer 2-3 times. The modified DNA is then eluted from the column and collected into a capped microcentrifuge tube. An elution solution could be DEPC-treated water or TE buffer (10 mM Tris-HCL, pH 8.0 and 1 mM EDTA). Both quality and quantity of eluted modified DNA can be measured by conventional techniques such as pico-green DNA measurement or by PCR amplification.
[0024] According to this invention, all of the components for DNA isolation, modification and purification of modified DNA are commercially available. This invention also provides a kit for coupled isolation and modification of DNA from blood and other body fluids, comprising a lysis buffer, a binding buffer and a modification buffer. In one embodiment, the kit further comprises an apparatus with a pre-inserted silica filter to capture modified DNA.
[0025] It has been discovered that use of the method of this invention is able to prevent degradation of DNA in DNA modification process, while a complete conversion of cytosine to uracil is performed. It has been also discovered that use of the method of this invention is able to greatly shorten the time required for DNA modification. It has been further discovered that use of the method of this invention can greatly reduce the DNA amount conventionally needed for chemical modification. It has been further discovered that use of the method of this invention can significantly increase yield of modified DNA from the described sample resource.
[0026] The method of this invention is applicable for isolating and modifying DNA from whole blood, plasma, serum and buffy coat. The method of this invention is also applicable for isolating and modifying DNA from other body fluids such as cerebro-spinal fluid, saliva, nasal swab or nasal aspirate, sputum, bronchoalveolar lavage, breast aspirate, breast lavage, cervical swab or vaginal fluid, semen, prostate fluid and urine. The method of this invention is further applicable for isolating and modifying DNA from a small amount of cells cultured in a 96-well plate and from media with floating cells or DNA released from apoptotic cells. The plasma or serum can be collected according to the methods described in prior art. The cells contained in other body fluids can be collected by various methods described or by simply centrifugation. By using the method of this invention, the required amount of plasma or serum for an assay point of gene methylation may be as low as 40 ul (assuming the minimum DNA amount in plasma/serum is 0.5 ng/ml). The required number of cells from other body fluids or small in vitro culture may be as few as 5 cells for an assay point of gene methylation.
[0027] The method of this invention for isolating and modifying DNA from blood and body fluids is further illustrated in the following examples:
Example 1
[0028] This experiment was carried out in two groups to show the recovery of DNA from serum by using the method of this invention. In group 1, the DNA extracted from blood of a volunteer was added into fetal calf serum (FCS) at different concentrations and mixed. 200 ul of FCS containing different concentrations of DNA were then added to an equal volume of lysis buffer, which comprises a solution of 0.3 M NaOAc and 5 M NaCl with pH 9.0 and 0.25% of proteinase K. The mixture was incubated for 10 min at 65° C. and DNA was then precipitated by adding 0.6 volume of 100% isopropnol followed by centrifugation. Precipitated DNA was kept in the same tube and denatured with 0.2 M NaOH. In comparison, in group 2, the DNA extracted from same blood was directly denatured with 0.2 M of NaOH. Both denatured DNA from group 1 and 2 were then treated with a modification solution for 1 h at 65° C. The modification solution comprises 3.2 M of Na 2 S 2 O 5 , 500 mM of KCl and 0.2 mM EDTA. The solution containing modified DNA was mixed with modified DNA binding buffer comprising non-chaotropic salts and added into a column apparatus with inserted DNA capture filter. Mixed solution passed through the column in a receiver tube by centrifugation. Modified DNA was desulphorated and eluted from the DNA capture filter. The amount of modified DNA from both group 1 and 2 was examined by real-time quantitative PCR. Relative level of isolated DNA from serum is calculated by using the equation: ½ |ΔCt| ×100%. A pair of primers and a probe designed to amplify both methylated and unmethylated alleles of b-actin were used to quantify DNA. Primer sequences of β-actin are: forward GGAGGTAGGGAGTATATAGGT (SEQ No. 1) and reverse CCAACACACAATAACAAACA (SEQ No. 2). The probe sequence of β-action is: TGATGGAGGAGGTTTAG (SEQ No. 3). As shown in FIG. 2 , the level of modified DNA measured in group 1 is approximately 77% and 81% of that in group 2 at 10 and 100 ng of DNA concentration, respectively. Thus an 80% level of DNA recovery from serum can be obtained by using the method of this invention, which is higher than a 50-60% level of DNA recovery from serum by using conventional methods.
Example 2
[0029] This experiment was carried out in three groups to determine the DNA degradation rate and DNA modification efficiency by using the method of this invention. In group 1, 2 and 3, different concentrations of DNA extracted from blood of a volunteer was denatured. Denatured DNA from group 1 was treated with a modification solution generated in this invention for 1 h at 65° C. The modification solution comprises 3.2 M of Na 2 S 2 O 5 , 500 mM of KCl, and 0.2 mM EDTA. Denatured DNA from group 2 was treated with a conventional modification solution for 1 h at 65° C. Denatured DNA from group 3 was treated with a conventional modification solution for 16 h at 50° C. The conventional modification solution comprises 5 M of sodium bisulfite and 8 mM of hydroquinone. After modification, the solution containing the modified DNA from group 1 were mixed with a modified DNA binding buffer comprising non-chaotropic salts and added into a column apparatus with inserted DNA capture filter. The mixed solution passed through the column by centrifugation in a receiver tube. The modified DNA was desulphorated and eluted from the DNA capture filter. The modified DNA from group 2 and 3 was captured, desulphorated and eluted according to the method described in prior of art (Herman et al., Proc. Natl. Acad. Sci. USA 93: 9821-9826, 1996). The amount of modified DNA from group 1, group 2, and group 3 was examined by real-time quantitative PCR. Relative level of modified DNA of different groups is calculated by using the equation: ½ ΔCT ×100%. A pair of primers and a probe designed to amplify both methylated and unmethylated β-actin were used to quantify the modified DNA. β-actin primer and probe sequences are described in Example 1. A pair of primers designed to amplify unmodified b-actin was used to quantify unmodified DNA from modification agent-treated DNA and modification agent-untreated input DNA. As shown in FIG. 3 , the average amount of modified DNA from group 1 is about 34% of input DNA, while the amount of unmodified DNA is about 0.02% of input DNA. In contrast, the amount of modified DNA from group 2 and group 3 is 97% and 80% less than that obtained from group 1. These results demonstrate that use of the method of this invention can greatly decrease the degradation of DNA in the modification process.
Example 3
[0030] This experiment is carried out to determine the minimum amount of DNA required for chemical modification by using the method of this invention. DNA extracted from blood of a volunteer was added into fetal calf serum (FCS) at concentrations of 0.05, 0.5, 5, and 50 ng/100 ul, respectively. 200 ul of FCS containing different concentrations of DNA were then added to an equal volume of lysis buffer, which comprises a solution of 0.3 M NaOAc and 5 M NaCl with pH 9.0 and 0.25% of proteinase K. The mixture was incubated for 10 min at 65° C. and DNA was then precipitated by adding 0.6 volume of 100% isopropnol followed by centrifugation. Precipitated DNA was kept in same tube and denatured with 0.2 M NaOH. Denatured DNA was then treated with a modification solution for 1 h at 65° C. The modification solution comprises 3.2 M of Na 2 S 2 O 5 , 500 mM of KCl and 0.2 mM EDTA. The solution containing modified DNA was mixed with modified DNA binding buffer comprising non-chaotropic salts and added into a column apparatus with inserted DNA capture filter. Mixed solution passed trough the column in a receiver tube by centrifugation. Modified DNA was desulphorated and eluted from the DNA capture filter with 20 ul water. 2 ul of eluted solution was used for real-time quantitative PCR to examine the amount of modified DNA. A pair of primers and a probe designed to amplify both methylated and unmethylated alleles of β-actin were used to quantify DNA. The sequences of primers and probe are described in Example 1. As shown in FIG. 4 , modified DNA was detected even in serum sample containing only 0.1 ng of genomic DNA. Therefore the required amount of DNA contained in a biological sample for chemical modification by using the method of this invention could be less than 0.1 ng. | This invention is related a method for rapidly isolating and modifying DNA from plasma/serum and body fluids. This invention provides a procedure and composition to obtain a high yield of modified DNA for methylation-specific PCR assay by coupling DNA isolation and modification courses. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for scooping, transporting and disguising animal feces. A fold-out, two-piece, disposable box is used to scoop, transport and disguise the animal feces. The box is comprised of a male and female section. When they are to be used, the flat male and female box halves unfold and snap open, forming the box components. The feces is scooped by pushing the male box half into the female box half, thereby enveloping the feces. The box, with a carrying handle or optional plastic bag lining, is formed around and about the feces which are no enclosed within the box.
A further feature of the present invention is that the interior of the formed box is layered with a moisture-impermeable substance such as polyethylene. The polyethylene may be coated with a normally dormant, moisture activated mixture containing an aroma and disinfectant. When the moist feces comes in contact with the coated box interior surface, the moisture dissolves the active ingredients and releases the aroma and disinfectant. The aroma masks the feces odor, and the disinfectant slows odor production by killing the feces bacteria.
2. Description of the Prior Art
The disposal of animal feces in populated areas, such as cities o mobile home parks, is a major problem for the pet owner. The owner will usually carry gloves or a scoop, and then place the feces in a bag for transportation and disposal. This method is obviously dirty and unsavory, and does not lend itself to transportation of the feces any substantial distance for sanitary disposal. The method is lacking and is in need of improvement.
The present invention overcomes the disadvantages of the prior art by providing a clean and easy method to accomplish the task of transportation and disposal of animal feces.
SUMMARY OF THE INVENTION
The general purpose of the present invention embodies a novel method and apparatus to scoop, transport and disguise animal feces. The present invention improves on prior art by providing a novel two-piece box design. Each component is flat and collapsible for convenient portability. Upon use, each flat, preformed box is simply folded open, automatically locking into place. The two box component halves are designed so that the male part slips into the female portion enveloping the feces and forming a box with a substantially tight pressure-fit seal. An alternative design includes a plastic bag liner affixed to the interior of each fold open box half.
One significant aspect and feature of the present invention is a box for the transportation of feces, which is designed with a handle for easy carrying.
Another significant aspect and feature of the present invention is that the box disguises the feces by decreasing and masking the odor. The moisture from the feces causes the release of a disinfectant and an aroma that is coated on the interior surface of the box. The present invention embodies a unique portable box design that functions as both a scoop and a carrying receptacle. It is unobtrusive, more convenient and much cleaner than the prior art scoop methods currently in use.
A further significant aspect and feature of the present invention is that the interior of the box contains a disinfectant and aroma to help mask the feces odor until it can be burned or buried or otherwise disposed of. No current technique is available to accomplish this task.
Yet another significant aspect and feature of the present invention are flat, low profile, easily stored box halves which are erected to form box halves.
Yet a further significant aspect and feature of the present invention is a box which includes a plastic bag lining on the interior of each box half.
DESCRIPTION OF THE DRAWINGS
Other objects of the present invention and many of the attendant advantages of the present invention will be readily appreciated as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, in which like reference numerals designate like parts throughout the figures thereof and wherein:
FIG. 1 illustrates a box separated into box halves;
FIG. 2 illustrates an end view of semi-erectile female box half taken along aspect line 2--2 of FIG. 1;
FIG. 3 illustrates an end view of the erected female box half of FIG. 2;
FIG. 4 illustrates a box separated into box halves where each half includes a plastic liner; and,
FIG. 5 illustrates a cross section of the box halves mutually engaged.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a perspective view of a box apparatus system 10 for disposing of animal excrement including a female box half 12 and a male box half 14. The female box half 12 includes a side 16, a side 18, a side 20 opposing side 18, an end 22 which snaps and locks into place as later described in detail, a side 24 opposing the side 16, an open end 26, and a handle 28 affixed to side 16. The male box half 14 is slightly smaller than the female box half 12 to be accommodated by the female box half 12 for a pressure fit, and includes a side 30, a side 32, a side 34, a side 38, an end 36 similar to end 22 which snaps and locks into place, and an open end 40. Sides 32 and 34 include triangular scoring line creases 42 and 44 as later described in detail.
The box may be fabricated from paper board stock with an interior which has been layered with a water impermeable plastic. A typical thickness of the board stock is 0.020 inches by way of example. Both the male 14 and the female 12 box halves are constructed with ends 36 and 22, respectively, that snap and lock into place when the flat sides 16, 18, 20, 24 and 30, 32, 34, and 38 are folded open, as also illustrated in FIG. 2. The female box half 12 is designed with a carrying handle 28 to provide convenient transportation when the final receptacle is formed around the feces.
The width and height of the male box half 14 is slightly less than the width and height of the female box half 12 so that the male box half 14 can be slipped inside, thereby enveloping the feces. Furthermore, the sides of the male box half 14 are creased, aiding the insertion of the male box half 14 into the female box half 12. A pressure fit holds the two box halves 12 and 14 together to provide a sealed container.
In accordance with the present invention, the box 10 may be formed from various materials. The box 10 could be formed from cardboard, layered with moisture-impermeable plastic so it forms a moisture barrier inside the box. Such plastic materials would include, but not be limited to, polyethylene, polypropylene, polyvinylidene chloride or polyvinylchloride. If only short term moisture-impermeability is desired, then the plastic layer may be omitted.
In accordance with the present invention, the box 10 may be formed from cardboard which has been coated with moisture-releasable substances, including odorants to mask the feces odor, and disinfectants to kill microorganisms that cause feces odor. The entrapped substances are held in a water-soluble polymer until the polymer is dissolved by the feces moisture, thus causing their release.
Any number of odor masks could be used. These would include pine or citrus scents, or any other number of commercial odorants.
Water soluble polymers that are useable in the coating process would include gum arabic, cellulose derivatives such as methyl hydroxypropylcellulose and carboxymethylcellulose, maltodextrins, carrageenan, certain proteins such as zein, casein or gelatin and synthetic polymers such as polyethylene glycol and polyvinyl alcohol.
Disinfectants that are useable in this process would include glutaraldehyde, GIV Guard DXN™, and quaternary ammonium salts. Different water-soluble polymers and anti-microbial agents can also be utilized.
The coating is put on the box material by depositing a dispersion/solution of the active ingredient in a carrier liquid such as water. This aqueous dispersion solution is deposited onto the box material with a spray, roller or other device. A preferred means of depositing the dispersion solution is with a rotograveur cylinder on a printing press. The carrier solvent (water) is dried, leaving an active surface of disinfectant and odorant entrapped in the water-soluble polymer. The box is formed with this active surface as the interior. A typical coating is set forth below in Table 1 in a preferred column, while Table 2 illustrates a column of ranges.
TABLE 1______________________________________Typical Coating Emulsion FormulaPreferred Percentage Weight by Percent______________________________________Water 52%Benzalkonium Chloride 5%Odorant 5%Water Soluble Polymer 35%Surfactant (Triton-x100) 3%______________________________________
TABLE 2______________________________________Typical Coating Emulsion FormulaPercentage Ranges Weiqht by Percent______________________________________Water 52%Benzalkonium Chloride 2-15%Odorant 2-15%Water Soluble Polymer 0-35%Surfactant (Triton-x100) 0.3-5%______________________________________
A surfactant may be selected from a vast array of materials including aryl and alkyl sulfonates, Surfynols™, polyethylene and polypropylene oxide, fluorinated alkyl quaternary ammonium salts or other amine derivatives.
FIG. 2 illustrates the end 22, a semi-erected female half 12, taken along aspect line 2--2 of FIG. 1 which is similar to the male box half end 36 of FIG. 1 where all numerals correspond to those elements previously described. End 36 is not described for purposes of brevity, and operates in a like mode of operation. Sides 16, 18, 20 and 24 each have tabs extending across the bottom area which ultimately unfold from a flat box half to engage with one another to form a planar box bottom 22 as illustrated and also described in FIG. 3. Sides 18 and 20 include triangular flaps 50 and 52, respectively. Sides 16 and 24 each have mirror-like flaps 54 and 56 including lock tabs 58 and 60, respectively, and quadrilateral portions 62 and 64. The quadrilateral portion 62 glues or otherwise affixes over the triangular flap 50 of the side 18, and the quadrilateral portion 64 likewise glues or otherwise affixes over the triangular flap 52 of the side 20. As the box sides are unfolded to form right angles with each other, triangular tabs 50 and 52 affixed to quadrilateral portions 62 and 64 actuate tabs 54 and 56 outwardly towards the plane of the end 2 and bending tabs 54 and 56 along crease lines 66 and 8 towards the plane of the end 22 thereby systematically engaging lock tabs 58 and 60 with each other to form a configuration as illustrated in FIG. 3.
FIG. 3 illustrates an end view of the fully erected box end 22 of FIG. 2 where all numerals correspond to those elements previously described. This loop end is like that of end 36 which is not described for purposes of brevity. The box end 22 is fully formed with lock tabs 58 and 56 engaged with one another after systematic deployment and engagement of the lock tabs by the action of manually erecting the respective box halves from a flat and folded position. End 36 of the male box half 14 is configured and operates in a manner similar to that shown for the female box end 22.
MODE OF OPERATION
The female and male box halves 12 and 14 of the box 10 are transported flat by the user. Prior to use, these sections are opened to form a male box half 14 which is pushed into the female box half 12, enveloping the feces therebetween in the formed box 10. A handle 28 is part of the box design, and is used to transport the feces to the final deposition. The male box half 14 is scored along lines 42 and 44 so that it can be slightly depressed to decrease the box cross section profile, thus facilitating insertion into the female box half 12.
FIG. 4 illustrates an alternative embodiment of an apparatus 70 including the female box half 12 and a male box half 14, each including a plastic liner bag glued or otherwise affixed to the interior or each of the box halves 12 and 14. Operation of the box halves 12 and 14 is identical to that previously described.
The outer edge opening perimeter 72 of a plastic liner bag 74 is glued, cemented or otherwise affixed to the inner planar perimeter portion 76, bound by the box edge and dashed line, of the box 12. The outer edge perimeter 78 of another plastic liner bag 80 is similarly attached to the inner planar perimeter portion 82 of the box 14, bound by the box edge and a dashed line, as illustrated with a dashed line. Plastic liner bags 74 and 80, each being affixed to the box inner perimeters at the bag liner opening perimeter, are afforded unrestricted movement within the interior of each box 12 and 14 prior to encapsulation of feces within the plastic bag liners 74 and 80 of box halves 12 and 14. When the box halves 12 and 14, containing plastic bag liners 74 and 80, are mutually accommodated, the feces is effectively double barrier sealed between layers of treated box material and layers of plastic liner material. Engaged box halves 12 and 14 are illustrated in FIG. 5.
FIG. 5 illustrates a cross section of the box halves 12 and 14 mutually and frictionally engaged and forming a double sealed apparatus 70 for the encapsulation and disposal of feces. Frictional engagement of the male box half 14 and the plastic liner bag 80 within the female box half 12 and the plastic liner bag 74 ensures a double barrier seal consisting of at least a treated box side or end and an enclosed plastic bag member in the area of the box half ends 22 and 36, and a quadruple barrier in the areas where the box sides and bags slide over each other such as the overlapping of box side 16 and plastic liner bag 74 of box 12 with box side 30 and plastic liner bag 80 of box 14. Also shown in this illustration are the areas 76 and 82 where the plastic liner bag perimeter is affixed to the box inner perimeter areas. The double sealed apparatus 70 thus forms a well sealed container offering double or quadruple odor, solid and liquid sealant protection.
Various modifications can be made to the present invention without departing from the apparent scope thereof.
Odorant only may be applied to the box if appropriate packaging is used to protect against odorant loss in distribution. | Method and apparatus for disposing of animal feces including a two piece box which folds out from a collapsible flat shape. The interior of this box is layered with a moisture impermeable material which is coated with a water soluble mixture. The water soluble mixture contains an aroma and a disinfectant, so when the surface comes into contact with moist feces, the aroma and disinfectant are released. The released aroma masks the feces odor, and the released disinfectant decreases microbiological growth, making the transportation and storage of the feces more acceptable until final disposal, burial or incineration. An alternative apparatus features an interior plastic bag linear for each of the box halves. | 8 |
[0001] This invention is entitled to the priority of U.S. provisional application Serial No. 60/261,851 filed Jan. 15, 2001, and is a division of Ser. No. 10/047,644, filed Jan. 15, 2002, now U.S. Pat. No. 6,718,963. The invention relates to archery bows and more particularly to compound archery bows utilizing separable limb and riser components.
BACKGROUND OF THE INVENTION
[0002] One of the problems with achieving accuracy has been the recoil vibration occurring as the arrow is released from the bow, which has resulted also in undue noise which startles the game. Another factor affecting accuracy is the alignment of the bow string which in the past has not provided the balance desired. To the best of my knowledge, the arrow released by prior art compound bows has not been vertically centered with the result that the torque and flex stresses on the bow upper and lower limbs has not been balanced, and accuracy has been sacrificed as a result. Moreover, the bow string has not been centered in the sense of vertical upper and lower pulley alignment and in the sense of vertical bisection of the handle.
[0003] Typical archery bows of the type presently utilized are disclosed in U.S. Pat. No. 5,975,067 issued Nov. 21, 1999, U.S. Pat. No. 6,035,841 issued Mar. 14, 2000, U.S. Pat. No. 6,082,346 issued Jul. 4, 2000, and U.S. Pat. No. 5,749,351 issued May 12, 1998 wherein the compound bow utilizes eccentric pulleys on the outer ends of the limbs to facilitate the draw and the arrow release. The present invention is directed to bows of this general character.
SUMMARY OF THE INVENTION
[0004] The present invention, in one aspect thereof, is concerned with the manner of mounting the resilient limbs to the handle riser as well as to the vertically centered alignment of the pulleys mounting the bow string along with the handle, and the positioning of the bow rest to achieve a vertically centered arrow relationship. This permits the archer to utilize a better balanced bow which is more accurate. Because of the balanced relationship achieved, the archer is presented with less torqueing stresses in the bow and less vibration is transferred via the bow limbs upon limb recoil and arrow release. Moreover, the positioning of the arrow in vertically centered position provides equal torque and flex forces on the limbs to generate more stored energy as the bow string is drawn. Another aspect of the invention is the provision of eccentric pulley assemblies which aid in achieving these desired characteristics.
[0005] A further object of the invention is to provide a limb mounting system which results in material vibration reduction and accordingly much less noise generation in the release of the arrow. This is accomplished by securing the limb inner ends to the handle riser ends by means of a novel vibration damping assembly. A limb bolt extends into a threaded vibration damping member carried by the riser at each end and a limb cup, constructed of anti-vibration material, is snugly utilized between the seat and the sides and inner end, as well as the bottom, of each limb. The installed cushioning limb cup restricts the limb from shifting laterally, and forwardly or inwardly, while permitting the limbs to flex or unflex when the archer adjusts the attachment bolt to his desired draw requirements and thereby controls the energy which will be stored in the deflected resilient limbs when the bow string is drawn.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] In the drawings:
[0007] [0007]FIG. 1 is a side elevational view of a relaxed compound single-cam archery bow utilizing the present inventive concepts;
[0008] [0008]FIG. 2 is a rear elevational view of a dual cam bow with the tensioning cable system omitted, illustrating various components of the bow shown in FIG. 1;
[0009] [0009]FIG. 3 is an enlarged fragmentary rear elevational view illustrating the relationship of the handle and bow string in more detail;
[0010] [0010]FIG. 4 is an enlarged perspective view of the handle illustrating the handle recess which mounts on the riser in a manner to provide the top to bottom centering of the bow string;
[0011] [0011]FIG. 5 is a somewhat enlarged side elevational view of the limb and riser assembly only;
[0012] [0012]FIG. 6 is an exploded view thereof on a slightly enlarged scale showing the various component parts thereof;
[0013] [0013]FIG. 7 is a similar exploded view on a more enlarged scale showing the parts at the inner end of the lower limb;
[0014] [0014]FIG. 7A is a perspective plan view showing the limb end received in the limb cup and limb seat;
[0015] [0015]FIG. 8 is a perspective elevational view of the limb pocket component on an enlarged scale;
[0016] [0016]FIG. 9 is an enlarged perspective view of the limb cup which fits in the limb pocket;
[0017] [0017]FIG. 9A is an exploded perspective plan view illustrating an alternative limb cup structure;
[0018] [0018]FIG. 10 is an enlarged perspective view of one of the identical limbs;
[0019] [0019]FIG. 10A is a perspective plan view of an alternative limb;
[0020] [0020]FIG. 11 is an enlarged perspective, exploded view of the limb bolt bushing assembly; and
[0021] [0021]FIG. 11A is a similar view disclosing an alternative embodiment;
[0022] [0022]FIG. 12 is a rear elevational view of a bow employing eccentric cam assemblies at each of its upper and lower ends;
[0023] [0023]FIG. 13 is an enlarged view of the upper end of the bow shown in FIG. 12;
[0024] [0024]FIG. 14 is an enlarged view of the lower end of the bow shown in FIG. 12;
[0025] [0025]FIG. 15 is a considerably enlarged view of eccentric pulley assembly which may be used at both ends of the bow;
[0026] [0026]FIG. 16 is an enlarged perspective view of the eccentric pulley assembly only; and
[0027] [0027]FIG. 17 is an edge elevational view of a base cam/power cam eccentric pulley assembly.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] Referring more particularly to the accompanying drawings, and in the first instance to FIG. 1 thereof, the bow assembly comprises generally upper and lower resilient limbs generally designated 10 and 11 joined in the manner to be disclosed to a rigid riser, generally designated 12 , which can be fashioned of aluminum or other suitable material. Revolvable mechanical advantage creating pulley members 13 and 14 are mounted laterally centrally at the outer ends of the limbs 10 and 11 . The members 13 and 14 may comprise regular idler pulleys or eccentric pulleys and in FIG. 1 a regular pulley is shown at 13 and an eccentric pulley at 14 . They operate in the usual manner to mount the bow string 15 shown in FIG. 1, which in the embodiment shown is part of the conventional tension cable system generally designated TC which extends between the opposite ends of the bow in the usual manner. The cables TC- 1 and TC- 2 of the conventional cable system, pass through spaced apart openings in a cable guard rod r which holds the cables laterally apart and displaced sufficiently from arrow 16 to avoid feather damage. Here the cable TC- 1 , which provides the bow string portion 15 , passes around pulley 13 and pulley 14 and secures at both ends to eccentric pulley 14 . Cable TC- 2 is shown as connected to limb 10 at one end and to the pulley 14 at the other. In FIG. 2, a conventional eccentric pulley is used in the upper end of the bow at 13 a and on the lower end of the bow at 14 . It will be noted that the arrow 16 is vertically centered with respect to the axes of axles 18 and 19 on which the pulleys 13 or 13 a and 14 are mounted for rotation. This tends to prevent the bow from tilting vertically on the draw.
[0029] As FIG. 3 further indicates, the pulleys 13 or 13 a and 14 are so aligned vertically, and the handle 12 a is so mounted on the riser 12 , that the string 15 vertically bisects the bow handle 12 a in a front to rear direction. While the bow string 15 is offset with respect to the mid-portion of the riser, it is substantially centered with respect to the handle 12 a , as FIG. 3 particularly indicates. This is possible because the vertical mounting recess 12 b (FIG. 7), in the handle 12 a is centrally offset in the handle to define narrow riser embracing leg 12 g and wider embracing leg 17 h. Handle leg 12 h fits within the recess 12 c provided in the one side face of the riser 12 . Cap screw openings x in the handle and riser, for accommodating a fastener such as a screw, align. Plainly this centering of the bow string 15 with respect to the handle 12 a, and consequent centering of the string and arrow 16 with respect to the handle 12 a , can be accomplished alternatively by offsetting the mounting portion of the riser sufficiently that the bow string 15 bisects a handle 12 a mounted non-eccentrically on the riser 12 . The riser 12 , as usual, has a number of weight reduction openings and an arrow rest surface 12 d which is equidistant from the axes of each pulley 13 or 13 a and 14 and aligns substantially with the vertical center of the bow string 15 .
[0030] Another important aspect of the present invention is the anti-vibration mounting of the limbs 10 and 11 to the riser as disclosed particularly in FIGS. 6-11. It will be observed that each of the composite material limbs 10 and 11 , which are identical, include outer end bifurcation slots 20 within which the inner portions of the pulleys may be rotatably received, and bores 21 for receiving and securing the pulley axle pins 18 and 19 . While a mediate slot 22 is provided in each of the limbs in FIG. 10 to increase flexing capability it will be noted that the slot 22 does not extend the full length of the limbs 10 or 11 and, rather, torsion restricting portions 23 are provided at each end of the slot 22 , as shown. The inner ends of the limbs 10 and 11 are similarly bifurcated as at 24 (FIG. 7) for a purpose to be presently described. An alternative limb 10 or 11 , using like numerals to designate the respective parts, is shown in FIG. 10A.
[0031] Bolted to the ends of the riser 12 , as with bolts 25 , are metallic (preferably aluminum) limb seats or pockets generally designated 26 (FIG. 8) having spaced openings 27 in their recessed bottom walls 26 a to accommodate the bolts 25 securing the seats 26 to the riser 12 ends. As indicated, the bottom surfaces of seat walls 26 a have recesses 26 b (FIG. 7) to receive the protrusion or key portions 12 f provided on the risers 12 to fit snugly therein. It will be noted that the limb seats or pockets 26 are of an elongate nature and have side walls (see FIG. 6) 28 joined by a generally curvilinear inner end wall 29 . The opposite end of each limb seat 26 is open as shown. An elongate opening 30 is also provided in the bottom wall 26 a of the limb seat to pass a limb attaching metallic (preferably steel) fastener assembly or bolt 31 (FIG. 7) in a manner to be presently described.
[0032] Provided to seat snugly within the limb seat 26 is a preferably molded, vibration damping limb receptor cup generally designated 32 (FIG. 9) which has similar side walls 33 joined by a similar generally curvilinear end wall 34 . Each limb cup 32 includes a bottom wall 32 a with an elongate opening 35 therein aligning with seat opening 30 to also pass the attachment bolt 31 . At its opposite end, the limb cup 32 is open to pass the inner end of the limb and mounts a pair of limb locator bosses 36 , as shown, which are received within the spaced apart blind openings 37 (FIG. 10) provided in the bottom surfaces of limbs 10 and 11 . The same bosses are provided, but not shown, in FIG. 10A. The walls 33 and 34 of each limb cup are snugly received within and braced by the walls 28 and 29 of the limb seat component 26 with a perimetral clearance of only about 0.005 of an inch. Provided on the limb cups 32 near their outer ends are curvilinear rockers 38 which are received in the curvilinear receiving recesses 39 provided in the seats 26 . In addition to permitting some adjustment pivoting when the bolt 31 is adjusted to tension the limbs 10 and 11 to adjust the weight of the bow, they also serve as locator mechanism. It is to be understood that the limb cups 32 are formed of a polyurethane or other suitable resilient synthetic plastic material having a durometer which typically may be 60. The particular durometers mentioned in this application are not to be considered as in any way limiting and other durometers will prove useful so long as they provide the anti-vibration characteristics. A durometer range for the cups 32 is believed to be 30-90. The limbs 10 and 11 are preferably constructed in the usual manner of a composite material such as fiberglass or graphite with embedded fibers which may typically be glass or carbon to provide the requisite strength. The cups 32 need not be completely formed of the same material. In FIG. 9A an improved alternative is disclosed wherein the bosses 36 and rocker 38 are unitarily molded of a harder material such as “delrin plastic”. The term Delrin is a trademark owned by E.I. du Pont de Nemours and Co. Inc. for its acetal homopolymer plastics which are mechanically strong while also having resilience. In this version, the upper wall of the rocker is flat as at 38 a to lie in the same plane as the outer limb receiving surface of the bottom wall when the bosses 36 are inserted up through the opening 38 b and the rocker 38 is secured in opening 38 b adhesively, or in any other suitable manner. Another alternative is to cut away part of the cup bottom wall 32 a as at 32 c to receive an insert plate 32 d of material having a lower durometer than wall 32 a . This lower durometer is in the range 10-30 and preferably about 20.
[0033] As shown in FIG. 7, the bolt 31 is part of a fastener assembly which includes an aluminum washer 40 and the polyurethane anti-vibration washer 42 , typically having a durometer rating in the 50-60 area. The bolt 31 extends through the slotted opening 24 in the inner end of limb 10 or 11 , through slotted opening 35 in the limb cup 32 and 30 in the limb seat 26 and through a slot 12 s in riser 12 into a polyurethane or similar bushing generally designated 43 having a bolt receiving bore 44 provided therein. Bushings 43 seat snugly within bores 12 e provided in each end of the riser 12 inboard of each seat 26 . Provided embedded within the bushing 43 is a preferably stainless steel cylinder 45 (FIG. 11) having a threaded bolt receiving bore 46 aligning with bore 44 . End caps 47 and 48 of greater external diameter than the bushing opening 12 e (FIG. 7) are received on the reduced ends 43 a of the bushing 43 . The end caps 47 and 48 are preferably adhesively secured to the bushing ends 43 a and bear against the marginal surface of the riser surrounding the opening 12 e in which the bushing 43 is received. The durometer of the molded sleeve member 43 with reduced ends 48 may typically be in the area of 70-90. The end cap 47-48 durometer is preferably in the range 30-50. The purpose of the polyurethane sleeve bushing 43 is to dampen recoil vibration transmitted by the attachment bolt 31 and to resist forces tending to twist the handle 12 a . The bushing 43 and cylinder 45 also resist outward pull of the bolt 31 . The provision of the cups 32 , which cushion or absorb the recoil of the limbs 10 and 11 , prevents much of the recoil vibration from reaching the limb seats 26 and, in addition to preventing torsional forces from reaching the riser and handle, also damps vibration resulting from the flexing of the bow limbs 10 and 11 .
[0034] In FIG. 11A an improved alternative embodiment is disclosed in which bushing 43 is eliminated and cylinder 45 is formed of “Delrin” plastic as a damping body. The ends of cylinder 45 are closed as at 50 except for openings 51 . The openings 51 receive projections 52 extending from cap 47 and cap 48 which may have a durometer rating in the 15-25 range. The noise reducing caps 47 and 48 are preferably adhesively secured to cylinder 45 .
[0035] Referring now more particularly to FIGS. 12-16 a three cable draw and tensioning system is disclosed wherein novel eccentric cam pulleys are utilized at both ends of the bow. It is to be understood that one of the eccentric pulleys could be replaced by an idler pulley in another modification of the system depicted in these figures. The base cam/power cam device disclosed in U.S. Pat. No. 5,975,067, which I incorporate herein by reference, could be employed as the eccentric pulleys, with the distinction that the base cam and the power cam, which in the patent are continuous, are separated by a shouldered portion which disposes the track in the power cam at a spaced axial distance from the track in the base cam so that the tracks are no longer side by side. The importance of this distinction and the function it achieves will be discussed subsequently. Alternatively, cams of the general nature of those disclosed in U.S. Pat. No. 5,975,067 which include the shouldered portions but not all of the features claimed may be employed.
[0036] Turning now more particularly to FIGS. 12-14, where like numerals to designate previous components have been employed, the three cable system used, as illustrated in the drawings, consists of the draw string or draw cable 15 , the power cable 54 which has a yoke connection 55 to the ends of the lower axle pin 19 as shown particularly in FIG. 14, and let out/take up cable 56 which has a yoke connection 57 to both ends of the axle pin 18 at the upper end of the bow.
[0037] The base cam/power cam assembly generally designated 58 is used at the lower end of the bow and a like base cam/power cam assembly 59 is used at the upper end of the bow. In both instances, the base cam/power cam assembly includes the partially elliptical base cam 59 having a pulley track 59 a for reception of the draw cable 15 and a power cam 60 having a pulley track 60 a for reception of one of the cables 54 or 56 . The upper eccentric mounts the cable 54 , the terminal lower end of the cable 54 a attaching to a post 61 projecting laterally from the base cam 59 , as shown particularly in FIG. 15. The upper base cam/power cam assembly mounts the terminal end of the cable 15 on its post 62 projecting laterally from base cam 59 . The lower end base cam/power cam assembly 59 mounts the cable 56 on its attachment projection 61 and the cable 56 has a yoke connection to both ends of the upper axle pin 18 .
[0038] In FIGS. 15-17, the power cam 60 is shown as including an end 60 y abutting a post 60 b on base cam 59 and an end 60 c which embraces a tubular post 60 d on base cam 59 which is journaled on the pulley pin 18 . As previously, the base cam 59 b and power cam 60 rotate in unison on the pin 18 . The upper terminal end 15 a of draw cable 15 has a yoke connection 15 a to a post 62 fixed on the opposite face of the base cam 59 b and the lower terminal end has a similar connection to the base cam 59 b of the lower eccentric assembly 58 . Both the base cam 59 and the power cam 60 are fixed to one another to move eccentrically about the pivot post 18 at the upper end of the bow, or 19 at the lower end of the bow. Where previously the base cam 59 and the power cam 60 have been side by side or adjacent to one another, they now are separated by a shoulder or axial projection 63 fixed on the base cam pulley 59 . This projection 63 which extends clockwisely from y to z substantially around power cam 60 in FIG. 16 reduces twisting forces and assures that the base cam/power cam assemblies will lie in vertical alignment. The projection 63 is not necessarily clockwisely continuous and may be sectionalized. Generally speaking, the axial projection of the shoulders 63 will be in the neighborhood of 0.5 to 1.25 inches around a substantive portion of the extent of the power cam 60 . In the lower part of the range, one of the shoulders 63 on the upper and lower eccentric pulleys will normally be at least sufficiently different in projection extent to best maintain cable separation. In the right hand bow depicted the projection 63 at the lower end of the bow will be the longer projection. In a left hander's bow, this will be reversed. When a sufficiently long shoulder projection in the neighborhood of 0.75 to 1.25 inches is provided, the cable guard rod r shown in FIG. 1 can be eliminated because the projections 63 on the eccentric pulley assemblies 58 and 59 hold the cables 56 and 54 sufficiently apart so that they do not touch one another or imperil the arrow feathers when the arrow is released. In the embodiment where an idler pulley is used in place of the upper eccentric, a hub part, of selected axial projection inwardly, may be used to locate the idler pulley track in vertical alignment with the lower eccentric base cam track.
The Operation
[0039] When the draw weight of the bow is adjusted via bolts 31 , the limbs 10 and 11 are free to flex or unflex with respect to bolts 31 slightly because of the slots 24 , 30 , 35 , and 12 s . The inner ends of limbs 10 and 11 are restricted resiliently by walls 34 from all but very limited, flexural movement inwardly. In operation, as the bow string 15 is pulled rearwardly to its position of maximum weight at mid-draw against the resistance of cable system TC, the limbs 10 and 11 will flex or curve in the usual manner and the cups or liners 33 will cushion the return from deflection when the arrow is released and the limbs 10 and 11 recoil. With the cups 32 constructed of a semi-rigid resilient anti-vibration material, the transfer of stresses to the limb seats or pockets and riser is dampened because the upstanding walls of the cups 32 are snugly received by the upstanding walls of the metallic limb seats and limb recoil vibration and noise is isolated. Any tendency of the limb cups 32 to rotate and impose torsional forces is also reduced and dampened because the walls 33 are snugly in engagement with the walls 28 , and walls 29 are snugly in engagement with the walls 34 . The limbs 10 and 11 are not of a thickness to project above the cup walls 33 and 34 . The provision of the washers 42 and the bushings 43 or the synthetic plastic vibration damping cylinder 45 with anti-vibration end caps 47 - 48 further damps the vibration which occurs at the moment of arrow release. The fact that the bow string 15 is in vertically centered relationship results in less torsional force being imposed on the limbs 10 and 11 and the centering of the arrow top to bottom provides greater accuracy in the shot.
Method of Construction
[0040] In constructing the bow, a normal first step is to secure the bow seats 26 to the opposite ends of the riser 12 by means of bolts 25 , with the riser surfaces 12 f fitting within the bottom recesses 26 b in cups 26 and the openings 12 s and 30 in alignment. Next the limb cups 32 are snugly fitted within the limb seats 26 , and the limbs 10 and 11 are inserted with the slots 24 in alignment with the limb cup openings 35 which are aligned with the pocket openings 30 . The anti-vibration members 43 are next inserted in the openings 12 e with the openings 44 and 46 aligned with openings 12 s , and caps 47 and 48 are then adhesively secured in position on opposite sides of the riser 12 . With the metallic washer 40 and the anti-vibration washer 42 in place on the bolts 31 , each bolt 31 is extended through the slotted openings 24 , 35 , 30 and 12 s into the bushing opening 34 and threaded into threaded opening 46 . Then, the handle 12 a, cable guard rod r, pulleys and axles, and the string and tension cable system TC may be installed in the usual manner.
[0041] The disclosed embodiment is representative of a presently preferred form of the invention, but is intended to be illustrative rather than definitive thereof. The invention is defined in the claims. | A compound archery bow with a handle-providing rigid riser and flexible limbs on the riser mounting bow string pulleys has damping interconnection mechanism between the limbs and riser. A damper is carried by each riser inboard of a riser limb seat. A resilient limb cup for each limb seat has portions for engaging the bottom, side walls and inner end wall of a limb and a fastener extends from each limb through each limb cup and limb seat to secure the limb to the damper. | 8 |
This application is a continuation of application Ser. No. 044,532 filed May 1, 1987, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a golf club, more particularly, to an improvement of a putter club (hereinafter, putter).
2. Description of the Related Arts
Japanese Examined Utility Model Publication No. 59-12916 discloses a putter having a head which comprises a rod-like body having a longitudinal axis. The rod-like body is provided at one end thereof with a thin face plate, for defining thereon a hitting surface for hitting a golf ball, extending in a direction perpendicular to the longitudinal axis of the rod-like body. The rod-like body is provided at the upper portion thereof with a shaft fixed thereto.
In the above-mentioned conventional putter, the distribution of weight of the head is concentrated substantially at the center axis of the hitting surface, and thus the hitting surface of the head has only a small sweet spot area. Accordingly, the above-mentioned conventional putter has a disadvantage in that when the golf ball is hit, the point of impact between the head and the ball is apt to be outside the sweet spot area of the head. This is particularly disadvantageous for a long put, since the distance run by the ball when hit by the head outside the sweet spot area becomes extremely short and the direction of run of the ball deviates greatly from a target line. Further, the head is apt to rotate about a center axis of the portion connecting the shaft to the rod-like body during a swing of the golf club, and thus it is difficult to keep the hitting surface of the head orientated on a target.
SUMMARY OF THE INVENTION
Therefore, according to the present invention, there is provided a golf club having a head and a shaft, the head comprising: a face plate having a hitting surface extending between opposite toe and heel sides of the head and a back surface extending substantially in parallel to the hitting surface; a pair of spaced rod-like bodies fixed to the back surface of the face plate at the toe and heel sides of the head, respectively, and extending backward and in a direction perpendicular to the hitting surface of the face plate; and a shaft-mounting body, for mounting the shaft thereon, fixedly disposed between the rod-like bodies.
In the golf club according to the present invention, the rod bodies fixed to the face plate are disposed at the toe and heel sides of the head, so that the weight of the head is distributed to the toe and heel sides of the head, and thus a sweet spot area of the hitting surface of the face plate is extended toward the toe and heel sides of the head. Therefore, when a golf ball is hit by the head at a position deviated from the center of the sweet spot area, the distance run by the ball is not greatly decreased and the direction of run of the ball does not greatly deviate from a target line. Further, since a moment of inertia of the head about the center of gravity of the head is increased due to the provision of the rod-like bodies at the toe and heel sides of the head, it is easy to prevent a rotation of the head about a center axis of a portion connecting the shaft-mounting body to the shaft to keep the hitting surface of the face plate orientated on a target during a swing of the golf club.
BRIEF EXPLANATION OF THE DRAWINGS
The foregoing and other features and advantages of the present invention will be better understood from the following description with reference to the preferred embodiments illustrated in the drawings; wherein
FIG. 1 is a perspective view of a head and a part of a shaft of a putter illustrating a first embodiment of the present invention;
FIG. 2 is a plan view of the head and the part of the shaft shown in FIG. 1;
FIG. 3 is a perspective view of a head and a part of a shaft of a putter illustrating a second embodiment of the present invention;
FIG. 4 is a plan view of the head and the part of the shaft shown in FIG. 3;
FIG. 5 is a perspective view of a head and a part of a shaft of a putter illustrating a third embodiment of the present invention;
FIG. 6 is a plan view of the head and the part of the shaft shown in FIG. 5;
FIG. 7 is a perspective view of a head and a part of a shaft of a putter illustrating fourth embodiment of the present invention; and
FIG. 8 is a plan view of the head and the part of the shaft shown in FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 illustrate a first embodiment of the present invention. Referring to these Figures, a golf club, i.e., a putter, comprises a head 10 and a shaft 16 having at the tip end thereof a rod-like hosel portion 15 fixed thereto. In this embodiment, the hosel portion 15 has substantially a crank-like shape. The head 10 comprises a thin face plate 11 having a hitting surface 11a extending between toe and heel sides of the head 10 and a back surface 11b extending substantially in parallel to the hitting surface 11a. A pair of spaced rod-like bodies 12 and 13, each having a substantially cylindrical outer surface, are fixed to the back surface 11b of the face plate 11 at the toe and heel sides of the head 10 and extend backward and in a direction perpendicular to the hitting surface 11a of the face plate 11. A rod-like shaft-mounting body 14 having a length shorter than those of the rod-like bodies 12 and 13 is fixedly disposed between the rod-like bodies 12 and 13. The shaft-mounting body 14 is fixed at the top surface thereof to the hosel portion 15 of the shaft 16.
The face plate 11 is formed at the top surface thereof with a pilot line 11c extending between the toe and heel sides of the head 10 in parallel to the hitting surface 11a, and the rod-like bodies 12 and 13 are formed at the top surfaces thereof with other pilot lines 12a and 13a, respectively, extending in a direction perpendicular to the hitting surface 11a of the face plate 11. Further, in this embodiment, the shaft-mounting body 14 is formed at the top surface thereof with another pilot line 14a extending in a direction perpendicular to the hitting surface 11a of the face plate 11. The pilot line 14a is formed so that the center of the hitting surface 11a of the face plate 11, i.e., the center of a sweet spot area, is located on the extension of the pilot line 14a.
In this embodiment, the shaft-mounting body 14 is fixedly connected to the rod-like bodies 12 and 13, and spaced from the back surface 11b of the face plate 11 to form a clearance therebetween. Preferably, the rod-like bodies 12 and 13 and the shaft-mounting body 14 are produced as one body by monoblock molding, to reduce the number of steps of the manufacturing process. The rod-like bodies 12 and 13 may be fixed to the face plate 11 by welding or screws (not shown). The rod-like bodies 12 and 13 and the shaft-mounting body 14 may be made of metal, such as Al (aluminum), Bs (brass) or Fe (ferrite), or plastic, or ceramic, and the face 11 may be made of the same material as those of the rod-like bodies 12 and 13 and the shaft-mounting body 14, or of transparent plastic.
In the putter having the above-mentioned construction, the rod-like bodies 12 and 13 fixed to the face plate 11 are disposed at the toe and heel sides of the head 10, so the weight of the head is distributed to the toe and heel sides of the head 10, and thus the sweet spot area of the hitting surface 11a of the face plate 11 is extended toward the toe and heel sides of the head 10. Therefore, when a golf ball is hit by the head 10 at a position deviated from the center of the sweet spot area of the head 10, a distance run by the ball is not greatly decreased and a direction of run of the ball does not greatly deviate from a target line. Further, since the moment of inertia of the head 10 about the center of gravity of the head 10 is increased due to the provision of the rod-like bodies 12 and 13 at the toe and heel sides of the head 10, it is easy to prevent rotation of the head 10 about a center axis of a connecting portion of the shaft-mounting body 14 with the hosel portion 15 of the shaft 16, to keep the hitting surface 11a of the face plate 11 orientated on a target during a swing of the golf club.
Furthermore, since the rod-like bodies 12 and 13 extending in a direction perpendicular to the hitting surface 11a of the face plate 11 are disposed at the toe and heel sides of the head 10, it is easy, when addressing the ball, to accurately orientate the hitting surface 11a of the face plate 11 on the target. In particular, the pilot lines 12a and 13a on the rod-like bodies 12 and 13 can serve, when addressing the ball, to provide a much better orientation of the hitting surface 11a.
FIGS. 3 and 4 illustrate a second embodiment of the present invention. In these Figures, constituent elements of the putter corresponding or similar to those of the first embodiment are denoted by the same reference numerals as those used in FIGS. 1 and 2, respectively.
Referring to FIGS. 3 and 4, the shaft-mounting body 14 fixed to the pair of rod-like bodies 12 and 13 is also fixed to the back surface 11b of the face plate, and has a length shorter than those of, the rod-like bodies 12 and 13, but greater than that of the shaft-mounting body 14 in the first embodiment. The rest of the construction of the putter in the second embodiment is the same as that of the first embodiment, and the constituent elements in the second embodiment can be made of the same materials as those of the corresponding constituent elements in the first embodiment, respectively, and in the same manner as that of the first embodiment described above.
The construction of the putter according to the second embodiment has an advantage in that a distance run by a ball hit by the head 10 at the central portion of the hitting surface 11a of the face plate 11 is further increased, compared to that obtained by the putter of the first embodiment, due to the provision of the shaft-mounting body 13 fixed to the face plate 11.
FIGS. 5 and 6 illustrate a third embodiment of the present invention. In these Figures, constituent elements of the putter correponding or similar to those of the first embodiment are denoted by the same reference numerals as those used in FIGS. 1 and 2, respectively.
Referring to FIGS. 5 and 6, the shaft-mounting body 14 fixed to the pair of rod-like bodies 12 and 13 is also fixed to the back surface 11b of the face plate 11, as in the second embodiment, but has a length greater than those of the rod-like bodies 12 and 13. The shaft-mounting body 14 in the third embodiment has therein a cylindrical cavity 14b extending in the longitudinal direction thereof to decrease the weight of the shaft-mounting body 14 and distribute the weight of the head 10 to the toe and heel sides of the head 10. The rest of the construction of the putter in the third embodiment is the same as that of the first and second embodiments, and the constituent elements in the third embodiment can be made of the same materials as those of the corresponding constituent elements in the first and second embodiments, respectively, and in the same manner as that of the first embodiment described above.
The shaft-mounting body 14 may be made of a material having a specific gravity less than those of the rod-like bodies 12 and 13, instead of forming a cavity therein.
FIGS. 7 and 8 illustrate a fourth embodiment of the present invention. In these Figures, constituent elements of the putter corresponding or similar to those of the first embodiment are denoted by the same reference numerals as those used in FIGS. 1 and 2, respectively.
Referring to FIGS. 7 and 8, the shaft-mounting body 14 disposed between the pair of rod-like bodies 12 and 13 is separated from the rod-like bodies 12 and 13 and fixed to the back surface 11b of the face plate 11. The rest of the construction of the putter in the fourth embodiment is the same as that of the first and second embodiments, and the constituent elements in the fourth embodiments can be made of the same materials as those of the corresponding constituent elements in the first, second, and third embodiments, respectively, and in the same manner as that of the first embodiment described above.
In the fourth embodiment, since the shaft-mounting body 14 is separated from the rod-like bodies 12 and 13, the weight of the head 10 can be efficiently distributed to the toe and heel sides of the head 10 by reducing the size of the shaft-mounting body 14, and it is easy to increase the length of the face plate 11 between the toe and heel sides of the head 10 to dispose the rod-like bodies 12 and 13 at positions away from the center of the hitting surface 11a of the face plate 11. Accordingly, a moment of inertia of the head 10 about the center of gravity thereof can be increased compared to those of the preceding embodiments.
While particular embodiments shown in the Figures and the disclosure of the present invention have been described, it will be understood that the present invention is not limited thereto, since modification can be made by those skilled in the art in the light of the foregoing teachings. For example, each of the rod-like bodies may have a cross-section other than a circular cross-section. The hosel portion of the shaft may be formed in any shape, and the shaft may be directly connected to the shaft-mounting body. | In a golf club for putting, the head of the club comprises a face plate having a hitting surface extending between opposite toe and heel sides of the head and a back surface extending substantially in parallel to the hitting surface. A pair of spaced rod-like bodies are fixed to the back surface of the face plate at the toe and heel sides of the head, respectively, and extend backward and in a direction perpendicular to the hitting surface of the face plate. A shaft-mounting body, for mounting the shaft thereon, is fixedly disposed between the rod-like bodies. A hosel member is attached to the top surface of said shaft-mounting body substantially at a center of the head, the hosel member extends upwardly from the shaft-mounting body to a position near a plane containing the face plate and is connected to the shaft at that position. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) and the benefit of U.S. Provisional Application No. 61/243,563 entitled T-FITTING MANUFACTURING METHOD AND TOOL, filed on Sep.18, 2009, by John W. Schlabach, the entire disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to the manufacturing of copper T-fittings.
[0003] FIG. 1 shows a diagram of prior art T-fittings manufactured by a hydro-forming process utilizing generally cylindrical end punches, as seen in the prior art manufacturing equipment of FIG. 12 . The punches move toward one another and engage a copper tube to compress the copper tube to form the orthogonal T-extension. The process includes the subsequent steps of cutting the end of the extending orthogonal section and sizing all three openings of the T for final dimensioning. With prior art processes and tooling, however, a relatively large amount of copper remains in the T at a position opposite the opening of the orthogonal T, as shown by arrow C in FIG. 1 . In view of the increasing cost of copper, this material, which does not provide a useful function to the T itself, is an unnecessary cost to the final product.
[0004] There exists a need, therefore, for a T-fitting design and manufacturing process in which the unnecessary material is eliminated while still employing the hydro-forming process.
SUMMARY OF THE INVENTION
[0005] The present invention reduces the amount of copper in a T-fitting by from 10% to 12% by providing a punch for forming opposite ends of a copper tube into a T, which includes a tapered or shovel-nose such that the spacing between the ends of the opposed punches is reduced, thereby reducing the excess copper remaining in the T once formed. The invention involves both a method of forming the fitting employing the shovel-nose punches in a hydro-forming process, the shape of the punch nose to accommodate such results, and the resultant fitting.
[0006] These and other features, objects and advantages of the present invention will become apparent upon reading the following description thereof together with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a cross-sectional view of a conventional T-fitting manufactured according to the prior art;
[0008] FIG. 2 is an improved T-fitting manufactured according to the present invention utilizing the tooling of the present invention;
[0009] FIG. 3 is a left end view of the fitting shown in FIG. 2 ;
[0010] FIG. 4 is a perspective view of one of the punch noses employed for compressing opposite ends of a copper pipe to form the T-fitting shown in FIGS. 2 and 3 ;
[0011] FIG. 5 is a cross-sectional view of the punch nose;
[0012] FIG. 6 is a bottom view of the punch nose;
[0013] FIG. 7 is a front elevational view of the punch nose;
[0014] FIG. 8 is a top view of the punch nose;
[0015] FIG. 9 is a side elevational view, partly in phantom, of the punch nose;
[0016] FIG. 10 is an exploded fragmentary view taken in the circled area X in FIG. 9 ;
[0017] FIG. 11 is a right end elevational view of the punch nose; and
[0018] FIG. 12 is a schematic view of the prior art hydro-forming press.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0019] Referring initially to FIG. 1 , there is shown a conventional T-fitting 10 in which a copper tube is formed by compressing under water at high pressure (about 10,000 psi) utilizing cylindrical punch noses compressing a straight section of cylindrical copper pipe in opposite directions indicated by arrows A and B in FIGS. 1 and 2 . The result is a domed cylindrical orthogonal T-extension 14 ( FIG. 12 ) to the otherwise cylindrical pipe 12 . The enclosed end of domed extension 14 is cut in a second step, after which each of the three open ends is sized in a sizing guide to form the finished product. The cylindrical punches are inserted in the pipe in opposite directions as indicated by arrows A and B, however, resulting in a buildup of copper in the area indicated by arrow C in FIG. 1 . This extends substantially the width of the of the diameter of the T-section 14 . This buildup of copper material provides no additional strength or functional value to the T-fitting 10 and represents a waste of material.
[0020] In order to reduce the excess material in area C ( FIG. 1 ), a new fitting 20 has been devised utilizing improved punch noses shown in FIGS. 4-11 . In fitting 20 , a straight cylindrical section of copper tube 22 is again formed into a T by utilizing the shovel-nose punches 50 of the configuration shown in FIGS. 4-11 in the hydro-forming equipment of FIG. 12 instead of the standard cylindrical prior art punch noses. The process takes place in a hydro-forming machine at a high pressure of about 10,000 psi. The utilization of the shovel or tapered punches results in a much smaller buildup of copper in the area shown by arrow D in FIG. 2 , which results in a 10% to 12% copper savings for the T-fitting 20 as compared to the T-fitting 10 for a given diameter fitting.
[0021] The method of manufacturing “T” 20 involves three steps, the first step being placing a copper tube of a diameter ⅛″ to about 4″ and having a length slightly longer than the desired final length of the T in a pair of dies in a hydro-forming machine. The lower die is semi-cylindrical and an upper die has the same shape but has a cylindrical opening to allow the projection 24 of fitting 20 to extend through the top die. Punches 50 are pushed in opposite ends to force the ductile copper (which is from 95% to 99% pure) through the opening in the upper die forming an extension 14 which, after the first step, is capped with a copper dome. The partially formed T is then removed from the hydro-forming press, which can be a press that is commercially available from Schuler, such as shown in FIG. 12 , and placed in a second die, which provides an alignment slot and chisel-like knife for slicing the domed end of projection 24 off, forming the open end 25 of the T, which also includes open ends 21 and 23 , as seen in FIGS. 2 and 3 . Finally, a finishing step is provided by placing the T-fitting 20 in a final die with three punches entering each of the openings 21 , 23 , and 25 to provide the final sizing and dimensions for receiving corresponding pipes in a plumbing system.
[0022] As can be seen by comparing FIGS. 1 and 2 , a significant percentage of copper is saved by reducing the amount of copper shown by arrow C in FIG. 1 to a significantly smaller amount, as shown by arrow D in FIG. 2 . The reduction in the amount of copper in that particular area can be as much as 300% or more and represents an overall copper savings for the T-fitting of from 10% to 12%. The ability to manufacture fitting 20 as shown in FIGS. 2 and 3 is achieved by the shape of the shovel-nose punch 50 shown in FIGS. 4-11 . One such punch is used at each of the open ends 21 and 23 ( FIG. 2 ) by the hydro-forming machine 30 ( FIG. 12 ).
[0023] Punch 50 includes a first end 52 which is coupled to a source of pressurized fluid, such as water, at a pressure of 10,000 pounds or the like and has a generally cylindrical body 54 terminating in a shovel-nosed end 56 . A cylindrical longitudinally extending passageway 55 allows water to pressurize the internal volume of the copper pipe placed in the hydro-forming press. The end 56 includes a lower tapered lip 58 (tapered at about 45°) extending forwardly and concavely curved through an arc of approximately 120°. Lip 58 is tapered upwardly to the opening 55 by a tapered conical transition zone 57 and lead-in zone 59 . Zone 57 circumscribes an arc of about 82° ( FIG. 5 ). The top 51 of the shovel-nose punch is also tapered at 61 at about 45° to form a semi-conical surface.
[0024] The hydro-forming machine uses two identical punches 50 with one on each end and the shovel-nosed ends 58 align with the lower section 27 ( FIG. 2 ) of the fitting 20 during the forming process, such that the edges 58 of the punch form the edges 26 and 28 of the copper shown by arrow D in FIG. 2 . By providing an outwardly projecting nose 56 and the angled end defined by side walls 63 and 65 terminating in the upper annular end 51 ( FIGS. 4 , 7 , and 8 ) allows the shovel-nose design of punch 50 when used in a hydro-forming process to form the fitting shown in FIGS. 2 and 3 with a reduced amount of excess copper, thereby greatly reducing the cost of the fitting itself and yet providing the same high quality T-fitting available with the prior art processes. The dimensions of the punch 50 are proportionally varied depending on the size of T-fitting 20 being manufactured, although the shovel-nose shape remains substantially as shown.
[0025] It will become apparent to those skilled in the art that the exact shape of the punch nose may be varied, as will the dimensions for different size T-fittings, without departing from the spirit or scope of the invention as defined by the appended claims. | A punch for forming opposite ends of a copper tube into a T includes a tapered or shovel-nose such that the spacing between the ends of the opposed punches is reduced, thereby reducing the excess copper remaining in the T once formed. A method of forming the fitting employs the shovel-nose punches in a hydro-forming process to accommodate such results. | 1 |
CROSS-REFERENCES TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT
Not applicable.
REFERENCE TO A BIOLOGICAL SEQUENCE LISTING
Not applicable.
BACKGROUND OF INVENTION
1. Field of the Invention
This invention is in the field of containment of trash in vehicles as well as prevention of littering on the highways
2. Description of the Related Art
An existing way of containing trash in a vehicle and preventing littering is a small trash can placed on the floor or other level surface such as a center console. Providing a means for preventing the can from tipping over is to add weight or flaps or both to the bottom, such as can be opened for viewing on a Web browser at: http://sell.lulusoso.com/selling-leads/1142984/car-waste-bin-car-trash-bin-car-waste-container.mht. A disadvantage to this is that if such a container cannot be positioned on a center console or on the floor between passengers, it takes up leg room somewhere else on the floor (and might be knocked over anyway as a result of being kicked). One way of surmounting this difficulty is taught by several patents and patent applications which suspend a trash receptacle from a seat part such as the top of the seat back, the seat back pocket behind the seat, or the head rest. Most of these contain rigid parts which can be dangerous to occupants in the event of a sudden stop or crash. Those that suspend from the top of the seat back or the seat back pocket are not conveniently used by front seat passengers. There is a U.S. patent on trash receptacles suspended between the front seats, U.S. Pat. No. 5,868,294, but it involves specially-fabricated receptacles, and hanging mechanisms that either span from the driver's head rest to the passenger's or require snaps sewn into the sides of the seats. This patent also discloses a receptacle with hooks for hanging over the middle of a bench-style front seat, but bench-style front seats are increasingly rare. The devices described in this patent are complex and/or require special installation. A U.K. patent publication, no. GB2439323, describes a way of suspending an essentially cost-free ordinary plastic grocery bag from one of the head rest supporting posts using a flexible strap, but still not in a position convenient to the front seat passengers. U.S. Pat. No. 5,791,614 describes a Head Rest Mounted Hanger that performs a similar function using both of the two head rest supporting posts on one of the front seats to suspend basically any bag with a strap close to the side of the seat. While it is true that the flexible hanger of U.K. publication GB2439323 and the hanger of U.S. Pat. No. 5,791,614 appear to be low in manufacturing cost, and capable of hanging a plastic grocery bag, neither of these hold the handles of such a bag apart so that trash can be put into the bag with one hand. The former of these has the further disadvantage of swinging on the head rest post during travel, and the latter has the further disadvantage of the bag handle slipping off the hanger during travel.
There is thus a need for an apparatus that permits hanging a recyclable and cost-free bag securely between the front seats and holding the handles apart regardless of the motion of the vehicle.
BRIEF DESCRIPTION OF THE INVENTION
The instant invention is an elongate strap that, by itself, enables a plastic grocery bag to be used conveniently and inexpensively for trash disposal in a vehicle. It has a specially-shaped head rest post catch portion at one end and a specially-shaped bag handle hook portion at the other. The catch portion is placed to partially encircle both head rest posts on a vehicle seat, allowing the strap to drape over the shoulder of the seat so that the hook portion hangs between the seats. The hook portion comprises two spaced-apart funnel shaped cuts which hold the handles of a plastic grocery bag apart for easy disposal of trash by either the left or the right seat occupant. The device is more flexible in the elongate direction than in the transverse direction so that it can easily drape over seat shoulders of varying widths and shapes while at the same time resisting the tendency of weight in the bag and motion of the vehicle to pull the bag handles towards each other.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the instant invention in use on a vehicle seat.
FIG. 2 is a plan view of the strap of the invention.
FIG. 3 is a close-up perspective view of the rear hook cutout of the instant invention gripping one handle of a plastic grocery bag under steady vehicle motion.
FIG. 4 is a close-up perspective view of the rear hook cutout of the instant invention gripping one handle of a plastic grocery bag under sudden acceleration.
FIG. 5 is a close-up perspective view of the rear hook cutout of the instant invention while a person is removing the bag from the hook.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, in which like reference characters refer to like elements among the drawings, FIG. 1 is a perspective view of the instant invention in use on the front passenger's vehicle seat 1 , as seen from behind the seat. The invention, a plastic bag holder, comprises an elongate flexible strap 2 , to which a flexible bag 3 is attached. The bag 3 , which serves the purpose of a trash receptacle, is most likely to be a recycled two-handled grocery bag having a rear handle 8 and a front handle 9 . The seat comprises a seat back 4 , a head rest 5 , a proximal head rest support post 6 and a distal head rest support post 7 . All parts shown except the strap 2 are environmental structure and are shown in dashed lines.
The strap 2 comprises two parts, a shaped catch portion 10 generally disposed along the top 11 of the seat 1 , and a shaped hook portion 12 generally disposed over the left shoulder 13 of the seat 1 . The catch portion 10 comprises a proximal catch cutout 14 which partially encircles the proximal head rest support post 6 , and a distal catch cutout 15 which partially encircles the distal head rest support post 7 . Although the invention is shown here mounted on the passenger's seat 1 , it may just as well be mounted in mirror image on the driver's seat because the strap 2 is thin and flexible and the hook portion 12 may be flexed oppositely with respect to the catch portion 10 .
The rear handle 8 of the bag 3 can be seen here inserted into a rear hook cutout 16 of the hook portion 12 , and the front handle 9 of the bag 3 is seen inserted into the front hook cutout 17 of the hook portion 12 .
FIG. 2 is a plan view of the strap 2 of the invention. In the preferred embodiment it is cut to the shape shown out of flexible, strong material of about ⅛ to ⅜ inch thick throughout, and preferably is less flexible in the horizontal direction (on the page) as in the vertical direction. This variation in rigidity exists, for example, in certain belt materials that are reinforced by embedded wires running in one direction.
The actual thickness of the strap 2 is not important so long as the strap resists tearing in its weakest direction under manual strength. An alternative embodiment can be made out of a material of constant flexural strength per unit thickness if the hook portion 12 (generally below the line A-A′) is thicker than the catch portion 10 . Yet another embodiment can achieve this effect by applying a reinforcing layer horizontally across the hook portion 12 .
The catch portion 10 of the instant invention comprises catch cutouts 14 and 15 for removably securing the strap 2 about the head rest posts 6 and 7 (not shown in this figure). These cutouts are specially shaped in accordance with the instant invention to secure the strap 2 to the head rest posts 6 and 7 in such a way as to prevent it from being inadvertently dislodged by motion of the vehicle or ordinary activity of the passengers. The proximal catch cutout 14 has a proximal slot 20 with a rounded proximal entrance 21 on the right edge 22 of the strap 2 , and the distal catch cutout 15 has a distal slot 23 with a rounded distal entrance 24 on the left edge 25 of strap 2 . The proximal slot 20 is cut out upwardly and to the left in this view at an angle of about 45 degrees, ending in a proximal circlet 26 near the elongate centerline B-B′ of the strap 2 . The distal slot 23 is cut out upwardly and to the right at about the same angle, terminating in a distal obround hole 27 .
The hook portion 12 of the strap 2 has rear and front hook cutouts 16 and 17 respectively for removably securing the handles of the waste bag 3 to the strap 2 . These cutouts are specially shaped in accordance with the instant invention to secure the handles of the waste bag 3 to the hook portion 12 in such a way as hold the handles apart and prevent the bag 3 from being inadvertently dislodged by motion of the vehicle or ordinary activity of the passengers. The rear and front hook cutouts 16 and 17 each have funnel portions 28 and 29 , respectively, which funnel into rear and front nips 210 and 211 , respectively, and then lead into rear and front teardrop holes 212 and 213 , respectively.
In addition to the generally J-shape of the strap 2 , the direction and shape of the cutouts in it are important to its proper functioning. The catch cutouts are positioned so that the proximal head rest post 6 will be seated within the proximal circlet 26 and the distal head rest post will be seated within the distal obround hole 27 . Because the center-to-center separation of typical head rest posts is in the range of about 6 to 7.25 inches, obround hole 27 is provided to accommodate head rest posts of separation within this range. Moreover, since the strap 2 material is flexible, the invention can be used with post separations somewhat smaller or larger. The distance between the lower center 214 of the obround hole 27 and the center of the proximal circlet 26 is about 6 inches, and the obround hole 27 is approximately 1¼ inches long in the vertical direction between the lower center 214 and upper center 215 of the obround hole 27 . Note that because the proximal and distal slots 20 and 23 are both aimed downward from the circlet 26 and the obround hole 27 respectively, the vertical distance between the rounded proximal entrance 21 and the rounded distal entrance 24 will also be roughly the same as the distance between the head rest posts. This enables the strap 2 to be installed easily by placing the upper end 216 of the strap 2 between the head rest posts 6 and 7 (not shown in this view) and guiding them into the rounded entrances 21 and 24 . Pulling the strap 2 downwardly in this view then secures the proximal head rest post 6 in the proximal circlet 26 , and seats the distal obround hole about the distal head rest post 7 . By having the slots 20 and 23 at 45 degree angles, neither forward nor backward acceleration, nor side-to-side acceleration of the vehicle can dislodge the strap from the head rest posts. It can also be seen readily that the weight of the trash bag (downward in this view) will tend to tighten the strap 2 against the head rest posts.
The shape of the hook cutouts 16 and 17 is designed to reliably retain the handles of a plastic bag during travel without making them difficult to detach for disposal. Each of the rear and front hook cutouts 16 and 17 respectively has a funnel portion 28 and 29 respectively which serves as a guide for inserting the rear and front bag handles 8 and 9 (not shown in this view) into the hook portion 12 of the strap 2 . Pulling down on the rear bag handle 8 will force it through the rear nip 210 and into the rear teardrop hole 212 . Likewise, pulling downward on the front bag handle 9 will force it through the front nip 211 and into the front teardrop hole 213 .
Finally as to FIG. 2 , note that the general J-shape of the strap 2 puts the front hook cutout 17 well forward of the vertical centerline B-B′ of the strap 2 . This places the trash bag 3 forward of where it would be otherwise and generally more accessible to the front seat occupants. I also keeps the bag from occupying part of the rear passengers' legroom.
FIG. 3 is a close-up perspective view of the rear hook cutout 16 of the instant invention gripping one handle, in this case rear handle 8 of a plastic grocery bag 3 , under steady vehicle motion. The rear nip 210 will keep the handle from emerging from the rear teardrop hole 212 during a sudden downward acceleration of the vehicle (as would occur driving over a deep pothole, for example).
FIG. 4 is a close-up perspective view of the rear hook cutout 16 of the instant invention gripping the rear handle 8 of a plastic grocery bag 3 under sudden acceleration. The combined force of gravity and forward acceleration pull the bag 3 and its contents in the direction C. However, no reasonable movement of the vehicle would rotate the rear bag handle 8 far enough upward or with enough force to pull it through the rear nip 210 and out of the rear teardrop hole 212 .
FIG. 5 is a close-up perspective view of the rear hook cutout 16 of the instant invention while a person is removing the bag 3 from the rear hook cutout 16 . Here, a person is holding the hook portion 12 with his or her left fingers 50 while pulling the rear bag handle 8 upward with the fingers of his or her right hand 51 . Because the material of the hook portion 12 is flexible and because the teardrop hole 212 is teardrop-shaped with the narrow part leading upward to the nip 210 , it is a simple matter for any person to pull the handle 8 through the nip 210 to release it from the funnel 28 . | An elongate strap to be used to hold a trash bag in a vehicle has a specially-shaped head rest post catch portion at one end and a specially-shaped bag handle hook portion at the other. The catch portion is placed to partially encircle both head rest posts on a vehicle seat, allowing the strap to drape over the shoulder of the seat so that the hook portion hangs between the seats. The hook portion comprises two spaced-apart funnel shaped cuts which hold the handles of a plastic grocery bag apart for easy disposal of trash by either left or right seat occupant. | 1 |
CROSS-REFERENCES TO RELATED APPLICATION
[0001] The present application claims priority under 35 U.S.C. §119(a) to Korean application number 10-2012-0090007, filed on Aug. 17, 2012, in the Korean Intellectual Property Office, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] 1. Technical Field
[0003] The present invention generally relates to a semiconductor device, and more particularly, to a semiconductor device capable of testing the bonding of a pad.
[0004] 2. Related Art
[0005] A semiconductor chip receives a signal through a pad from an exterior. Generally, the pad of the semiconductor chip is wire-bonded to a terminal of a semiconductor substrate which directly receives an external signal. Recently, in order to reduce the pitch and pad size of a semiconductor chip, a package method using bump bonding, instead of wire bonding, has been proposed. The bump bonding is a method of directly connecting the pad of a memory chip to the terminal of the semiconductor substrate through a bump in a wireless bonding manner. The packaging scheme using bump bonding as described above is called a flip chip.
[0006] The use of flip chip bonding enables reduction of the pad size of the semiconductor chip. Therefore, when a scratch or the like occurs on a pad, bump bonding is not normally achieved. When bump bonding is not normally achieved, a semiconductor chip cannot input and output a signal through the pad, so that the semiconductor chip can not sufficiently show the function thereof.
[0007] When the bump bonding is not completely formed, it is impossible to input and output a signal through a pad, so that the defects of the bump bonding can be easily detected. However, when bump bonding is incompletely achieved, such as when only a part of the bump bonding is formed, the defects of the bump bonding cannot be easily detected because signals can be inputted and outputted through a pad. When bump bonding is incomplete, an input signal can be delayed, which can cause malfunction of an internal circuit of a semiconductor chip. However, since there is no method of making it possible to accurately detect a partial defect of the bump bonding, it is difficult, when malfunction of a semiconductor chip occurs, to determine whether the malfunction is caused by a defect of bump bonding or by a defect of an internal circuit.
SUMMARY
[0008] A test circuit capable of accurately detecting whether bonding of a pad is normally achieved, and a semiconductor device including the same are described herein.
[0009] In an embodiment, a test circuit includes: a phase difference detection unit configured to detect a phase difference between a first signal received through a first pad and a second signal received through a second pad; and a determination unit configured to compare the detected phase difference with a preset amount of delay, and to output a result signal.
[0010] In an embodiment, a semiconductor device includes: a first pad; a second pad; a first reception unit configured to receive a first signal which is inputted through the first pad; a second reception unit configured to receive a second signal which is inputted through the second pad; a phase difference detection unit configured to detect a phase difference between the outputs of the first and second reception units; and a determination unit configured to compare the phase difference with a preset amount of delay, and to output a result signal.
[0011] In an embodiment, a semiconductor device includes: a plurality of pads configured to receive external signals; a phase difference detection unit configured to detect a phase difference between the external signals received through the plurality of pads; and a determination unit configured to compare the phase difference with a preset amount of delay, and to output a result signal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Features, aspects, and embodiments are described in conjunction with the attached drawings, in which:
[0013] FIG. 1 is a diagram schematically illustrating the configuration of a semiconductor device according to an embodiment;
[0014] FIG. 2 is a block diagram schematically illustrating a configuration capable of being implemented in a test circuit of FIG. 1 ;
[0015] FIG. 3 is a diagram illustrating a configuration capable of being implemented in a phase difference detection unit of FIG. 2 ;
[0016] FIG. 4 is a diagram illustrating a configuration capable of being implemented in a determination unit of FIG. 2 ;
[0017] FIG. 5 is a diagram illustrating the phase differences of received signals with respect to when bump bonding of the first and second pads is normally formed and when the bump bonding is incompletely formed; and
[0018] FIGS. 6 a and 6 b are timing diagrams illustrating the operation of a semiconductor device according to an embodiment.
DETAILED DESCRIPTION
[0019] Hereinafter, a semiconductor device capable of testing the bonding of a pad according to the various embodiments will be described below with reference to the accompanying drawings through the embodiments.
[0020] FIG. 1 is a diagram schematically illustrating the configuration of a semiconductor device 1 according to an embodiment. In FIG. 1 , the semiconductor device 1 may include a first pad 10 , a second pad 20 and a test circuit 30 . The first and second pads 10 and 20 receive external signals applied from an exterior. The first pad 10 can receive a first signal SIG 1 , and the second pad 20 can receive a second signal SIG 2 . The first and second signals SIG 1 and SIG 2 can be signals different from each other, or especially, can be the same signal for a test operation. That is to say, in a normal operation of a semiconductor device, the first and second pads 10 and 20 can receive signals coinciding with the respective functions, and can receive an external signal which is simultaneously inputted in a test operation, to which the embodiments are not delimited.
[0021] The first and second pads 10 and 20 are input/output pads, and can receive one among an address signal, a command signal, and data. Otherwise, in a test operation, a specific signal inputted from test equipment or a controller can be received. According to an embodiment, the first and second pads 10 and 20 can include a flip chip bonding pad or a bump bonding pad.
[0022] The test circuit 30 receives the first signal SIG 1 through the first pad 10 and receives the second signal SIG 2 through the second pad 20 . The test circuit 30 can determine whether or not the bump bonding of the first and second pads 10 and 20 have been normally formed depending on the phase difference between the first signal SIG 1 and the second signal SIG 2 . When an external signal is applied to the first and second pads 10 and 20 at the same time point, and the first and second pads 10 and 20 are normally achieved, the phase difference between a signal inputted through the first pad 10 and a signal inputted through the second pad 20 becomes very small. Ideally, the phase difference becomes zero. In contrast, when the first and second pads 10 and 20 are incompletely formed, the phase difference between a signal inputted through the first pad 10 and a signal inputted through the second pad 20 becomes larger than a threshold value. Therefore, the test circuit 30 may sense the phase difference between the first signal SIG 1 received through the first pad 10 and the second signal SIG 2 received through the second pad 20 , and can determine that the bump bonding of the first and second pads 10 and 20 is incomplete when the phase difference is larger than a threshold value, and that the bump bonding of the first and second pads 10 and 20 has been normally and completely formed when the phase difference is smaller than the threshold value.
[0023] The threshold value can be a preset amount of delay, and the preset amount of delay can optionally vary by a delay selection signal, a description of which will be given later in this document. The test circuit 30 can receive a test mode signal TM to perform a test operation of the semiconductor device 1 . The test mode signal TM is a signal for distinguishing a test operation from the other operations, and can be enabled when the test operation is performed.
[0024] In FIG. 1 , the semiconductor device 1 can additionally include a first reception unit 40 and a second reception unit 50 . The first and second reception units 40 and 50 may be connected with the first and second pads 10 and 20 , respectively. The first reception unit 40 buffers the first signal SIG 1 received through the first pad 10 . The second reception unit 50 buffers the second signal SIG 2 received through the second pad 20 . The first and second reception units 40 and 50 may be normal receiver circuits or buffer circuits.
[0025] FIG. 2 is a block diagram schematically illustrating a configuration capable of being implemented in the test circuit 30 of FIG. 1 . In FIG. 2 , the test circuit 30 may include a phase difference detection unit 100 and a determination unit 200 . The phase difference detection unit 100 receives the first and second signals SIG 1 and SIG 2 from the first and second pads 10 and 20 or from the first and second reception units 40 and 50 . The phase difference detection unit 100 generates a detection signal DET which has a pulse width corresponding to the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 . That is to say, the phase difference detection unit 100 generates the detection signal DET having a narrow pulse width when the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 is small, and generates the detection signal DET having a wide pulse width when the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 is large.
[0026] The determination unit 200 may compare the phase difference between the first and second signals SIG 1 and SIG 2 sensed by the phase difference detection unit 100 with a preset amount of delay to generate a result signal P/F. For example, the determination unit 200 can generate the result signal P/F which may be disabled when the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 is smaller than the preset amount of delay, and generate the result signal P/F which may be enabled when the phase difference is larger than the preset amount of delay. The determination unit 200 receives the detection signal DET. The determination unit 200 can compare the detection signal DET with the preset amount of delay and generate the result signal P/F.
[0027] FIG. 3 is a diagram illustrating a configuration capable of being implemented in the phase difference detection unit 100 of FIG. 2 . In FIG. 3 , the phase difference detection unit 100 may include an exclusive-OR gate XOR. The exclusive-OR gate XOR receives the first and second signals SIG 1 and SIG 2 from the first and second pads 10 and 20 , and generates the detection signal DET. The exclusive-OR gate XOR generates the detection signal DET which has a phase width corresponding to the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 .
[0028] FIG. 4 is a diagram illustrating a configuration capable of being implemented in the determination unit 200 of FIG. 2 . In FIG. 4 , the determination unit 200 may include a comparison unit 210 and an output unit 220 . The comparison unit 210 may compare the pulse width of the detection signal DET with a preset amount of delay, and may generate an enable signal EN. For example, the comparison unit 210 can disable the enable signal EN when the pulse width of the detection signal DET is smaller than the preset amount of delay, and can enable the enable signal EN when the pulse width of the detection signal DET is larger than the preset amount of delay.
[0029] The comparison unit 210 may include a variable delay unit 211 , and an enable signal generation unit 212 . The variable delay unit 211 may provide the preset amount of delay. The variable delay unit 211 may receive the detection signal DET, delay the detection signal DET by the preset amount of delay, and may output a delayed detection signal DETD. The amount of delay of the variable delay unit 211 can be set by a delay selection signal dsel<0:n>.
[0030] The enable signal generation unit 212 may generate the enable signal EN in response to the detection signal DET and the delayed detection signal DETD. The enable signal generation unit 212 can enable the enable signal EN when the pulse of the detection signal DET and the pulse of the delayed detection signal DETD overlap each other. In FIG. 4 , the enable signal generation unit 212 may include an AND gate. The AND gate receives the detection signal DET and the delayed detection signal DETD, and generates the enable signal EN.
[0031] The output unit 220 may generate a result signal P/F in response to the enable signal EN. When the enable signal EN is enabled, the output unit 220 may generate the result signal P/F, for example, having a high level (i.e., high voltage logic level or voltage level), and maintains the result signal P/F at the high level. In FIG. 4 , the output unit 220 may include a PMOS transistor PM, an NMOS transistor NM, and a latch unit LAT. The PMOS transistor PM may receive an inversion signal of a test mode signal TM, and provides an external voltage to a first node n 1 . The NMOS transistor NM may receive the enable signal EN, and provide a ground voltage to the first node n 1 . The latch unit LAT inverses and latches a signal of the first node n 1 to generate the result signal P/F. When the test mode signal TM is enabled, the output unit 220 drives the first node n 1 to be a high level, and the latch unit LAT latches the result signal P/F to a low level (i.e., low voltage logic level or voltage level). When the enable signal EN is not enabled, the output unit 220 may maintain the result signal P/F at a low level without any change. When the enable signal EN is enabled, the NMOS transistor NM may drive the first node n 1 with the ground voltage, and the latch unit LAT transitions the result signal P/F to a high level and maintains the result signal P/F at the high level.
[0032] In FIG. 4 , the determination unit 200 can additionally include an input unit 230 . The input unit 230 may enable the detection signal DET to be inputted to the comparison unit 210 in a test operation. The input unit 230 may include an AND gate. The AND gate receives the detection signal DET and the test mode signal TM. Accordingly, when the test mode signal TM is enabled, the input unit 230 can provide the detection signal DET to the comparison unit 210 .
[0033] FIG. 5 is a diagram illustrating the phase differences of received signals with respect to when bump bonding of first and second pads 10 and 20 is normally formed and when the bump bonding is incompletely formed, and FIGS. 6 a and 6 b are timing diagrams illustrating the operation of a semiconductor device 1 according to an embodiment. The following description will be given with respect to the operation of a semiconductor device 1 according to an embodiment with reference to FIGS. 1 to 6 b .
[0034] As illustrated in FIG. 5 , when the bump bonding of the first pad 10 is normally formed, and the bump bonding of the second pad 20 is incompletely formed, a phase difference occurs between signals received through the first and second pads 10 and 20 although the signals have been inputted at the same time point from an exterior.
[0035] For a test operation, a test mode signal TM is enabled. The phase difference detection unit 100 generates a detection signal DET which has a phase width corresponding to the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 . The comparison unit 210 of the determination unit 200 delays the detection signal DET to generate a delayed detection signal DETD, wherein depending on the detection signal DET and the delayed detection signal DETD overlap each other, it is determined whether or not to enable the enable signal EN.
[0036] As illustrated in FIG. 6 a , when the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 is small, the detection signal DET having a narrow pulse width is generated. Since the delayed detection signal DETD obtained by delaying the detection signal DET by a preset amount of delay has no portion overlapping with the detection signal DET, the comparison unit 210 maintains the enable signal EN at a disable state. When the enable signal EN is maintained at a disable state, the output unit 220 maintains a result signal P/F at a low level. When the result signal P/F is at a low level, it can be determined that the bump bonding of the first and second pads 10 and 20 has all been normally formed.
[0037] As illustrated in FIG. 6 b , when the phase difference between the first and second signals SIG 1 and SIG 2 received through the first and second pads 10 and 20 is large, the detection signal DET having a wide pulse width is generated. Although the detection signal DET is delayed by a preset amount of delay, a portion overlapping with the delayed detection signal DETD occurs because the pulse width of the detection signal DET is wide. When the pulse of the detection signal DET and the pulse of the delayed detection signal DETD overlap each other, the comparison unit 210 enables the enable signal EN. When the enable signal EN is enabled, the output unit 220 transitions the result signal P/F to a high level and maintains the result signal P/F at the high level. When the result signal P/F is at a high level, it can be determined that the bump bonding of one of the first and second pads 10 and 20 has been incompletely formed.
[0038] In an embodiment, in order to increase the accuracy of the test operation according to an embodiment, it is possible to apply external signals to three or more pads, to detect phase differences between signals received through the respective pads, and to obtain the result signal. Otherwise, it is possible to set one pad as a reference pad, to compare an external signal received through the reference pad with each of external signals received through a plurality of other pads, and to simultaneously or individually test whether or not bump bonding of all the pads has been normally formed.
[0039] While various embodiments have been described above, it will be understood to those skilled in the art that the embodiments described are by way of example only. Accordingly, the device described herein should not be limited based on the described embodiments. | A test circuit includes a phase difference detection unit and a determination unit. The phase difference detection unit detects a phase difference between a first signal received through a first pad and a second signal received through a second pad. The determination unit compares the detected phase difference with a preset amount of delay and outputs a result signal. | 7 |
BACKGROUND
The invention relates to a valve assembly and particularly to a valve assembly for fluid flow into a chamber having a pair of independent subchambers separated by a flexible wall.
Many structural arrangements where fluid is to flow into a fluid chamber utilize valve assemblies to control the inlet to the chamber. A common valve assembly used for this purpose is a check type valve assembly where a valve member is operable to open or close the inlet by movement into and out of engagement with a valve seat in the valve assembly. Usually such a valve member is designed to open by the force of fluid pressure against a biasing force tending to hold the valve member seated or in its closed position.
In inflatable products such as aircraft escape slides, rafts or flotation tubes, gas is used to inflate the product through an inlet into a main inflation chamber defined by the flexible outer walls of the product. Many of these inflatables are currently designed such that the inflation chamber is in reality two fluidly independent subchambers separated internally by a fluid impervious wall sometimes referred to as a "bulkhead". This feature assures that in the event of puncture, tear, etc., at an outer wall portion of the inflatable, complete deflation of the articles will not occur because one or the other of the independent subchambers remains intact and inflated.
To satisfactorily inflate such subchambered structures it is often necessary to provide separate inlets to each subchamber fitted with independent valves so that the subchambers remain fluidly independent. However, spatial requirements and/or other environmental factors render such separate inlets impractical. For example, wheeled helicopters are often fitted with inflatable flotation tubes at the hub portion of each wheel. The limited space allowed for inlet into the inflatable flotation tube dictates a minimization of hoses, tubing, etc., making independent inlets to each of subchamber undesirable.
SUMMARY
The present invention provides a valve assembly particularly adaptable for fluid inlet to a chamber which is divided into fluidly independent subchambers. Specifically, the valve assembly includes a housing, the forward or upstream portion of which is a fluid conduit provided with a valve seat at its rearward or downstream end. The valve housing further includes a downstream flange portion which is attachable to the inlet to the main chamber structure and which flange includes a central opening or bore concentric with the upstream conduit.
Within the housing, disposed between the conduit and flange portions, a valve member is disposed to open and close communication between the fluid conduit portion and the inflation chamber. When closed, this valve member engages the valve seat at the downstream end of the fluid conduit portion. Biasing means such as springs are used to hold the valve member closed. The valve member opens by pivotable movement of a pair of its constituent portions in the downstream direction about a common axis extending substantially parallel to the midplane of the valve member. The flexible wall or bulkhead dividing the independent subchambers is attached to the valve member adjacent this common axis effecting a splitting of the fluid flow into the respective subchambers on either side of the bulkhead.
Thus, the valve assembly according to this invention effects independent inflation of subchambers through a valve housing having a single conduit inlet into the such housing.
THE DRAWINGS
In the drawings which are part of this specification:
FIG. 1 is a plan view of a valve assembly according to the present invention; and
FIG. 2 is a section of the valve assembly shown in FIG. 1, through lines 2--2 thereof.
DETAILED DESCRIPTION
The invention according to a presently preferred embodiment is exemplified in the views of the accompanying drawing wherein like reference characters are used to refer to like structural details throughout the views.
In FIGS. 1 and 2, a portion of a flexible, inflatable article 10, such as a helicopter flotation tube, is shown having an inlet opening 12 defined by a thickened circular flange portion 14 of the the outer wall 11 of article 10. An impervious flexible wall or bulkhead 20 divides a main inflation chamber within outer wall 11 into two (2) fluidly independent subchambers 22 and 24. The article 10 is typically made of rubberized fabric material such as neoprene coated nylon. A valve assembly 30 according to the present invention is shown secured to the inflatable article 10 at the inlet opening 12.
Valve assembly 30 comprises a housing 32 consisting essentially of an upstream generally cylindrical fluid conduit portion 34 and a downstream larger diameter annular flange portion 36. Conduit portion 34 contains a gas flow inlet passage 35 therethrough while flange portion 36 also contains a fluid passage 37 which is an extension of and is concentric with passage 35. The upstream side of flange portion 36 contains an annular recess 33 at a radially inward location thereof wherein the thickedned circular flange 14 defining inlet opening 12 into article 10 is disposed to position valve assembly 30 relative to the article 10. An annular series of openings 40 through flange portion are provided to mount the valve assembly, as for example within a helicopter wheel hub, by adequate securing means such as bolts (not shown). When securing the assembly by bolts through openings 40, the bolts also pass through adjacent portions of the outer wall 11 of inflatable 10 thereby serving to secure the inflatable between the flange portion 36 and the structure to which the flange is bolted.
Fluid communication between inlet conduit 34 and the inside of inflatable 10 is controlled by a valve member 50 disposed within valve housing 32. Valve member 50 is shown in FIG. 2 is closed position by solid lines and in open position by broken lines.
Valve member 50 is preferably a molded elastomeric member comprising a circular disc-like closure portion 52 of sufficient diameter to close off passage 35. The annular edge of disc-like portion 52 is shown adapted to seat against the downstream annular edge 38 of conduit 34. An O-ring 39 is positioned along edge 38 to provide an adequate seal. Valve member 50 also comprises a pair of parallel extensions 54 integral with and extending downstream from the downstream side of disc-like closure portion 52. Extensions 54 traverse the disc-like closure 52 diametrically and are preferably of greater width than the diameter of closure portion 52.
The upstream surface of closure portion 52 has a pair of attachment lugs 56 affixed thereto. The downstream surface of closure 52 has a pair of semi-circular, thin rigid plates 58 affixed thereto. These plates 58 serve to stiffen the elastomeric closure portion 52 against back pressure from subchambers 22 and 24 in inflatable 10.
A pair of springs 60 are positioned within inlet passage 35 such that one end of each spring is secured to one of the pair of attachment lugs 56. The other end of each spring 60 is secured to a bar 62 spanning passage 35 and held in position by its ends being disposed within diametrically opposed notches 64 at the upstream end of conduit portion 34.
A pivot bar member 70 having a length substantially equal to the width of valve member extensions 54 spans extension passage 37 of flange portion 36. Each extension 54 of valve member 50 is adhered to bar 70 so as to coextend with opposite sides of bar 70 for about half of its width. Bar 70 is held secure by means of suitable securing means (not shown) connecting the ends of the bar 70 to the flange portion 36 of valve housing 32.
The edge 21 of flexible wall 20 is adhered to one side of bar 70 with the end of such edge abutting the end of one of the valve member extensions 54. On the opposite side of the bar 70 a sheet or tape 23 of the same material as bulkhead 20 is adhered to bar 70 and joins to wall 20 downstream of the downstream edge of bar 70. In this manner, it is noted that bulkhead 20 separating independent subchambers 22 and 24 connects directly to valve member 50 through bar 70.
In operation, fluid, such as pressurized gas, from a source (not shown) enters the valve assembly 30 in the direction of arrow A and applies force against the upstream surface of closure portion 52 of valve member 50 and the valve member 50 opens by semi-circular portions of closure 52 pivoting about bar 70 against the bias forces of springs 60. The fluid flow is then split into each subchamber 22 and 24 as indicated by arrows B and C respectively. When each subchamber fills, back pressure will move the semi-circular portions of valve member back to their closed position with assistance by forces applied by springs 60.
It is evident that variations and departures may be made from the structure described herein, without the same falling outside the scope of the present invention measured by the attached claims. | A valve assembly for use in inflating a chamber which comprises two independent subchambers separated by a flexible wall utilizes a single fluid inlet with a valve member controlling communication to the subchambers. The valve member comprises two pivotable portions which move downstream to split the inlet flow to fill each subchamber independently. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a hydrofoil blade for use in a paper making machine of the type wherein hydrofoil blades are positioned beneath a forming medium and extended in the cross machine direction relative to the forming medium for draining water through the forming medium from a paper web being formed on the forming medium and for forming the paper web.
2. Description of the Prior Art
In the typical Foundrinier papermaking machine, an aqueous suspension of fibers, called the "stock" is flowed from a headbox onto a traveling Fourdrinier wire or medium, generally a woven belt of wire and/or synthetic material, to form a continuous sheet of paper or paper-like material. In this connection, the expression "paper or paper-like material" is used in a broad or generic sense and is intended to include such items as paper, kraft, board, pulp sheets and non-woven sheet-like structures. As the stock travels along the Fourdrinier wire, formation of a paper web occurs, as much of the water content of the stock is removed by draining. Water removal is enhanced by the use of such well-known devices as hydrofoil blades, table rolls and/or suction devices. This invention relates to hydrofoil blades.
The hydrofoil blades used in papermaking perform two functions. The first function is to create a vacuum pulse over the downward inclined face of the hydrofoil blade. This pulse removes a portion of the white water from the lower side of the stock which lays upon the forming medium and causes fibers to be laid down and formed into a web. The amount of such water removal and web formation over a given hydrofoil blade is small, and therefore a considerable number of blades is required to form all of the fibers in the stock suspension into a two dimensional web. For example, the use of ten to fifty hydrofoil blades is not uncommon. In other words, the sheet forming process is a step-by-step filtration process as the forming medium travels over the hydrofoil blades, with some of the fibers in the lower portion of the stock suspension over the partially-formed web being added to the web at each successive foil blade. The average net change in fiber concentration or consistency of this process ranges from the headbox consistency, which is usually about 0.4 percent to about 1 percent, up to about 2.5 percent.
The second function of a hydrofoil blade is to maintain the fibers which are still is suspension throughout the forming process in an as-well-as dispersed condition as possible; i.e., in a deflocculated condition. This function is extremely important as fibers in the 0.5-2.0 percent consistency range have a strong tendency to flocculate into clumps on their own in a matter of milliseconds once the fiber dispersive forces have decayed. This flocculation causes the final paper to be highly non-uniform or flocculated in appearance.
The realization in the 1970's that papermaking stocks at commercially used consistencies reflocculate in milliseconds once floc dispersing forces on the papermaking machine decay has led to an array of devices to deliver such forces into the stock remaining to be formed into a web throughout the sheet forming process. The two key requirements of these floc dispersing forces are (1) that their size or scale is sufficiently small so that they only break up the fiber flocs, but do not disrupt the overall large scale mass of the suspension, and (2) that their intensity is sized likewise.
Both the intensity and scale of the turbulence generated by conventional foil blades of the type first described by Wrist, US Pat. No. 2,948,465 are a function of the square of both their angle to the forming fabric and the speed of the papermaking machine. As a result, the turbulence they generate is rarely optimum on papermachines producing a variety of grades over a wide speed range.
A further disadvantage of such conventional foils is that their dewatering rate and the intensity of the turbulence they generate are directly related to each other. That is, if more turbulence is required and a large foil angle is employed, then more dewatering is invariably obtained as well. Such an effect is often undesirable, especially during the early stages of sheet formation where considerable redispersion of the stock prior to sheet formation is often highly desirable. This is usually the case, for example, with older, overloaded headboxes delivering suspensions which are poorly dispersed and contain large scale eddy currents.
One device developed recently in an effort to overcome these shortcomings of such conventional foils is the multi-step foil blade described in Kallmes, US Pat. No. 4,687,549. Such foils dewater stock in a controllable manner without generating any turbulence whatsoever. Its use in a redispersing system relies on the continuous cross machine direction shear generated by the phase-changing ridges produced either by a serrated slice or a formation shower to keep the stock dispersed throughout the sheet-forming process. This cross machine direction shear acts on the stock remaining to be formed into a sheet in a manner similar to the well-known shake of slow running papermachines.
One of the key characteristics of a sheet forming process employing a serrated slice or a formation shower to keep the stock dispersed and the multi-step foil described in US Pat. No. 4,687,549 to provide turbulence-free controlled dewatering only is that it separates these two functions. That is, the pressure of the formation shower controls the intensity of the cross machine direction shear generated while the overall angle of inclination of the multi-step foil blade to the forming fabric controls the rate of dewatering.
The cross machine direction shear generated by the phase changes of the ridges produced by either a serrated slice or a formation shower are highly effective in improving the formation quality of virtually all types of paper. However, both serrated slices and formation showers have certain undesirable characteristics. Serrated slices are fixed structures which cannot be adjusted at will, and their design, like that of foil blades, is not optimum at all machine speeds on multi-grade papermachines. Formation showers also have their limitations in that, for example, their nozzles often plug, and they tend to catch stock sprayed off the forming fabric which can build up fiber clumps on them and then drop off to cause sheet breaks. Thus, there are many papermakers who shy away from using these devices for practical operating reasons.
It is desirable to overcome the foregoing shortcomings by providing a multi-step foil blade which produces floc-dispersing turbulence of controllable scale and intensity, and simultaneously independently controls the rate of dewatering.
SUMMARY OF THE INVENTION
This invention achieves these and other objects by providing a hydrofoil blade for use in a paper making machine of the type wherein hydrofoil blades are positioned beneath a forming medium and extended in the cross machine direction relative to the forming medium for draining water through the forming medium while a paper web is being formed on the forming medium and for forming the paper web. The hydrofoil blade comprises a forming medium bearing surface having a leading edge, a lower surface spaced from the forming medium bearing surface, and at least one dewatering surface diverging downward towards the lower surface from a respective of at least one crease line. The dewatering surface and/or other downstream surfaces are configured having specific angular orientation as disclosed herein for producing floc-dispersing turbulence having controllable scale and intensity while independently controlling the rate of dewatering.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic representation of one embodiment of the present invention;
FIG. 2 is a partial view of a diagrammatic representation of another embodiment of the present invention;
FIG. 3 is yet another partial view of a diagrammatic representation of another embodiment of the present invention;
FIG. 4 is a partial diagrammatic representation of the embodiment of FIG. 2 but depicting various alternative surface orientations;
FIG. 5 is another partial view of a diagrammatic representation of another embodiment of the present invention;
FIG. 6 is yet another partial view of a diagrammatic representation of another embodiment of the present invention; and,
FIG. 7 is a section of FIG. 6 take along lines 7--7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The embodiment of the invention which is illustrated in FIG. 1 is one which is particularly suited for achieving the objects of this invention. FIG. 1 diagrammatically depicts a portion of the forming section of a paper making machine of the type wherein a forming medium 2 receives stock from a headbox at a first end (not shown) and transfers a substantially self-supporting paper web from the forming medium 2 at a second end (not shown), the forming medium travelling in the machine direction generally designated by arrow 4. Hydrofoil blades are provided beneath the forming medium 2. The hydrofoil blades extend in the cross machine direction relative to the forming medium, the cross machine direction generally designated by arrow 6. The functions of hydrofoil blades are to drain water through the forming medium 2 while the paper web 8 is being formed on the forming medium and to form the paper web. In the present invention, a hydrofoil support or box 10 is provided which includes at least a first hydrofoil blade 12 comprising a forming medium bearing portion 14 having a leading edge 16 and a lower portion 18 spaced from the forming medium bearing portion. At least one dewatering surface 20 diverges downward towards the lower portion 18 from a respective of at least one crease line 22. At least one vacuum decay-turbulence generating planar surface 24 diverges upward from a respective dewatering surface 20 to a respective of at least one other crease line 22.
In operation, the forming medium 2 first contacts the multi-step hydrofoil blade in a manner familiar to those skilled in the art of papermaking at the forming medium bearing portion which is oriented parallel to and is fully in contact with the forming medium. Dewatering of the stock forming paper web 8 is initiated by the vacuum created in the nip formed over the first surface 20 immediately following the bearing portion 14, the surface 20 being inclined slightly away from a plane in which the forming medium bearing portion 14 extends in the direction 4. For example, the angle of inclination 26 of the surface 20 away from the forming medium is small, somewhere between 0.1 degrees and 5 degrees.
In the preferred embodiment, the initial contact portion 14 and inclined surface 20 of the multi-step foil blade have a length of the same order-of-magnitude, usually between about 3 and 10 cm. The surface 24 immediately following the inclined surface 20 has a smaller angle of inclination, relative to the plane in which the forming medium bearing portion lies, than the surface 20. For example, in the embodiment of FIG. 1, surface 24 is inclined upward towards such plane at a small angle 28 in the direction of travel 4. One or more pairs 20, 24 may be provided in hydrofoils contemplated by the present invention. The purpose of the section of the foil blade above each surface 24 is not to cause dewatering, but rather to permit the vacuum generated in the dewatering section above the surface 20 immediately ahead of it to decay and to generate turbulence of controlled scale and intensity in the stock above the forming medium by forcing a small proportion of the water removed from it through the forming medium back up through the forming medium and the partially-formed web, thereby creating a floc-dispersing, turbulance-generating pressure pulse.
In an alternative embodiment of the present invention as depicted in FIG. 2 a hydrofoil blade 30 is provided comprising a forming medium bearing surface 32 having a leading edge 34 and a lower surface 36 spaced from the forming medium bearing surface. At least one dewatering surface 38 diverges downward towards the lower surface 36 from a respective of at least one crease line 40. At least one intermediate surface 42 extends from a respective dewatering surface 38 to a crease line 44. Each intermediate surface includes in tandem in the machine direction (a) a vacuum decay surface 46 extending from a dewatering surface 38; (b) a turbulence generating surface 48 extending upward away from lower surface 36 from the vacuum decay surface 46; and, (c) a trailing surface 50 extending from the turbulence generating surface 48 to crease line 44.
Although not necessary, additional combination dewatering/intermediate surfaces can be provided at a location downstream of the combination dewatering surface 38/intermediate surface 42. Such additional combination(s) can be provided immediately adjacent to or even further downstream of the combination dewatering surface 38/intermediate surface 42. For example, in FIG. 2 a similar combination dewatering surface 38'/ intermediate surface 42' is provided. In such embodiment, surface 38' would again provide a dewatering section like that above surface 38. This dewatering section would be followed by another turbulence generating section 42', including sub-sections 46' 48', 50', whose orientation to the forming medium 2 in the direction 4 would be like that of those of 42, or 46, 48, 50, except that the surface or surfaces would be displaced downward away from the forming medium 2 due to the intervening presence of the downwardly inclined (in the direction 4) dewatering section 38'. The total number and location of successive pairs of dewatering and turbulence generating sections would be governed by the weight of the sheet being produced, the amount of water that has to be removed from the stock suspension, and by the physical size of the beam on which the multi-blade foil is mounted. Thus, for example, a given multi-blade foil might consist of two to eight pairs of dewatering and turbulence generating sections.
The angular orientation of surfaces 46 and 50 can be varied as desired, and FIG. 4 schematically depicts such variation. For example, as depicted in FIG. 4, vacuum decay surface 46 extends upward at a first angle 52 relative to a first plane 54 of forming medium bearing surface 32 away from the lower surface 36. First plane 54 of forming medium bearing surface 32 is defined to mean a plane in which surface 32 lies as schematically depicted in FIG. 4. The turbulence generating surface 48 diverges upward at a second angle 56 relative to first plane 54 away from the lower surface 36. In the embodiment of FIG. 4 the trailing surface 50 extends in a second plane schematically represented at 58 which is parallel to first plane 54. Alternatively, the trailing surface extends, as depicted at 50", downward at a third angle 60 relative to plane 54 towards lower surface 36.
Regardless of whether trailing surface 50 extends in a second plane 58 which is parallel to the first plane 54 or extends, as depicted at 50", downward at a third angle 60 relative to plane 54, at a smaller angle to plane 54 then the angle of the preceding dewatering surface zone 38, a vacuum decay surface can be provided which as depicted at 46", extends in a plane schematically represented at 62 which is parallel to plane 54, or which extends, as depicted at 46"', downward at an angle 52' relative to plane 54 towards lower surface 36.
By further way of example, and without limitation, the first sub-sections 46 of the intermediate surface 42 might be (a) oriented downward at a smaller angle 52' than surface 38, such as 0.5 degrees to 1.0 degree; (b) oriented parallel to the plane of the forming medium bearing surface 32; or (c) inclined upward at a small angle 52 relative to the plane of forming medium bearing surface 32 in the direction of travel 4 of between 0.1 degree and 5 degrees. In case (a), the vacuum created in the preceding section above the surface 38 will diminish in the sub-section above the subsurface 46; in (b), the vacuum in sub-section 46 will decay virtually completely; and in (c), the vacuum will decay and some white water will be forced back up through the forming fabric to cause a small pressure pulse.
The sub-section 48 of the turbulence generating zone immediately following sub-section 46 is inclined upward at a small but greater angle 56 relative to the plane of the forming medium bearing surface in the direction 4 than the surface of the preceding sub-section 46 to generate turbulence in the unformed stock above the partially-formed web. The larger its upward angle in the direction 4 relative to the forming medium bearing surface 32, the more intense the turbulence generated, and vice versa. The greater the length of this inclined surface 48, the larger the scale, or the greater the distance over which the turbulence is applied. For example, an inclined length for surface 48 or one cm. long and having an angle of 0.5 degree would generate a small weak pulse, whereas an inclined length of one cm. long but with an angle of 1.5 degrees would generate a much more intense pressure pulse.
These dimensions are provided merely as examples, and the angle and length of an inclined sub-section 48 required to produce a turbulence pulse of a given scale and intensity on a given papermachine depend on several factors such as the operating speed of the papermachine, the thickness of the layer of stock to be kept dispersed, and the thickness and density of the partially-formed web which acts as a resistance or dampener to the applied pressure pulse. The faster the machine, and the thinner the stock layer and partially-formed web, the less energy is required to produce a turbulence pulse of the desired scale and intensity, and so the shorter and shallower the inclined section, and vice versa.
The sub-section 50 following the turbulence generating subsection 48 might be oriented parallel to the forming medium bearing surface, or it may have a small angle 60 of inclination away from the forming medium bearing surface in the direction 4 to reinitiate dewatering and/or to bring the fabric-to-blade surface distance of separation at the end of the sub-section 50 to the same height as it was at the beginning of the sub-section 46. In this case, there would essentially be no gain or loss in the amount of water removed from the stock by dewatering across the blade section 46, 48, 50.
In a further embodiment of the present invention as depicted in FIG. 2, a hydrofoil blade is provided comprising at least one turbulence generating area 70 including in tandem in the machine direction, a vacuum decay section 72 extending from a dewatering surface such as surface 38", and a turbulence generating section including a first surface 74 diverging downward towards lower surface 36 from the vacuum decay section 72 and a second surface 76 diverging upward away from such lower surface from the first surface 74. In a preferred form, a surface 72 of the subsection of the turbulence generating area 70 might be parallel to plane 54 to permit the vacuum generated over the surface of a preceding dewatering section 38" to decay. The following turbulence generating surface formed by surfaces 74 and 76 would then be in the form of a V, with the first surface 74 inclined towards lower surface 36 in the direction 4, and the second surface 76 away from it. The greater the intensity of the turbulence desired, the larger the angles of the surfaces 74 and 76 relative to the plane 54 and the greater its desired scale, the greater their length, and vice versa.
The number of sub-sections of a turbulence generating section such as 42, 42', or 70 is not limited to three subsections, but may include more or less of such sub-sections, each of which includes surfaces, as discussed above, individual of such surfaces being at the same or a slightly different small angle relative to the plane 54 as discussed above.
The division of the surfaces of the multi-blade foil into turbulence generating surfaces or portions is not limited to the vacuum decay zones such as the surfaces 42 and 42'. For example, a dewatering surface can be replaced with the surfaces or portions which comprise the surface 80 as schematically shown in FIG. 3. For example, surface 80 can be sub-divided in a similar manner into portions 82, 84 and 86, with the one additional stipulation that the last portion 86 have an angle of inclination away from the plane 54 in the direction 4 of such a size that the distance of separation of its end point 88 below the plane 54 is greater than that of front end 90 of its initial portion 82. The greater the height difference between these two gaps, that is between the point 90 of FIG. 3 in the plane 54, and between the point 88 below the plane 54, and more dewatering is obtained across the dewatering zone provided at portions 82, 84, 86. The particular hydrofoil blade of this embodiment includes at least one surface 80 generally diverging downward towards lower surface 36 from a respective crease line at front end 90. At least one of such surfaces includes in tandem in the machine direction, a dewatering surface 82 diverging from a respective crease line, a vacuum decay/turbulence generating surface 84 diverging upward from dewatering surface 82 away from lower surface 36, and trailing surface 86 diverging downward from the vacuum decay/turbulence generating surface 84 towards lower surface 36 to another crease line at end point 88. In this embodiment, the crease line at end point 88 lies between the immediately preceding crease line at front end 90 and lower surface 36.
Another embodiment of a turbulence-generating multi-blade foil of the present invention is shown in FIG. 5. The base of the hydrofoil blade 100 is a steel plate 102 with high density, high molecular weight polyethylene half-tees 104 attached to its lower surface affixing it to at least two conventional tees 106 of a conventional foil beam 108.
A set of steel tees 110 is affixed to the top surface of the plate 102 at equidistant spacing along its length in the direction 4. The foil blade 112 mounted on the first tee provides the contact surface 114 comparable to, for example, forming medium bearing surface 32. The hydrofoil blade 116 mounted on the next downstream tee provides the first dewatering surface 118 comparable to, for example, dewatering surfce 38. The leading edge of blade 116 is in contact with the trailing edge of blade 112 at cross machine direction crease line 120.
Several sets of hydrofoil blades 116 are provided. The first set of such blades all have the same height between the steel plate 102 and the crease line 120 but have different descending angles in the direction 4 away from the plane 54 between 0.1 degree and 5 degrees to provide different rates of dewatering in the first dewatering section. The several blades of each of the other sets have the same series of angles. However, the overall height between the top surface of the steel plate 102 and their respective leading edge 120 of each of these sets is slightly different, about a fraction of a millimeter or a few millimeters, for their use at successive locations in blade positions 116 where the vertical gap between plane 54 and the leading edge of the dewatering blades increases stepwise due to the presence of dewatering blades upstream.
In like manner, several turbulence generating hydrofoil blades 122 with surface configurations like, for example, 46, 48 and 50 and 72, 74 and 76, of FIG. 2, are provided for each of the turbulence generating areas at blades 122. Again, the overall height of the blades of each set, that is, the gap equal to the distance between the equivalent leading edge or crease line 120 and the top surface of the support plate 102 differs slightly, such as, a fraction of a millimeter or a few millimeters among the different sets for their use at successive locations downstream on the support plate.
It will be apparent from the foregoing and from FIG. 5 that a hydrofoil blade is provided which comprises a plurality of separate segments such as, for example, 116 and 122, each of which is composed of one or more surfaces such as, for example, forming medium bearing surface 14, 32, 114, dewatering surface 20, 38, 82, 118, vacuum decay surface 46, 72, turbulence generating surface 48, 74, trailing surface 50, 76, 86, and vacuum decay-turbulence generating surface 24, 84. By selectively assembling such segments as depicted, for example, in FIG. 5, a hydrofoil blade having the desired characteristics can be provided. It should be emphasized that any desired combination of segments can be provided.
Another form of a turbulence-generating multiblade hydrofoil is shown in FIGS. 6 and 7. These Figures show a blade, as for example of the type depicted in FIG. 1, wherein the generation of turbulence is facilitated at points along the length of the blade by the selective removal of small, controlled amounts of water across the width of the papermaking machine. This water is removed from the surfaces 20, 24 of the blade through small channels 130, 132 cut into it. These channels are tapered downwardly in the cross machine direction plane 7--7 of FIG. 6 as shown in FIG. 7 to effect uniform or controllable removal of water. The lower end of the tapered channels feed tubes 134 which extend in the cross direction of the machine to its front and back side where valves 136 control the rate of their discharge into the wire pit (not shown). In operation, the downward removal of water through the channels 130, 132 from the small space 138 between the forming medium and the surfaces 20, 24 creates a small downward force on the fabric. When this force on the fabric is terminated by its travel in the machine direction 4 past a respective channel, such a downward force decays instantly, and allows the forming medium to spring back upward to its original plane of travel. This upward spring of the fabric causes stock jump or turbulence in the same manner as the instantaneous decay of the vacuum force created by conventional foil blades.
The purpose of the valves 136 in the discharge lines 134 of the channels is to be able to control the rate of dewatering across the machine. Such regulation provides the papermaker with an additional profiling tool to control the cross-directional moisture profile of the sheet of paper.
The embodiments which have been described herein are but some of several which utilize this invention and are set forth here by way of illustration but not of limitation. It is apparent that many other embodiments which will be readily apparent to those skilled in the art may be made without departing materially from the spirit and scope of this invention. | A hydrofoil blade for use in a paper making machine wherein a plurality of variously angulated surfaces is provided for producing turbulence having controllable scale and intensity while independently controlling the rate of dewatering. | 3 |
The present application is related to U.S. Pat. No. 6,023,486, which issued on Feb. 8, 2000, titled SOLDERED FAN ASSEMBLY FOR ELECTRIC DISCHARGE LASER, U.S. Pat. No. 6,034,984, which issued on Mar. 7, 2000, titled TANGENTIAL FAN WITH CUTOFF ASSEMBLY AND VIBRATION CONTROL FOR ELECTRIC DISCHARGE LASER, U.S. Pat. No. 6,061,376, which issued on May 9, 2000, titled TANGENTIAL FAN FOR EXCIMER LASER, U.S. Pat. No. 6,195,378 which issued on Feb. 27, 2001, titled, TWISTED BLADE TANGENTIAL FAN FOR EXCIMER LASER, U.S. Pat. No. 6,144,686 which issued on Nov. 7, 2000, titled TANGENTIAL FAN WITH CUTOFF ASSEMBLY AND VIBRATION CONTROL FOR ELECTRIC DISCHARGE LASER, and U.S. Pat. No. 6,765,946 which issued on Jul. 20, 2004, titled FAN FOR GAS DISCHARGE LASER, the entire contents of each of which are hereby incorporated by reference herein.
FIELD OF THE INVENTION
The present invention relates to pulsed, gas discharge lasers. The present invention is particularly, but not exclusively useful as a cross-flow fan impeller for a transversely excited, pulsed, gas discharge laser.
BACKGROUND OF THE INVENTION
Gas discharge lasers such as excimer lasers are well known light sources useful for integrated circuit lithography. These lasers typically include two elongated discharge electrodes (for example, about 30 cm in length) that are separated by about 5-20 mm to establish a discharge region between the electrodes. A high voltage pulse power source provides high voltage electrical pulses to produce discharges between the electrodes to create a gain region in a laser gas. A laser gas circulation system is generally employed to produce sufficient laser gas flow between the electrodes to remove from the discharge region substantially all of the heated, ionized gas volume and erosion debris particles produced by each discharge prior to the next succeeding discharge. For this purpose, it is typically desirable to establish a gas flow through the discharge region that is relatively uniform along the length of the electrodes. For this reason, cross-flow fans (also referred to in the art as tangential fans) have been used. For example, co-owned U.S. Pat. Nos. 6,023,486, 6,034,984, 6,061,376, 6,195,378, 6,144,686 and 6,765,946 disclose several cross-flow fan designs, each of which is hereby incorporated by reference herein.
Structurally, cross-flow fans include an elongated, somewhat cylindrical, impeller (also sometimes referred to as a squirrel cage rotor) which is rotated about a longitudinal axis by one or more motors. For example, the impeller may include a plurality of annularly shaped hubs that are spaced apart along the rotation axis and oriented orthogonal to (and substantially centered on) the rotation axis. For the impeller, each hub-pair may constitute an impeller segment and a number of blades may be provided connecting the hubs together at or near the periphery of each segment. In this manner, the blades surround a somewhat cylindrical internal impeller volume. In use, the impeller is typically disposed within and rotates relative to a flow guiding structure which establishes an intake side and a discharge side of the impeller. For some arrangements, this flow guiding structure may include one or more so-called flow cutoff members. When the fan impeller is rotated, laser gas is drawn through the blades into the internal cylindrical volume over the entire length of the fan impeller. Inside the impeller, the laser gas flow is diverted and accelerated by a vortex that is created by the rotation of the impeller. The laser gas then exits over the entire length of the impeller on the discharge side.
As the impeller blades pass the director(s), e.g. flow cutoff member, they may adversely affect laser performance in two ways. First, a mechanical vibration may be produced in the cut-off member structure that may be transmitted to the optical components defining the laser cavity. Second, the flow produced by the impeller may not be smooth, but instead, may consist of many small pressure pulses. Some of these pressure pulses may reach the gain volume where they may perturb the gain media's index of refraction. This perturbation, in turn, may result in an undesirable deterioration of one or more laser performance parameters such as spectral bandwidth, divergence, pulse-to-pulse energy stability, etc. In general, laser performance deterioration is more pronounced at discharge repetition rates which corresponding to the impeller's blade pass frequency and its sub-harmonics (each of which is a function of the impeller rotation speed and the number of blades distributed around the impeller's periphery). As used herein, the term “blade pass frequency” and its derivatives means the reciprocal of the time duration between successive passes of a blade by a stationary point during an impeller rotation. Applicant's have found that an impeller with an even number of blades may generate more undesirable sub-harmonics than an impeller with an odd number of blades, and moreover, impellers having a prime number of blades may generate fewer sub-harmonics than impellers having a non-prime number of blades.
With the above considerations in mind, Applicants disclose a cross-flow fan impeller and cross-flow fan system for a gas discharge laser.
SUMMARY OF THE INVENTION
In a first aspect, a cross-flow fan impeller for circulating gas in a transversely excited, pulsed, gas discharge laser is disclosed. For this aspect, the impeller may comprise at least three hubs, the hubs spaced apart along an impeller rotation axis with each pair of adjacent hubs establishing an impeller segment and each segment having a peripheral region. One of the segments may have n number of blades located at the segment's peripheral region and another segment may have m number of blades located at the segment's peripheral region, with m≠n, and each segment may generate a flow speed in a range of 40 to 60 m/s at a fan rotation speed of about 3500 rpm, and in specific cases may generate a flow speed in a range of 45 to 55 m/s at a fan rotation speed of about 3500 rpm. In one embodiment, the impeller may be configured with n=29 and m=23 and in another embodiment, the impeller may be configured with n=23 and m=19.
The impeller may be configured wherein n and m are prime numbers. Each blade may be aligned parallel to the rotation axis or an impeller may be configured wherein one or more blades are aligned nonparallel to the rotation axis. In one implementation, the segment having n number of blades may be adjacent to the segment having m number of blades. In one arrangement the impeller may comprises more than 15 segments. In one setup, blades in each segment may be azimuthally offset from blades in adjacent segments. Each blade may have a length and a curved cross-section normal to it's length. The blades in each segment may be nonuniformly spaced around the peripheral region. In some arrangements, each hub may be annularly shaped.
In another aspect, a cross-flow fan impeller for circulating gas in a transversely excited, pulsed, gas discharge laser may comprise a plurality of hubs, the hubs spaced apart along the impeller's rotation axis and establishing at least two impeller segments wherein a first segment has an output flow within 80-120% of a second segment and the first and second segment having differing blade pass frequencies, and in specific cases the first segment may have an output flow within 90-110% of the second segment, the first and second segment having differing blade pass frequencies. In some embodiments of this aspect, the first segment may have n number of blades, the second segment m number of blades, with m≠n. In one embodiment, the impeller may be configured with n=29 and m=23 and in another embodiment, the impeller may be configured with n=23 and m=19. The impeller may be configured wherein n and m are prime numbers.
Another aspect is disclosed in which a cross-flow fan system for circulating gas in a transversely excited, pulsed, gas discharge laser may comprise an impeller defining a rotation axis, the impeller comprising a plurality of hubs, the hubs spaced apart along the axis and establishing at least two impeller segments wherein a first segment has an output flow within 80-120% of a second segment and the first and second segment having differing blade pass frequencies, and in specific cases the first segment may have an output flow within 90-110% of the second segment, the first and second segment having differing blade pass frequencies. For this aspect, the fan system may further comprise at least one motor for rotating the impeller about the axis; and a flow guiding structure which establishes an intake side and a discharge side of the impeller. In some embodiments of this aspect, the first segment may have n number of blades the second segment m number of blades, and m≠n. In one embodiment, the impeller may be configured with n=29 and m=23 and in another embodiment, the impeller may be configured with n=23 and m=19. The impeller may be configured wherein n and m are prime numbers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a simplified, perspective, partially exploded view of a transverse discharge gas laser;
FIG. 2 shows a simplified sectional view of a laser chamber as seen along line 2 - 2 in FIG. 1 ;
FIG. 3 shows a perspective view of a cross-flow fan impeller having eighteen segments;
FIG. 4 shows a sectional view of the impeller shown in FIG. 3 as seen along line 4 - 4 in FIG. 3 showing a segment having 19 blades;
FIG. 5 shows a sectional view of the impeller shown in FIG. 3 as seen along line 5 - 5 in FIG. 3 showing a segment having 23 blades;
FIG. 6 shows measured flow performances (fan speed in RPM v. flow speed in m/s) for several fan configurations;
FIG. 7 shows measured flow performances (motor power in kW v. flow speed in m/s) for several fan configurations; and
FIG. 8 shows measured flow performances (motor current in A v. flow speed in m/s) for several fan configurations.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring initially to FIG. 1 , a simplified, partially exploded view of portions of a transverse discharge gas laser device are shown and generally designated 20 . For example, the device 20 may be a KrF excimer laser, an XeF excimer laser, an XeCl excimer laser, an ArF excimer laser, a molecular fluorine laser or any other type of transverse discharge gas laser known in the pertinent art. As shown, the device 20 may include a two-part chamber housing 22 a,b being formed of a chamber wall that may be made of a conductive, corrosion resistant material, e.g., nickel-plated aluminum. As further shown in FIG. 1 , window assemblies 24 a,b may be provided at each end of the chamber housing 22 a,b to allow light to enter, exit and pass through the chamber housing 22 a,b along a common beam path. With this structure, the hollow chamber housing 22 a,b and window assemblies 24 a,b may surround a volume which holds a gas medium under pressure together with other components suitable to create a discharge in the medium. These other components may include, for example, a pair of discharge electrodes (not shown in FIG. 1 ), a fan system to circulate the gas (not shown in FIG. 1 ), heat exchangers to cool the gas (not shown in FIG. 1 ), etc. It is to be appreciated that the chamber housing 22 a,b may also be formed with a number of sealed inlets/outlets (not shown in FIG. 1 ), to allow gas to be introduced/extracted from the chamber, to allow conductors 26 to deliver an excitation voltage to the electrodes, etc.
In addition to the chamber, FIG. 1 shows that the device 20 may also include a beam reverser 28 and output coupler 30 cooperatively arranged to form an optical cavity. For the device 20 , the beam reverser 28 may be as simple as a flat, fully reflective mirror or as complex as a grating-based line-narrowing unit. Continuing with FIG. 1 , the device 20 may also include a pulse power system 32 delivering electrical pulses to electrodes located within the chamber housing 22 a,b via conductors 26 . FIG. 1 further illustrates that during operation of the device 20 , a laser beam 34 is created which exits the optical cavity via the output coupler 30 .
It is to be appreciated that the use of the fan impeller and fan system described infra is not limited to the stable, standing wave cavity alluded to above, rather, the fan system and fan impeller described herein may be employed within other optical arrangements such as a one-pass amplifier, multi-pass amplifier, traveling wave amplifier such as a ring amplifier, unstable cavities, etc.
FIG. 2 shows the inside of the chamber in greater detail. As seen there, chamber components may include chamber housing upper 22 a and lower 22 b , cathode 36 and anode 38 (which are spaced apart to establish a discharge region 40 ), preionizer tube 42 , anode support flow shaping structure 44 , flow shaping structure 46 , fan impeller 48 , and four water cooled heat exchanger units 50 a - d.
Cross referencing FIGS. 2 and 3 , is can be seen that the device 20 includes a cross-flow fan system for circulating laser gas through the chamber. As shown, the fan system may include an impeller 48 defining a rotation axis 52 , a motor 54 (note: in some cases, two motors may be used with one on each end of the impeller) for rotating the impeller 48 about the axis 52 ; and a flow guiding structure which establishes an intake side and a discharge side of the impeller 48 . For the arrangement shown in FIG. 2 , flow guiding structure includes directors 56 a,b with director 56 a (sometimes referred to as a so-called flow cutoff member) extending from the anode support flow shaping structure 44 to a location proximate the impeller 48 and director 56 b attached to the housing wall and extending therefrom to a location proximate the impeller 48 , as shown. Typically, each director 56 a,b is configured to extend along the length of the impeller 48 . With the arrangement shown in FIG. 2 , gas from the discharge region 40 flows in the direction of arrow 58 and passes through the heat exchanger units 50 a - d where it is drawn into the central volume 60 of the impeller 48 . Gas is then discharged from the impeller 48 and directed to the discharge region 40 .
As best seen in FIG. 3 , the impeller may include a plurality of annularly shaped hubs (of which hubs 62 a - c have been identified with reference numerals). Although an impeller 48 with nineteen hubs is shown in FIG. 3 , it is to be appreciated that more than nineteen and as few as three hubs may be used. Also shown, the hubs 62 a - c may be spaced apart along the axis 52 , centered on the axis 52 and oriented orthogonal to (and centered on) the rotation axis 52 , with each adjacent hub pair establishing an impeller segment (of which segments 64 a - c have been identified with reference numerals). Although an impeller 48 with eighteen segments is shown in FIG. 3 , it is to be appreciated that more than eighteen and as few as two segments may be used.
Cross referencing FIGS. 3 and 4 , it can be seen that segment 64 a may include a plurality of blades 66 (of which blades 66 a - c have been identified with reference numerals in FIG. 4 ) connecting hub 62 a to hub 62 b at or near the periphery of the segment 64 a . As best seen in FIG. 4 , segment 64 a includes nineteen blades 66 , with each blade 66 having a curved cross section normal to the rotation axis 52 . Although the blades 66 are shown uniformly distributed around the periphery of the segment in FIG. 4 , in other embodiments, the spacing between adjacent blades within a segment may vary around the segment periphery. FIG. 3 also shows that the blades 66 may be relatively straight along their length and aligned substantially parallel with the rotation axis 52 .
Cross referencing FIGS. 3 and 5 , it can be seen that segment 64 b may include a plurality of blades 68 (of which blades 68 a - c have been identified with reference numerals in FIG. 5 ) connecting hub 62 c to hub 62 b at or near the periphery of the segment 64 b . As best seen in FIG. 5 , segment 64 b includes twenty three blades 68 , with each blade 68 having a curved cross section normal to the rotation axis 52 . Although the blades 68 are shown uniformly distributed around the periphery of the segment in FIG. 5 , in other embodiments, the spacing between adjacent blades within a segment may vary around the segment periphery. FIG. 3 also shows that the blades 68 may be relatively straight along their length and aligned substantially parallel with the rotation axis 52 .
With the above-described cooperation of structure, it can be seen that adjacent impeller segments may have a different number of blades. Thus, for example, the impeller may be configured having nine segments with nineteen blades and nine segments with twenty-three blades, the dissimilar segments alternating along the length of the impeller. Alternatively, several adjacent segments may have the same number of blades. FIG. 3 also shows that a blade in one segment may be azimuthally offset from a corresponding blade in an adjacent segment.
FIG. 6 shows measured flow performances (fan speed in RPM v. flow speed in m/s) for fans having 23 blades in all segments and 0.65, 0.76 and 0.85 inside diameter to outside diameter ratio (ID/OD), fans having 19 blades in all segments and 0.65 and 0.76 ID/OD and a fan having 29 blades in all segments and 0.85 ID/OD. FIG. 7 shows measured flow performances (motor power in kW v. flow speed in m/s) for fans having 23 blades in all segments and 0.65, 0.76 and 0.85 ID/OD, fans having 19 blades in all segments and 0.65 and 0.76 ID/OD and a fan having 29 blades in all segments and 0.85 ID/OD. FIG. 8 shows measured flow performances (motor current in A v. flow speed in n/s) for fans having 23 blades in all segments and 0.65, 0.76 and 0.85 ID/OD, fans having 19 blades in all segments and 0.65 and 0.76 ID/OD and a fan having 29 blades in all segments and 0.85 ID/OD.
FIGS. 6-8 illustrate and support the proposition that an impeller having segments with different numbers of blades can be configured having an acceptably uniform flow speed along the length of the impeller.
While the particular aspects of embodiment(s) described and illustrated in this patent application in the detail required to satisfy 35 U.S.C. §112 is fully capable of attaining any above-described purposes for, problems to be solved by or any other reasons for or objects of the aspects of an embodiment(s) above described, it is to be understood by those skilled in the art that it is the presently described aspects of the described embodiment(s) of the present invention are merely exemplary, illustrative and representative of the subject matter which is broadly contemplated by the present invention. The scope of the presently described and claimed aspects of embodiments fully encompasses other embodiments which may now be or may become obvious to those skilled in the art based on the teachings of the Specification. The scope of the present invention is solely and completely limited by only the appended claims and nothing beyond the recitations of the appended claims. Reference to an element in such claims in the singular is not intended to mean nor shall it mean in interpreting such claim element “one and only one” unless explicitly so stated, but rather “one or more”. All structural and functional equivalents to any of the elements of the above-described aspects of an embodiment(s) that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Any term used in the specification and/or in the claims and expressly given a meaning in the Specification and/or claims in the present application shall have that meaning, regardless of any dictionary or other commonly used meaning for such a term. It is not intended or necessary for a device or method discussed in the Specification as any aspect of an embodiment to address each and every problem sought to be solved by the aspects of embodiments disclosed in this application, for it to be encompassed by the present claims. No element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element in the appended claims is to be construed under the provisions of 35 U.S.C. §112, sixth paragraph, unless the element is expressly recited using the phrase “means for” or, in the case of a method claim, the element is recited as a “step” instead of an “act”.
It will be understood by those skilled in the art that the aspects of embodiments of the present invention disclosed above are intended to be preferred embodiments only and not to limit the disclosure of the present invention(s) in any way and particularly not to a specific preferred embodiment alone. Many changes and modification can be made to the disclosed aspects of embodiments of the disclosed invention(s) that will be understood and appreciated by those skilled in the art. The appended claims are intended in scope and meaning to cover not only the disclosed aspects of embodiments of the present invention(s) but also such equivalents and other modifications and changes that would be apparent to those skilled in the art. | A cross-flow fan impeller for circulating gas in a transversely excited, pulsed, gas discharge laser is disclosed and may comprise a plurality of hubs, the hubs spaced apart along the impeller's rotation axis and establishing at least two impeller segments wherein a first segment has an output flow within 80-120% of a second segment and the first and second segment having differing blade pass frequencies. In some embodiments of this aspect, the first segment may have n number of blades the second segment m number of blades, and m≠n. In one embodiment, the impeller may be configured with n=29 and m=23 and in another embodiment, the impeller may be configured with n=23 and m=19. The impeller may be configured wherein n and m are prime numbers. | 7 |
FIELD OF THE INVENTION
[0001] This invention relates to pneumatic tires having a carcass and a belt reinforcing structure, more particularly to high speed heavy load radial ply tires such as those used on aircraft.
BACKGROUND OF THE INVENTION
[0002] Pneumatic tires for high speed applications experience a high degree of flexure in the crown area of the tire as the tire enters and leaves the contact patch. This problem is particularly exacerbated on aircraft tires wherein the tires can reach speed of over 200 mph at takeoff and landing.
[0003] When a tire spins at very high speeds the crown area tends to grow in dimension due to the high angular accelerations and velocity tending to pull the tread area radially outwardly. Counteracting these forces is the load of the vehicle which is only supported in the small area of the tire known as the contact patch.
[0004] In U.S. Pat. No. 5,427,167, Jun Watanabe of Bridgestone Corporation suggested that the use of a large number of belt plies piled on top of one another was prone to cracks inside the belt layers which tended to grow outwardly causing a cut peel off and scattering of the belt and the tread during running. Therefore, such a belt ply is not used for airplanes. Watanabe found that zigzag belt layers could be piled onto the radially inner belt layers if the cord angles progressively increased from the inner belt layers toward the outer belt layers. In other words the radially inner belt plies contained cords extending substantially in a zigzag path at a cord angle A of 5 degrees to 15 degrees in the circumferential direction with respect to the equatorial plane while being bent at both sides or lateral edges of the ply. Each of the outer belt plies contains cords having a cord angle B larger than the cord angle A of the radially inner belt plies.
[0005] In one embodiment each of the side end portions between adjoining two inner belt plies is provided with a further extra laminated portion of the strip continuously extending in the circumferential direction and if the radially inner belt plies have four or more in number then these extra laminated portions are piled one upon another in the radial direction. The inventor Watanabe noted the circumferential rigidity in the vicinity of the side end of each ply or the tread end can be locally increased so that the radial growth in the vicinity of the tread end portion during running at high speed can be reduced.
SUMMARY OF THE INVENTION
[0006] A pneumatic tire having a carcass and a belt reinforcing structure wherein the belt reinforcing structure is a composite belt structure having at least one pair of radially outer zigzag layers and at least one spirally wound belt layer with cords inclined at an inclination of 5 degrees or less relative to the tire's centerplane and located radially inward of and adjacent to the at least two radially outer zigzag belt layers.
[0007] The at least two radially outer zigzag belt layers have cords inclined at 5 degrees to 30 degrees relative to the tire's centerplane and extending in alternation to turnaround points at each lateral edge of the belt layer. At each turnaround point the cords are folded or preferably bent to change direction across the crown of the carcass thus forming a zigzag cord path.
[0008] In a preferred embodiment at least two radially inner zigzag belt layers are positioned between the carcass and the at least one spirally wound belt layer. Each of the radially inner zigzag belt layers has cords wound at an inclination of 5 degrees to 30 degrees relative to the centerplane of the tire and extending in alternation to turnaround points at each lateral edge of the belt layers.
[0009] The cords of the at least two radially inner spirally wound belt layers are wound from a single cord or from a group of 2 to 20 cords which continuously extend to form spirally wound belt layer and the at least two radially outer belt layers.
[0010] Alternatively, the cords of the spirally wound belt layer in a single cord or a group of 2 to 20 cords may be continuously wound to form the at least two radially outer belt layers.
[0011] As described above the tire should have three belt layers, preferably five, as a minimum as measured at the tire's center.
[0012] The tire is well suited for high speeds and large loads such as found in aircraft tires.
DEFINITIONS
[0013] “Apex” means a non-reinforced elastomer positioned radially above a bead core.
[0014] “Aspect ratio” of the tire means the ratio of its section height (SH) to its section width (SW) multiplied by 100% for expression as a percentage.
[0015] “Axial” and “axially” mean lines or directions that are parallel to the axis of rotation of the tire.
[0016] “Bead” means that part of the tire comprising an annular tensile member wrapped by ply cords and shaped, with or without other reinforcement elements such as flippers, chippers, apexes, toe guards and chafers, to fit the design rim.
[0017] “Cut belt or cut breaker reinforcing structure” means at least two cut layers of plies of parallel cords, woven or unwoven, underlying the tread, unanchored to the bead, and having both left and right cord angles in the range from 10 degrees to 33 degrees with respect to the equatorial plane of the tire.
[0018] “Bias ply tire” means a tire having a carcass with reinforcing cords in the carcass ply extending diagonally across the tire from bead core to bead core at about a 25°-50° angle with respect to the equatorial plane of the tire. Cords run at opposite angles in alternate layers.
[0019] “Carcass” means the tire structure apart from the belt structure, tread, undertread, and sidewall rubber over the plies, but including the beads.
[0020] “Circumferential” means lines or directions extending along the perimeter of the surface of the annular tread perpendicular to the axial direction.
[0021] “Chafers” refer to narrow strips of material placed around the outside of the bead to protect cord plies from the rim, distribute flexing above the rim, and to seal the tire.
[0022] “Chippers” mean a reinforcement structure located in the bead portion of the tire.
[0023] “Cord” means one of the reinforcement strands of which the plies in the tire are comprised.
[0024] “Equatorial plane (EP)” means the plane perpendicular to the tire's axis of rotation and passing through the center of its tread.
[0025] “Flipper” means a reinforced fabric wrapped about the bead core and apex.
[0026] “Footprint” means the contact patch or area of contact of the tire tread with a flat surface at zero speed and under normal load and pressure.
[0027] “Innerliner” means the layer or layers of elastomer or other material that form the inside surface of a tubeless tire and that contain the inflating fluid within the tire.
[0028] “Net-to-gross ratio” means the ratio of the tire tread rubber that makes contact with the road surface while in the footprint, divided by the area of the tread in the footprint, including non-contacting portions such as grooves.
[0029] “Nominal rim diameter” means the average diameter of the rim flange at the location where the bead portion of the tire seats.
[0030] “Normal inflation pressure” refers to the specific design inflation pressure and load assigned by the appropriate standards organization for the service condition for the tire.
[0031] “Normal load” refers to the specific design inflation pressure and load assigned by the appropriate standards organization for the service condition for the tire.
[0032] “Ply” means a continuous layer of rubber-coated parallel cords.
[0033] “Radial” and “radially” mean directions radially toward or away from the axis of rotation of the tire.
[0034] “Radial-ply tire” means a belted or circumferentially-restricted pneumatic tire in which the ply cords which extend from bead to bead are laid at cord angles between 65° and 90° with respect to the equatorial plane of the tire.
[0035] “Section height” (SH) means the radial distance from the nominal rim diameter to the outer diameter of the tire at its equatorial plane.
[0036] “Zigzag belt reinforcing structure” means at least two layers of cords or a ribbon of parallel cords having 2 to 20 cords in each ribbon and laid up in an alternating pattern extending at an angle between 5° and 30° between lateral edges of the belt layers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] [0037]FIG. 1 us a schematically section view of a first embodiment of the tire according to the invention;
[0038] [0038]FIG. 2 is a partially cutaway top view of the tire shown in FIG. 1;
[0039] [0039]FIG. 3 is a schematically perspective view of an inner or outer zigzag belt layer in the middle of the formation;
[0040] [0040]FIG. 4 is a schematically developed view of the inner or outer zigzag belt layers In the middle of the formation;
[0041] [0041]FIG. 5 is an enlargedly developed view of the inner or outer zigzag belt layers in the vicinity of the side end of the ply in the middle of the formation;
[0042] [0042]FIG. 6 is an enlargedly developed view of another embodiment of the inner belt layer in the vicinity of the side end of the ply in the middle of the formation;
[0043] [0043]FIG. 7 is a schematically enlarged section view of the composite belt layers in the vicinity of side end portions of these plies;
[0044] [0044]FIG. 8 is a schematically developed view of the inner layer located at an outmost side;
[0045] [0045]FIG. 9 is a schematically enlarged section view of another embodiment of plural inner belt plies in the vicinity of side end portions of these plies.
DETAILED DESCRIPTION OF THE INVENTION
[0046] In FIGS. 1 and 2, numeral 21 is a radial tire of the preferred embodiment of the invention, as shown, to be mounted onto an airplane, which comprises a pair of bead portions 23 each containing a bead core 22 embedded therein, a sidewall portion 24 extending substantially outward from each of the bead portions 23 in the radial direction of the tire, and a tread portion 25 of substantially cylindrical shape extending between radially outer ends of these sidewall portions 24 . Furthermore, the tire 21 is reinforced with a carcass 31 toroidially extending from one of the bead portions 23 to the other bead portion 23 . The carcass 31 is comprised of at least two carcass plies 32 , e.g. six carcass plies 32 in the illustrated embodiment. Among these carcass plies 32 , four inner plies are wound around the bead core 22 from inside of the tire toward outside thereof to form turnup portions, while two outer plies are extended downward to the bead core 22 along the outside of the turnup portion of the inner carcass ply 32 . Each of these carcass plies 32 contains many nylon cords 33 such as nylon-6,6 cords extending substantially perpendicular to an equatorial plane E of the tire (i.e. extending in the radial direction of the tire). A tread rubber 36 is arranged on the outside of the carcass 31 in the radial direction.
[0047] A belt 40 is arranged between the carcass 31 and the tread rubber 36 and is comprised of plural inner belt plies or layers 41 located near the carcass 31 , i.e. two radially inner belt layers 41 in the illustrated embodiment and plural radially outer belt layers 42 located near to the tread rubber 36 , i.e. two radially outer belt layers 42 in the illustrated embodiment. As shown in FIGS. 3 and 8, each of the radially inner belt plies 41 is formed by providing a rubberized strip 43 of one or more cords 46 , winding the strip 43 generally in the circumferential direction while being inclined to extend between side ends or lateral edges 44 and 45 of the layer forming a zigzag path and conducting such a winding many times while the strip 43 is shifted at approximately a width of the strip in the circumferential direction so as not to form a gap between the adjoining strips 43 . As a result, the cords 46 extend substantially zigzag in the circumferential direction while changing the bending direction at a turnaround point at both ends 44 , 45 and are substantially uniformly embedded in the first inner belt layer 41 over a full region of the first inner belt layer 41 . Moreover, it is intended to form the radially inner belt layer 41 by the above method, the cords 46 lie one upon another, so that two first and second inner belt layers 41 are formed while crossing the cords 46 of these plies with each other. Similarly the radially outer belt layers 42 are made using the same method. Interposed between the inner layers 41 and outer layers 42 is at least one spirally wound layer 39 of cords 46 , the cords being wound at an angle of plus or minus 5 degrees or less relative to the circumferential direction.
[0048] In the pneumatic radial tire for airplanes, there are various sizes, the tire illustrated is a 42×17. OR18 with a 26 ply rating and the tire 21 has the belt composite reinforcing structure as shown in FIG. 9. As shown the tire of FIG. 9 has two inner zigzag layers 41 and three spiral layers 39 and two outer zigzag layers 42 . In any such tire size, the cords 46 of the inner belt plies 41 cross with each other at a cord angle A of 5 degrees to 15 degrees with respect to the equatorial plane of the tire when the strip 43 is reciprocated at least once between both side ends 44 and 45 of the ply within every 360 degrees of the circumference as mentioned above.
[0049] In the illustrated embodiment, the widths of the inner belt layers 41 become narrower as the ply 41 is formed outward in the radial direction or approaches toward the tread rubber 36 . Further, when the inner belt layers 41 is formed by winding the rubberized strip 43 containing plural cords 46 arranged in parallel with each other as mentioned above, a period for forming the ply layer 41 can be shortened and also the cord 46 arrangement can be made accurate. However, the strip 43 is bent at the side ends 44 , 45 of the ply with a small radius of curvature R as shown in FIG. 5, so that a large compressive strain is produced in a cord 46 located at innermost side of the curvature R in the strip 43 to remain as a residual strain. When the cord 46 is nylon cord, if the compressive strain exceeds 25%, there is a fear of promoting the cord fatigue. However, when a ratio of R/W (R is a radius of curvature (mm) of the strip 43 at the side ends 44 , 45 of the layer, and W is a width of the strip 43 ) is not less than 2.0 as shown in FIG. 6, the compressive strain produced in the cord 46 can be controlled to not exceed 25%. Therefore, when the inner belt layer 41 is formed by using the rubberized strip 43 containing plural nylon cords 46 therein, it is preferable that the value of R/W is not less than 2.0. In addition to the case where the strip 43 is bent at both side ends 44 , 45 of the ply in form of an arc as shown in FIG. 5, the strip 43 may have a straight portion extending along the side end 44 ( 45 ) and an arc portion located at each end of the straight portion as shown in FIG. 6. Even in the latter case, it is favorable that the value of R/W in the arc portion is not less than 2.0. Furthermore, when the strip 43 is wound while being bent with a given radius of curvature R at both side ends 44 , 45 of the ply, a zone 47 of a bent triangle formed by overlapping three strips 43 with each other at a half width of the strip as shown in FIG. 7 is repeatedly created in these bent portions or in the vicinity of both side ends 44 , 45 of the ply in the circumferential direction as shown in FIG. 5. These two strips 43 are usually overlapped with each other by each forming operation. The width changes in accordance with the position in the circumferential direction continuously in the circumferential direction. Moreover, these laminated bent portions 47 turn inward in the axial direction as they are formed outward in the radial direction as shown in FIG. 7 because the widths of the inner belt layers 41 become narrower toward the outside in the radial direction as previously mentioned. In the bent portion 47 , the outer end in widthwise direction of the middle strip 43 c sandwiched between upper and lower strips 43 a and 43 b overlaps with the zone 47 located inward from the middle strip 43 c in the radial direction as shown in FIG. 7. When the belt 40 is constructed with these inner belt layers 41 , the total number of belt layers or plies can be decreased while maintaining total strength but reducing the weight and also the occurrence of standing wave during the running at high speed can be prevented.
[0050] The middle layers 39 of the composite belt structure 40 are spirally wound around the radially inner belt layers 41 . As shown in FIG. 7 the spirally wound layer 39 extends completely across the two radially inner belt layers 41 and ends at 39 a just inside the end 41 a . The cords 46 within each strip 39 extend at an angle of 5 degrees or less relative to the circumferential equatorial plane. As shown four cords are in each strip. In practice the strips 41 , 39 ,and 42 could be wound using a single cord 46 or plural cords 46 in a strip or ribbon having plural cords in the range of 2 to 20 cords within each strip. In the exemplary tire 21 of the size 42×17.OR18 strips 43 having 8 cords per strip 42 were used. The strips 43 had a width W, W being 0.5 inches. It is believed preferable that the strip width W should be 1.0 inch or less to facilitate bending to form the zigzag paths of the inner and outer layers 41 , 42 .
[0051] In the most preferred embodiment the layers 41 , 39 , and 42 are all formed from a continuous strip 43 that simply forms the at least two radially zigzag layers 41 and then continues to form the at least one spirally wound layer 39 and then continues on to form the at least two radially outer layers 42 . Alternatively, the spirally wound layers 39 could be formed as a separate layer from a strip 43 . This alternative method of construction permits the cords 46 to be of different size or even of different materials from the zigzag layers 41 and 42 . What is believed to be the most important aspect of the invention is the circumferential layer 39 by being placed between the zigzag layers 41 and 42 greatly-reduces the circumferential growth of the tire 21 in not only the belt edges 44 , 45 but in particular the crown area of the tread 36 . The spirally wound circumferential layer 39 , by resisting growth in the crown area of the tire, greatly reduces the cut propensity due to foreign object damage and also reduces tread cracking under the grooves. This means the tire's high speed durability is greatly enhanced and its load carrying capacity is even greater. Aircraft tires using multiple layers of only zigzag ribbons on radial plied carcasses showed excellent lateral cornering forces. This is a common problem of radial tires using spiral layers in combination with cut belt layers which show poor cornering or lateral force characteristics. Unfortunately, using all zigzag layered belt layers have poor load and durability issues that are inferior to the more conventional spiral belt layers in combination with cut belt layers.
[0052] The present invention has greatly improved the durability of the zigzag type belt construction while achieving very good lateral force characteristics as illustrated in FIG. 10. The all zigzag belted tire A is slightly better than the tire B of the present invention which is shown better than the spiral belt with a combination of cut belt layers of tire C in terms of lateral forces. Nevertheless the all zigzag belted tire A cannot carry the required double overloads at inflation whereas the tire B of the present invention easily meets these load requirements.
[0053] The tire of the present invention may have a nylon overlay 50 directly below the tread. This overlay 50 is used to assist in retreading. | A pneumatic tire having a carcass and a belt reinforcing structure wherein the belt reinforcing structure is a composite belt structure having at least one pair of radially outer zigzag layers and at least one spirally wound belt layer with cords inclined at an inclination of 5 degrees or less relative to the tire's centerplane and located radially inward of and adjacent to the at least two radially outer belt layers. The at least two radially outer zigzag belt layers have cords inclined at 5 degrees to 30 degrees relative to the tire's centerplane and extending in alternation to turnaround points at each lateral edge of the belt layer. At each turnaround point the cords are folded or preferably bent to change direction across the crown of the carcass thus forming a zigzag cord path. | 8 |
FIELD OF THE INVENTION
The present invention relates to the class of fishing lures known as spoons.
BACKGROUND OF THE INVENTION
Artificial fishing lures shaped like spoons are well known. Most have a hook and weedguard attached by soldering, welding or by a screw means such as illustrated in U.S. Pat. No. 3,869,821. They are commonly called spoons because of their body shape. They are attached to fishing lines and pulled through the water where they assume a horizontal position. Spoons are usually metal with a high polished or bright painted scheme to attract fish. The spoon shape is designed to ensure that the lure will not rise to the top of the water at high trolling speeds.
A typical spoon is disclosed in C. F. Pflueger U.S. Pat. No. 1,992,766 issued on Feb. 26, 1935 for "Trolling Spoon". It incorporates a removable hook and weedguard secured screws. The screws are a labor intensive means to assemble the device, adversely affect the action of the lure when trolled, and work loss and fail.
H. C. Toepper U.S. Pat. No. 2,167,163 issued on July 25, 1939 illustrates a spoon assembly which attempts to solve the problems created by screws. A lug is pressed snugly against the loop of the eye retaining both weedguard and hook permanently to the spoon body. The screws are eliminated but the result is a non-removable hook and weedguard.
R. C. Arnold in U.S. Pat. No. 2,519,338 issued Aug. 22, 1950 illustrates the continued reliance on screws for securing removable weedguards and hooks.
C. F. Mellin illustrates the persistence of screws in U.S. Pat. No. 2,619,764 issued Dec. 2, 1952. He teaches a removable hook and weedguard both retained by a screw.
A still further example of the persistence of the use of screws to secure hooks and weedguards is issued to R. O. Tibbetts in U.S. Pat. No. 2,895,252 issued July 21, 1959.
Thus the industry has accepted the inevitable use of screws to secure hooks and weedguards to spoons but a few are valiantly trying to improve the art and avoid the penalties extracted by the screw.
D. F. Hyland in U.S. Pat. No. 2,567,813 issued Sept. 11, 1951 teaches a removable hook which is retained by a snap but the weedguard is part of the stamped spoon body and not removable.
E. A. Ebert in U.S. Pat. No. 2,989,816 issued June 27, 1961 avoids the screw but the hook and weedguard are not removable.
The foregoing represents the various attempts to improve spoon type artificial baits. They all have one thing in common--they are costly and thus the spoons are not economically feasible to manufacture.
Soldering or welding have been used as an alternative to screws and crimping but the spoon, hook and weedguard have to be jigged to hold the parts during joining. When the parts are soldered or welded, they are annealed by the heat required to perfect the bonding. Because of the annealing which takes the temper out of the metal, the entire assembled spoon must be heat-treated to make the weedguard harden enough to be springy again.
The soldering or welding and heat-treating cause the assembly to be unsightly and it must be cleaned and polished to receive any plating that may be desired.
Polishing the assembled spoon is a very dangerous procedure due to the sharp pointed hook and weedguard. Because the hook and weedguard are attached, each spoon must be polished one at a time.
A further disadvantage resulting from soldering or welding is the effects of the required pickling acids on equipment, buildings and personnel.
With the present invention, both the manufacturer and end user gains. Some of the gains to the manufacturer have been eluded to. Exemplary gains to the end user follow:
When a soldered or crimped spoon breaks either the hook or the weedguard is useless and the metal spoon is thrown away. This wastefulness can be eliminated if the parts are replaceable. Screws provide this advantage but require a repair facility that is not normally available at the fishing site.
In summary, present day spoons are lacking because hooks, if removable, cannot be removed without tools, hooks and/or weedguards cannot be rapidly changed when a different size is desired, and weedguards cannot be added or removed as required.
OBJECTIVES OF THE INVENTION
Accordingly, it is the primary objective of the present invention to provide an artificial fishing lure of the spoon type which completely eliminates all the manufacturing steps now used in jigging and soldering spoons, hooks and weedguards into an assembly.
Another objective is the elimination of the cost to the manufacturer for bonding metals such as silver base solder required in order to be able to plate the spoon body at the end of the manufacturing process.
Another objective is the elimination of costly clean-up from plating of the final product.
Another objective is the elimination of the cost of the gases used in soldering the hook and the weedguard to the spoon body.
Another objective is eliminating having to plate the spoon bodies due.
Another objective is to produce a spoon that can be tumble polished.
Another objective is to make it possible for the manufacturer to add the detachable hook as a last step before he packages the finished product.
Another objective is to minimize the number of persons exposed to attached hooks, thereby decreasing the manufacturer's insurance cost and reducing the dangers to the workers.
Another objective is to completely eliminate the need to polish spoons with hooks attached.
A still further objective is to eliminate the need to heat treat the metals that were previously annealed during the soldering process.
Yet another objective is to make it possible for the end user to replace either the hook or the weedguard, or both.
A still further objective is to make it possible for the fisherperson to change the diameter of the wire used in the weedguard in order to make the weedguard easier for the fish to become hooked, which objective will also make it possible for the fisherperson to change to a weedguard of large diameter wire to make the weedguard stiffer.
A still further objective is to provide a spoon on which wrong sized or broken hook may be replaced without tools.
Another objective is to make it possible for the manufacturer to polish large quantities of spoon bodies at the same time rather than one at a time as is now done due to the permanently attached hook on the spoon body.
A still further objective of the invention is to produce a spoon type artificial lure with removable, replaceable hooks and weedguards.
Another objective is to completely eliminate the soldering, welding, screwing or crimping phases of manufacturing and makes it possible to polish the spoon body with the hook and weedguard unattached.
A further objective is a spoon on which the weedguards can be changed in the field without tools and in seconds so one can use different diameter weedguards to make the weedguard harder to unseat or easier to unseat.
Another objective of the present invention is to make it possible to change the hook size as well as replace broken hooks on spoons in the field without tools.
Another objective of this invention is to provide great savings in the time to manufacturer and the cost to manufacturer by eliminating the manufacturing steps of jigging to hold the parts to be assembled. Soldering, crimping or screwing steps, and the hardening steps of the annealed parts while providing the ability to polish in large quantities greatly reduces the overall cost.
Another objective is to make a fishing spoon by a means which greatly reduces the cost to manufacturers and allows the fisherperson to rapidly replace broken hooks and/or weedguards without tools. Spoons in use to date have their hooks soldered as well as the weedguard soldered to them.
The foregoing and other objectives of the invention will become apparent in light of the specification and claims presented herein.
SUMMARY OF THE INVENTION
The present invention is an artificial spoon type fishing lure including openings through the spoon body which are positioned and dimensioned to permit cooperation between the shape of the spoon and the structure of associated hooks and weedguards whereby the hooks and weedguards may be attached and secured to the spoon by the spring tension inherent in the parts.
DESCRIPTION OF THE DRAWINGS
FIG. 1 a 3/4 view of the concave surface of the spoon body.
FIG. 2 is a top view of spoon body looking at its inside concave surface.
FIG. 3 is a top view of the outside convex surface of spoon body.
FIG. 4 is a side view of the spoon body.
FIG. 5 is a side view of a removable, replaceable fish hook of the type having its eye bent up 90 degrees to the hook's shank. A patented connector, U.S. Pat. No. 3,869,821 is fitted through the eye.
FIG. 6 is a standard hook with the eye laying in the same plane as curve of the hook.
FIG. 7 is a detachable, replaceable weedguard.
FIG. 8 is a top view of a left hand version of the weedguard.
FIG. 9 is a top view of a right hand version of the weedguard.
FIG. 10 illustrates the first step in attaching the removable hook to the spoon body.
FIG. 11 illustrates the position of the hook at the second step in attaching it to the spoon body. Note the hook's point 19 has entered aperture 7 in the spoon's body.
FIG. 12 illustrates the detachable, removable hook as it is positioned in the third step of attaching it to the spoon's body.
FIG. 13 illustrates the hook positioned at the final step of attaching it to the spoon's body. The hook has been rotated 180 degrees from its position shown in FIG. 12.
FIG. 14 illustrates a hook of the type illustrated in FIG. 6, positioned same as the hook in FIG. 13.
FIG. 15 illustrates the first step of attaching removable weedguard to the spoon's body using an aperture common with the hook. Note that the weedguard has entered the front aperture in the spoons' body.
FIG. 16 illustrates the removable, replaceable weedguard as it is positioned in the second step of attaching it to the spoon's body using an aperture common with the hook and an alternate weedguard 15A having different spring properties. Note that one free end of the weedguard is in one aperture of the spoon's body and the long straight part of the weedguard is in another aperture in the spoon's body.
FIG. 17 illustrates the weedguard as it is positioned in the third step of being attached to the spoon's body using an aperture common with the hook. The weedguard is secured onto the spoon's body.
FIG. 18 illustrates the weedguard's free end positioned under the hook's point. The spoon is ready for the fishing line to be attached.
FIG. 19 is same configuration as FIG. 18 except the hook is the type illustrated in FIG. 6.
FIG. 20 illustrates the first step of attaching removable weedguard to the spoon's body using an auxiliary aperture. Note that the weedguard has entered the front aperture in the spoons' body.
FIG. 21 illustrates the removable, replaceable weedguard as it is positioned in the second step of attaching it to the spoon's body using an auxiliary aperture. Note that one free end of the weedguard is in one aperture of the spoon's body and the long straight part of the weedguard is in another aperture in the spoon's body.
FIG. 22 illustrates the weedguard as it is positioned in the third step of being attached to the spoon's body using an auxiliary aperture. The weedguard is secured onto the spoon's body.
FIG. 23 illustrates the weedguard's free end positioned under the hook's point. The spoon is ready for the fishing line to be attached.
FIG. 24 is same configuration as FIG. 23 except the hook is the type illustrated in FIG. 6
DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a top 3/4 view of the spoon's concave inner surface. A portion 4 of the spoon is bent up 90 degrees to the remainder of the spoon's body to form a tab. A front aperture 5 is provided in the tab 4 and may continue through the bend 11 and into the spoon body as illustrated. An aperture 6 is provided in the middle of the spoon body 8 and an aperture 7 is located at the large end of the spoon. An optional small aperture 22 is offset from aperture's 5, 6, and 7. The foregoing features and the general overall shape of the spoon may be more clearly understood by comparing the top views of the concaved side of the spoon in FIGS. 1 and 2 with the convexed bottom view of FIG. 3 and side view of FIG. 4. The groove 10 of FIG. 3 is stamped or ground into the spoon to lock the hook in position.
FIG. 5 illustrates a fishing lure attachment or component better known as a hook that may be used in the present invention. This hook incorporates a patented coupling device, (U.S. Pat. No. 3,869,821 issued Mar. 11, 1975) in its eye 2 which is bent up at 90 degrees to the hook's shank 3. FIG. 6 illustrates an alternate hook that may be used with this invention. It includes a point 19 and a barb 18 connected to the main shank 3A by a curved section 17. This is a standard straight shank hook with an eye in the same plane as the hook's curved section. The hooks illustrated are exemplary. The invention may be used with all hook styles, including multi-pointed hooks.
FIGS. 7, 8 and 9 illustrate another fishing lure attachment or component, a removable, replaceable, spring wire weedguard 12. It includes an end portion 13 which is received by a hook barb 18. Two opposing bends 14 and 16 are separated by the straight section 15. The bends 14 and 16 secure the weedguard appliance into apertures 5 and 6 of spoon's body 8 so that the spring section 12 can protect the hook opening.
FIG. 8 illustrates a top view of a weedguard appliance with the weedguard tip 13A bent to the left side. In FIG. 9, the tip 13B is bent to the right side. Thus creating right and left handed weedguards.
A preferred method of producing the spoon is to punch spoon blanks, including holes or apertures 5, 6, 7 and 22 from sheets of metal, die form the convex shape, bent tab 4 and recess 10, polish or otherwise provide a suitable surface finish and snap on the components such as hooks and weedguards as illustrated in FIGS. 10 through 24.
To add a hook to the spoon body, the point 19 of the hook is passed through aperture 5 in the spoon's body 8 as illustrated in FIG. 10. The hook shank 3 is slid through aperture 5, rotated 180 degrees and the hook point 19 is placed in aperture 7 as shown in FIG. 11.
The curved portion 17 of the hook is pushed down and moved towards the small end of spoon to force the hook point 19 and curved portion 17 through the aperture as shown in FIG. 12.
The hook is rotated 180 degrees to the position illustrated in FIG. 13. When the 180 degree rotation of hook takes place and the spoon is configured as in FIG. 13, the shank area 3 of the hook is on the inside of the concave portion of the lure body 8. In this position, the entire hook's shank is under stress and the shank can be seen to be curved upwards from the concave portion of the spoon if the spring of the hook is less than the spoon body. This curve, or arching, acts as the tension means to retain the hook and spoon in the position seen in FIG. 13 where it is locked in position by the groove 10 illustrated in FIG. 3 and into which the portion of the shank 3 transitioning into the curved portion 17 snaps when the hook is rotated to the position shown in FIGS. 13 and 14.
FIG. 14 shows a hook with a standard eye 21 in sam plane as curve in hook. Regardless of hook style, the basic procedures illustrated by FIGS. 10 through 13 are used to attach the hook, however when the hook is rotated from the FIG. 12 position to the FIG. 14 position, the hook eye 21 functions as a cam surface against the edges of aperture 5 which forces the spoon tab 4 toward aperture 7 to create a spring bias which snaps the hook into position because of the elliptical shape of aperture 5. Once snapped in position, the differential spring tension between the hook and spoon body hold the hook securely in position as illustrated in FIG. 14 and the groove 10 may be eliminated.
One method of attaching a weedguard is illustrated by FIGS. 15 through 19. In FIG. 15, the hook engaging end 13 is passed through aperture 5. Next, the spring section 12 is slid through aperture 5 and maneuvered so that the bent end 16 passes through aperture 6 as illustrated in FIG. 16. The weedguard end 13 is pulled up and toward the hook end of the spoon until the bend 14 snaps into place as shown in FIG. 17. It is held in this position by the relative spring force exerted between the spoon body and the section of the weedguard including bends 14 and 16 and the wire therebetween.
The spring section 12 of the weedguard is bent and manipulated so that the hooked end 13 engages the barb 18 and wraps about the hook point as illustrated in FIGS. 18 and 19. The assembled spoon is now ready to be secured to the fishing line and fished through weeds.
The weedguard and hook may be removed from the spoon body 8 by reversing the steps shown in FIGS. 10 through 24. The Weedguard 12 can be removed and replaced while the hook is attached to the spoon body to make it possible for the fisherperson to change the diameter of the wire used in the weedguard in order to make the weedguard easier for the fish to become hooked or make it possible for the fisherperson to change to a weedguard of larger diameter wire to make the weedguard stiffer. This principle may be extended to the fish hooks so that they may also be exchanged for hooks having different wire diameters or other properties.
FIGS. 20 through 24 illustrate attaching a weedguard to a spoon using an auxiliary aperture 22 instead of aperture 5. Aperture 22 is offset from apertures 5, 6, 7 in the spoon's body 8. This offset keeps the weedguard from coming in contact with the hooks shank 3 as it does in FIGS. 15 through 19. By keeping the weedguard out of contact with the hook's shank 3, the weedguard is allowed free movement in all directions as compared to the restricted or laterally biased movement which occurs when the weedguard is allowed to come in contact with the hook's shank 3. With restricted or laterally biased movement of the weedguard, there is a tendency for the weedguard tip 13 to become locked under the hook's point. This is undesirable, therefore the preferred embodiment is shown in FIGS. 20 through 24 using offset aperture 22 to allow unbiased up and down movement of the weedguard.
The procedures for using aperture 22 to install a weedguard begin with FIG. 20 where the hook engaging end 13 is passed through aperture 22. Next the spring section 12 is slid through aperture 22 and maneuvered so that the bent end 16 passes through aperture 6 as illustrated in FIG. 21. The weedguard end is pulled up and toward the hook point end of the spoon until the bend 14 snaps into place as shown in FIG. 22. The spring section 12 of the weedguard is bent and manipulated so that the hook end 13 engages the barb 18 and wraps about the hook point as illustrated in FIGS. 23 and 24
Although the preferred embodiments of this invention have been illustrated and described, variations and modifications may be apparent to those skilled in the art. Therefore, I do not wish to be limited thereto and ask that the scope and breadth of this invention be determined from the claims which follow rather than the above description. | An artificial spoon type fishing lure including openings through the spoon body which are positioned and dimensioned to permit cooperation between the shape of the spoon and the structure of associated hooks and weedguards whereby the hooks and weedguards may be attached and secured to the spoon by the spring tension inherent in the parts. | 0 |
RELATED PATENT APPLICATION
U.S. Provisional application Ser. No. 60/006,196, filed Nov. 2, 1995.
FIELD OF THE INVENTION
The present invention relates to an adjustable valve for controlling the amount of water refilling a toilet bowl and, more particularly, to such a valve which adjusts the rate of flow of water refilling the toilet bowl.
BACKGROUND OF THE INVENTION
A concerted effort is now afoot to now conserve fresh potable water. Flush toilets use enormous amounts of water, consuming four to five gallons per flush. A lot of the water consumed is used to fill toilet bowls after flushing. Several quarts of water may be required to fill the bowl and, in many cases, this amount of water is unnecessary. The water level in some toilet bowls is so high that, on occasion, a person using the toilet gets wet when they sit. The present invention allows one to adjust the water level in the bowl to a suitable level which results in extensive water savings.
U.S. Pat. No. 3,086,546 includes an element for adjusting the rate of water flow to an overflow tank but the adjustment is hidden and not readily retrofitted.
SUMMARY OF THE INVENTION
In view of the aforementioned considerations it is a feature of the present invention to provide a new and improved apparatus for adjustably controlling the rate of water flow from a water inlet to an overflow pipe in a flush toilet.
In view of this feature and other features the present invention is directed to a valve which is inserted in a tubular connection between a flush tank inlet line and an overflow pipe. The valve is adjustable from a location outside of the tubular connection.
In a more specific aspect, the valve is a ball valve and, in a still more specific aspect, the valve is mounted in the tank by either a strut connected to the overflow pipe or by a bracket fitted over an upper edge of the flush tank.
Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
Various other features and attendant advantages of the present invention will be more fully appreciated as the same becomes better understood when considered in conjunction with the accompanying drawings, in which like reference characters designate the same or similar parts throughout the several views, and wherein:
FIG. 1 is a front view, with portions broken away, of a toilet bowl flush tank employing the present invention;
FIG. 2 is an enlarged view of a valve and associated mounting bracket configured in accordance with the principles of the present invention;
FIG. 3 is a view of a second embodiment of a valve of the present invention;
FIG. 4 is an end view of the valve of FIGS. 1-3; and
FIG. 5 is a side view of the valve showing alternative screw-in nipples.
DETAILED DESCRIPTION
Referring now to FIG. 1, there is shown a conventional flush tank 10 for a toilet bowl (not shown). The flush tank includes a water inlet line 12 and a conventional main valve 14 which is opened by an operating handle 16 and closed by a float 17. The main valve 14 is connected by first a tube 18 to a secondary valve 20 configured in accordance with the principles of the present invention. The secondary valve 20 is connected by a second tube 22 to an overflow pipe 24 that is connected by a passage 26 to the toilet bowl (now shown). If the water level in the tank 10 rises above the top of the overflow pipe 24 due to a malfunction in the valve 14, then the water drains down the overflow pipe 24 and into the toilet bowl where it passes through the drain line of the bowl and into the sewer system.
When the toilet is flushed, it is necessary to replenish water in the toilet bowl as well as the flush tank 10. This is ordinarily accomplished by water from the inlet line 12 flowing through main the valve 14 and the tube 18 directly into the overflow pipe 24. Thus, as the flush tank 10 fills, so does the toilet bowl. By filling the toilet bowl with water, sewer gases are blocked from venting through the toilet bowl into the lavatory or bathroom. Unfortunately, many toilet bowls fill to an unnecessarily high level, thereby wasting water and on occasion soaking portions of the person sitting on the toilet.
The secondary valve 20 of the instant invention prevents this by controlling the rate of water flow into the overflow pipe 24. By reducing the rate of water flow into the overflow pipe 24, the amount of water which can flow into the overflow pipe before the float 17 terminates the flow of water into the inlet tube 12 can be reduced substantially. This is because the reduced flow rate multiplied by time results in less water volume.
The secondary valve 20 is preferably a ball valve in which a spherical valve element 28 having a passage 29 rotated by an operator such as a handle 30 to align the passage 29 with inlet passage 31a and outlet passage 31b which are axially aligned in the valve body 32. The amount of water in the toilet bowl is determined by observing the water level and adjusting the rate of flow through the valve 20 by turning the handle 30.
The valve 20 may be supported in the tank 10 by a bracket 40 shown in solid lines in FIGS. 1 and 2 and dotted lines in FIGS. 3 and 4 which has a U-shaped support 42 that fits over the top of the tank wall 44 and a shelf 46 having a pair of arcuate retainers 48 and 50 that are fit around barrel portions 52 and 54 of the valve 20. The bracket 40 is preferably made of a flexible plastic material so that the circular retainers 48 and 50 can be bent or deflected to easily position the valve 20 therein.
An alternative approach to the bracket 40 is a strut support 60. The strut support 60 comprises a strut 62 which has a resilient clamp 64 at a first end thereof which clamps around the overflow pipe 24, as is seen in FIG. 4. Note in FIG. 4 that there are two ends 65 and 66 separated by a space 67. Since the clamp 64 is resilient, it is spread to receive the pipe 24 and released to resiliently clamp therearound. At the top or second end of the strut 60, a support plate 46 similar to the support plate that is used with the bracket 40. When using the strut support 60, the U-shaped retainer 42 is no longer needed. The clamp 64 is adjustable on the overflow pipe 24 so that it can be raised and lowered within the flush tank 10 to accommodate flush tanks of different heights. Accordingly, the position of the secondary valve 20 is variable within the flush tank 10.
In the embodiment of FIG. 3, the outlet is an elbow tube 70 that dispenses directly into the overflow pipe 24. Accordingly, there is no need for no additional tubing such as the tube 22.
Referring now to FIG. 5, it is seen that the valve 20 can be furnished with alternative inlet nipples 70 and 72 each of which has a projecting end with annular barbs 73 which retain tubes 18 of various sizes on the valve 14 (see FIGS. 1, 2 and 3). The threaded ends 76 of the nipples 70 and 72 which are threaded into the body of the valve 20 have the same diameter, but the projecting ends 78 and 79 are of differing diameters so as to accommodate tubes 18 of different diameters.
The aforedescribed configuration for the valve assembly provides a easily installed convenient device for controlling the level of water in a toilet bowl.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. | An adjustable valve is inserted in a tubular connection extending between an inlet lien and overflow pipe in the flush tank of a flush toilet. By adjusting the rate of flow through the valve, the level of water standing in the toilet is determined. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/151,712, entitled “CAPACITIVE MEASUREMENT SYSTEM AND METHOD,” filed on Jun. 2, 2011 (now U.S. Pat. No. 8,368,409), which is a continuation of U.S. patent application Ser. No. 12/381,741, entitled “CAPACITIVE MEASUREMENT SYSTEM AND METHOD,” filed Mar. 16, 2009 (now U.S. Pat. No. 7,982,471). Each of these applications is incorporated herein by reference for all purposes.
BACKGROUND OF THE INVENTION
The present invention relates generally to circuits and techniques for measurement of capacitance, and more particularly to such circuits and techniques adapted for use in touch-screen applications, touch-pad applications, and the like.
Touch screen controller circuits for use in touch screen, touch pad, and touch button applications have generally included digital controller circuitry and analog circuitry for detecting the presence of capacitance if a user touches a point on a touch screen (or a touch pad or touch button). The presence or movement of a user's finger in the vicinity of the electric field associated with the capacitance of the touch screen, touch button, etc., disturbs or impedes the electric field and therefore modifies the capacitance. The capacitance measurement circuit therefore indicates the presence of the finger as a change in the modified touchscreen or touch button capacitance. The prior art typically utilizes current sourcing/sinking circuitry, RC networks, and counters to provide a digital indication of the measured capacitance, which, in a touch screen controller, can be used to precisely identify/indicate the screen location being touched.
FIG. 1A illustrates part of a touch screen panel 1 - 1 which includes a suitable number of horizontal transparent conductors 2 disposed on one surface of a thin, transparent insulative layer (not shown). A suitable number of vertical transparent conductors 3 are disposed on the other surface of the insulative layer. The left end of each of the horizontal conductors 2 can be connected to suitable current sourcing or drive circuitry. The bottom end of each of the vertical conductors 3 can be connected to suitable current sinking or receiving circuitry. A cross-coupling capacitance C SENj occurs at an “intersection” of each horizontal conductor such as 2 -I and each vertical conductor such as 3 - j , the intersection being located directly beneath a “touch point” 13 . Note that the touching by a user's finger does not necessarily have to occur directly over a touch point. If multiple touch points 13 are sufficiently close together, then a single touching may disrupt the electric fields of a number of different cross-coupling capacitances C SENj . However, the largest change in the value of a particular cross-coupling capacitance C SENj occurs when the touching occurred directly over that particular cross-coupling capacitance.
FIG. 1B illustrates any particular horizontal conductor 2 -I and any particular vertical (as in FIG. 1A ) conductor 3 - j and the associated cross-coupling capacitance C SENj between them, I and j being row and column index numbers of the horizontal conductors 2 and the vertical conductors 3 , respectively. (By way of definition, the structure including the overlapping conductors 2 -I and 3 - j which result in the cross-coupling capacitance C SENj is referred to as “capacitor C SENj ”. That is, the term “C SENj ” is used to refer both to the capacitor and its capacitance.)
The drive circuitry for horizontal conductor 2 -I can include a drive buffer 12 which receives appropriate pulse signals on its input 4 . The output of drive buffer 12 is connected to the right end of conductor 2 -I, which is modeled as a series of distributed resistances RA and distributed capacitances CA each connected between ground and a node between two adjacent distributed resistances RA. The receive circuitry for conductor 3 - j is illustrated as being connected to the right end of vertical conductor 3 - j . A switch S 1 j is connected between conductor 3 - j and V SS . A sampling capacitor C SAMPLE has one terminal connected to conductor 3 - j and another terminal connected by conductor 5 to an input of a comparator 6 , one terminal of a switch S 2 j , and one terminal of a resistor R SLOPE . The other terminal of switch S 2 j is connected to V SS . The other terminal of resistor R SLOPE is connected to the output of a slope drive amplifier 9 , the input of which receives a signal SLOPE DRIVE. The other input of comparator 6 is connected to V SS . The output of comparator 6 is connected to an input of a “timer capture register” 7 , which can be a counter that, together with resistor R SLOPE and capacitor C SAMPLE , perform the function of generating a digital output signal on bus 14 representing the value of C SENj .
A problem of the above described prior art is that the time required for the capacitance measurement is time-varying in the sense that a lower value of the capacitance C SENj requires less counting time by timer capture register 7 , whereas a higher value of the capacitance C SENj requires more counting time by timer capture register 7 . The widely variable capacitance measurement times may be inconvenient for a user. Also, the system is quite susceptible to noise because comparator 6 in Prior Art FIG. 1B is connected via C SAMPLE during the entire capacitance measurement process.
Thus, there is an unmet need for a capacitance measurement system that is capable of making accurate measurements of a broader range of capacitances than the prior art.
There also is an unmet need for an improved digital circuit and method for making touch screen capacitance measurements in a touchscreen controller circuit or a touch button circuit.
There also is an unmet need for a digital capacitance measurement system and method having greater capacitance measurement sensitivity than the prior art.
There also is an unmet need for a digital capacitance measurement system and method having greater capacitance per LSB measurement sensitivity than the prior art.
There also is an unmet need for a digital capacitance measurement system and method having greater touch screen capacitance per LSB measurement sensitivity than the prior art.
The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a capacitance measurement system that is capable of making accurate measurements of a broader range of capacitances than the prior art.
It is another object of the invention to provide an improved digital circuit and method for making touch screen capacitance measurements in a touchscreen controller circuit or a touch button circuit.
It is another object of the invention to provide a digital capacitance measurement system and method having capacitance measurement sensitivity greater than that of the prior art.
It is another object of the invention to provide a digital capacitance measurement system and method having capacitance per LSB measurement sensitivity greater than that of the prior art.
It is another object of the invention to provide a digital capacitance measurement system and method having touch screen or touch button capacitance per LSB measurement sensitivity greater than that of the prior art.
It is another object of the invention to provide a capacitance measurement system and method that are integral with and include a SAR converter.
It is another object of the invention to provide a constant-data-rate stream of touch screen panel touch point cordinate measurements or corresponding touch point capacitance measurements that do not vary with capacitance value.
Briefly described, and in accordance with one embodiment, the present invention provides a capacitance measurement system which precharges first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of a plurality of capacitors ( 25 - 0 . . . 25 - k . . . 25 ), respectively, of a CDAC (capacitor digital-to-analog converter) ( 23 ) included in a SAR (successive approximation register) converter ( 17 ) to a first voltage (V DD ) and also precharges a first terminal ( 3 - j ) of a capacitor (C SENj or C SEN ) to a second voltage (GND). The first terminals of the CDAC capacitors are coupled to the first terminal of the capacitor to redistribute charges therebetween so as to generate a first voltage on the first terminals of the CDAC capacitors and the first terminal of the capacitor, the first voltage being representative of a capacitance of the first capacitor (C SENj ). A SAR converter converts the first voltage to a digital representation (DATA) of the capacitor. The capacitance can be a touch screen capacitance or a touch button capacitance.
In one embodiment, the invention provides a passive capacitance measurement system including a successive approximation register analog-to-digital conversion circuit (SAR ADC) ( 17 ) which includes a comparator ( 26 ). An output of the comparator ( 26 ) is coupled to an input of SAR logic and switch circuitry ( 28 , 30 ) which produces a digital output (DATA) on a digital bus ( 32 ). A passive network ( 16 ) for coupling a capacitor (C SENj in FIG. 2A or C SEN in FIG. 2F ) to be measured to the SAR ADC ( 17 ) includes a measurement conductor ( 20 ) coupled to a first terminal ( 3 - j ) of the capacitor (C SENj ), a first switching circuit (S 0 , . . . Sk, . . . Sn) which is also included in the SAR ADC ( 17 ) for coupling the measurement conductor ( 20 ) to a plurality of conductors ( 21 - 0 , . . . 21 - k , . . . 21 - n ) included in both the passive network ( 16 ) and the SAR ADC ( 17 ), and a divider/CDAC (capacitor digital-to-converter) ( 23 ) which is included in both the passive network ( 16 ) and the SAR ADC ( 17 ). The divider/CDAC includes a plurality of weighted capacitors ( 25 - 0 , . . . 25 - k , . . . 25 - n ) each having a first terminal coupled to a corresponding one of the plurality of conductors ( 21 - 0 , . . . 21 - k , . . . 21 - n ), respectively, each of the weighted capacitors having a second terminal coupled by a first conductor ( 24 ) to a first input (+) of the comparator ( 26 ). The passive network ( 16 ) also includes a first switch (S 6 ) having a first terminal coupled to the first input (−) of the comparator ( 26 ). The SAR logic and switch circuitry ( 28 , 30 ) is coupled to control the plurality of conductors ( 21 - 0 , . . . 21 - k , . . . 21 ) during a SAR conversion.
In a described embodiment, a second switch (S 1 j ) selectively couples the first terminal ( 3 - j ) of the capacitor (C SENj ) to be measured to a first reference voltage (GND), and a third switch (S 2 j ) selectively couples the first terminal ( 3 - j ) of the capacitor (C SENj ) to be measured to the measurement conductor ( 20 ). In one embodiment, the capacitor (C SENj ) to be measured is a cross-coupling capacitor ( 13 in FIG. 1A ) formed by an intersection of first ( 2 -I) and second ( 3 - j ) conductors of a touch screen panel ( 13 A). In another embodiment, the capacitor (C SEN ) to be measured is a touch button capacitor ( 13 B), the capacitor (C SEN ) to be measured having a second terminal coupled to a fixed reference voltage (GND).
In a described embodiment, the first switching circuit (S 0 . . . Sk . . . Sn) includes a first group of switches (S 0 . . . Sk . . . Sn) which are opened during a precharge phase to allow a second group of switches (S 7 k ) in the SAR logic and switch circuitry ( 28 , 30 ) to precharge the plurality of capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) to a predetermined precharge voltage (V DD ). The switches (S 0 . . . Sk . . . Sn) of the first group are closed during a measurement phase after the precharge phase to allow redistribution of charges of the capacitor (C SENj ) to be measured to produce a measurement voltage on the measurement conductor 20 and the plurality of conductors ( 21 - 0 . . . 21 - k . . . 21 - n ). The first group of switches (S 0 . . . Sk . . . Sn) are opened during a conversion phase after the measurement phase to allow the SAR ADC ( 17 ) to successively generate bits of the digital output (DATA). In a described embodiment, the plurality of CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) are binarily weighted.
In one embodiment, the passive capacitance measurement system includes a pump capacitor (C P ) coupled between the measurement conductor ( 20 ) and a predetermined low reference voltage (GND) during the precharge phase and a predetermined high reference voltage (V DD ) during the measurement phase.
In one embodiment, the passive capacitance measurement system includes auto-zeroing circuitry having an auto-zeroing switch (S 3 ) coupled between the first input (+) of the comparator ( 26 ) and a comparator reference voltage (V AZ ) coupled to a second input (−) of the comparator ( 26 ).
In one embodiment, the passive capacitance measurement system includes a secondary passive network ( 16 A,C REF in FIG. 5 ) having an output ( 24 A) coupled to a second input (−) of the comparator ( 26 ), the secondary passive network ( 16 A) being substantially similar to the passive network ( 16 ) together with the capacitor (C SENj ) to be measured.
In one embodiment, the invention provides a method for measuring a capacitance (C SENj in FIG. 2A , C SEN in FIG. 2F ) of a first capacitor (C SEN in FIG. 2A , C SEN in FIG. 2F ), including precharging at least one of a plurality of first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of a plurality of weighted CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 ), respectively, of a CDAC (capacitor digital-to-analog converter) ( 23 ) included in a SAR (successive approximation register) converter ( 17 ) to a first reference voltage (V DD ) during a precharge phase, coupling the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) to a first terminal ( 3 - j ) of the first capacitor (C SENj ) to redistribute charges among the first capacitor (C SENj in FIG. 2A , C SEN in FIG. 2F ) and at least one of the plurality of CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 ) so as to generate a first voltage on the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) and the first terminal ( 3 - j ) of the first capacitor (C SENj ) during a measurement phase, the first voltage being representative of the capacitance (C SENj ) of the first capacitor (C SENj ), and performing a successive approximation conversion operation on the first voltage to generate a digital representation (DATA) of the first capacitance (C SENj ). In a described embodiment, the method includes precharging the first terminal ( 3 - j ) of the first capacitor (C SENj ) to a second reference voltage (GND) during the precharging. The method includes opening a first group of switches (S 0 . . . Sk . . . Sn) during the precharge phase and closing at least some of the switches of a second group of switches (S 7 k ) to precharge at least some of the plurality of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) to a predetermined precharge voltage (e.g., V DD ) during the precharge phase. The method includes closing the first group of switches (S 0 . . . Sk . . . Sn) during the measurement phase after the precharge phase to allow redistribution of charges on the first capacitor (C SENj ) to produce a measurement voltage on the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ). The method includes opening the first group of switches (S 0 . . . Sk . . . Sn) during a conversion phase after the measurement phase and operating the SAR ADC ( 17 ) to successively generate bits of the digital representation (DATA) of the first capacitance (C SENj ).
In one embodiment, the method includes coupling a pump capacitor (C P ) between the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) and a predetermined low reference voltage (GND) during the precharge phase and coupling the pump capacitor (C P ) between the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) and a predetermined high reference voltage (V DD ) during the measurement phase to boost the voltage of the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) to improve the sensitivity of the measuring with respect to relatively high values of the capacitance (C SENj ) of the first capacitor (C SENj ).
In one embodiment, the invention provides a passive capacitance measurement system including means ( 30 ) for precharging at least one of a plurality of first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of a plurality of weighted CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 ), respectively, of a CDAC (capacitor digital-to-analog converter) ( 23 ) included in a SAR (successive approximation register) converter ( 17 ) to a first reference voltage (V DD ) and means (SW for precharging a first terminal ( 3 - j ) of a first capacitor (C SENj ) to a second reference voltage (GND), means (S 2 j , S 0 . . . Sk . . . Sn) for coupling the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) to the first terminal ( 3 - j ) of the first capacitor (C SENj ) to redistribute charges among the first capacitor (C SENj in FIG. 2A , C SEN in FIG. 2F ) and at least one of the plurality of CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 ) so as to generate a first voltage on the first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of the CDAC capacitors ( 25 - 0 . . . 25 - k . . . 25 - n ) and the first terminal ( 3 - j ) of the first capacitor (C SENj ), the first voltage being representative of a capacitance (C SENj ) of the first capacitor (C SENj ), and means ( 17 ) for performing a successive approximation conversion operation on the first voltage to generate a digital representation (DATA) of the capacitance (C SENj ) of the first capacitor (C SENj ).
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
FIG. 1A illustrates a plan view diagram of upper and lower orthogonal transparent, conductive strips of a touch screen panel;
FIG. 1B is a schematic diagram representing circuitry associated with an “intersection” of a horizontal conductive, transparent strip and a vertical conductive, transparent strip of a touch screen panel, cross coupling capacitance, and circuitry for sensing the presence of a person's finger close to the intersection;
FIG. 2A is a block diagram illustrating an architecture of an embedded SAR based passive capacitance measurement system of the present invention;
FIG. 2B is a timing diagram of clock signals used to operate the capacitance measurement system of FIG. 2A ;
FIG. 2C is a block diagram useful in explaining operation of the capacitance measuring system of FIG. 2A during a precharge phase;
FIG. 2D is a block diagram useful in explaining operation of the capacitance measuring system of FIG. 2A during a measurement phase;
FIG. 2E is a block diagram useful in explaining operation of the capacitance measuring system of FIG. 2A during a SAR analog-to-digital conversion phase;
FIG. 2F is a simplified schematic diagram of a touch button circuit which can be connected to measurement conductor 20 in FIG. 2A instead of touchscreen panel 13 A;
FIG. 3 is a block diagram illustrating a charge pump enhanced embedded SAR based passive capacitance measurement system of the present invention;
FIG. 4A is a graph which shows digital values of capacitance measured by the capacitance measurement systems of FIGS. 2A and 3 ;
FIG. 4B is a graph which shows measurement sensitivity of the capacitance measurement systems of FIGS. 2A and 3 ; and
FIG. 5 is a block diagram of a differential implementation of the capacitance measurement system of FIG. 2A .
DETAILED DESCRIPTION
Refer now to the drawings wherein depicted elements are, for the sake of clarity, not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views.
FIG. 2A shows a single-ended (i.e., not differential) embodiment of an embedded SAR based passive capacitance measurement system 15 of the present invention. Capacitance measurement system 15 includes a passive network 16 and a SAR (successive approximation register) type of ADC (analog-to-digital converter) 17 . Passive network 16 is coupled by conductor 3 - j to a touch screen capacitance C SENj . C SENj can be the same as a cross-coupling capacitance of an external touchscreen panel 13 A as shown in Prior Art FIGS. 1A and 1B . (Alternatively, the capacitance C SENj can be a capacitance C SEN or C BUTTON of a touch button with one terminal connected to ground as shown in subsequently described FIG. 2F , rather than a touchscreen panel 13 A as shown in FIG. 2A .) The capacitance C SENj (or C SEN ) is decreased by the presence of a human finger or the like in the electric field associated with that capacitance.
In FIG. 2A , the lower left corner shows an external touch screen panel 13 A. One cross-coupling capacitance C SENj at an intersection between a conductor 3 - j and a conductor 2 -I of external touch screen panel 13 A is illustrated, with conductor 2 -I of cross-coupling capacitance C SENj being coupled by a switch 25 to V DD during the subsequently described precharge phase (P) and coupled by switch 29 to ground during the subsequently described measurement phase (M in FIG. 2B ). The top terminal of capacitance C SENj can be coupled by conductor 3 - j and an optional switch S 2 j to measurement conductor 20 . (Note that optional switch S 2 j can be replaced by connecting conductor 3 - j directly to measurement conductor 20 in the more common case wherein passive network 16 A is multiplexed with a number of touch screen panels or a number of touch buttons.) As previously mentioned, the value of C SENj is affected by the touch or proximity or movement of a user's finger, depending on how close the finger approaches the intersection of conductors 2 -I and 3 - j (as in FIGS. 1A and 1B ) of touchscreen panel 13 A or how close the finger approaches the C SEN area of touch button 13 B in FIG. 2F . Various parasitic capacitances, having a total capacitance value C PARASITIC are in effect coupled between conductor 3 - j and ground, as generally shown in FIG. 2A .
Touch screen panel 13 A and switches 25 and 29 in FIG. 2A can be replaced by the illustrated touch button switch circuit shown in above mentioned FIG. 2F . Referring to FIG. 2F , the touch button switch circuit includes a touch button capacitor 13 B having a capacitance C SEN , also referred to as C BUTTON . The lower terminal of touch button capacitor 13 B is connected to a fixed reference voltage, such as ground. The upper terminal of touch button capacitor 13 B is coupled by switch S 1 to ground during precharge phase P and is coupled by switch S 2 to measurement conductor 20 during measurement phase M.
In FIG. 2A , passive network 16 includes switch S 1 j and optional switch S 2 j , each having a first terminal connected to conductor 3 - j . The second terminal of switch S 1 j is connected to ground, and the second terminal of switch S 2 j is connected to measurement conductor 20 of passive network 16 . Passive network 16 also includes switches S 0 . . . Sk . . . Sn, each having a first terminal connected to measurement conductor 20 . The second terminals of switches S 0 . . . Sk . . . Sn are connected to CDAC bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n , respectively. Passive network 16 and SAR ADC circuit 17 are connected to and disconnected from each other by the array of interface switches S 0 . . . Sk . . . Sn switches in response to measurement phase clock signal M. A divider/CDAC (capacitor digital-to-analog converter) 23 is included in passive network 16 , and includes a “top plate” conductor 24 connected to one terminal of a switch S 6 , the other terminal of which is connected to an auto-zeroing voltage V AZ . Switch S 6 is controlled by the signal PM in FIG. 2B . (A typical value of V AZ would be V DD /2. However, V AZ also could be ground or V DD , depending on how SAR comparator 26 is configured.)
Top plate conductor 24 is connected to a first terminal of each of binarily weighted capacitors 25 - 0 . . . 25 - k . . . 25 - n . The second terminal of each of capacitors 25 - 0 . . . 25 - k . . . 25 is connected to a corresponding one of bottom plate conductors 21 - 0 , 1 . . . k . . . n, respectively.
SAR ADC converter 17 shares the above mentioned switches S 0 . . . Sk . . . Sn, bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n , divider/CDAC circuit 23 , and switch S 6 with passive network 16 . SAR ADC 17 further includes an SAR comparator 26 having a (+) input connected to top plate conductor 24 and a (−) input connected to receive auto-zeroing voltage V AZ . (Note, however, that ordinarily the input applied to the (−) input of SAR comparator 26 is the analog output of another CDAC which is either being used in a mirror or “dummy” circuit or is being used to sample ground.) Top plate conductor 24 of divider/CDAC 23 , rather than the bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n thereof, preferably is connected to the (+) input of SAR comparator 26 because top plate conductor 24 typically has less parasitic capacitance. (Auto-zeroing circuitry for a SAR comparator is conventional, and can be readily implemented by those skilled in the art.) The output of SAR comparator 26 is connected by conductor 27 to the input of conventional SAR logic circuitry 28 , the output bus of which is connected to the input of a conventional SAR DAC (digital-to-analog converter) switch bank circuit 30 . SAR logic circuit 28 and SAR DAC switch bank 30 are clocked by a clock signal CLK.
SAR-DAC switch bank 30 includes the bank of switches S 7 k and S 8 k that pulls any particular CDAC capacitor to either a high level or a low level. Completion of a SAR conversion results in the final value of DATA<11:0>. SAR logic 28 performs the function of controlling the switches in SAR DAC switch bank 30 . During the precharge phase, SAR-DAC switches 30 must drive the various bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of any or all of CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n , respectively, to either V DD or to ground. This provides an “offset” of sorts that allows for different values of voltages that may appear on measurement conductor 20 by the end of measurement phase M.
It should be understood that there are a number of choices as to how the various CDAC capacitors and measurement capacitor C SENj can be precharged during the precharge phase. For example, if all of the CDAC capacitors are precharged to V DD and the C SENj capacitor is precharged to ground, then, in the touch button case, the charge redistribution during the measurement phase occurs across CDAC 23 , producing a particular voltage on conductor 20 . Alternatively, it would be possible to precharge only half of the CDAC capacitors, or even just the MSB CDAC capacitor, to V DD and precharge all of the other CDAC capacitors to ground. Or, all of the CDAC capacitors could be precharged to ground and the button capacitor to could be precharged to V DD . The results of such different precharging strategies would be that the charge redistribution during the measurement phase would advantageously result in different voltages on conductor 20 .
Each of bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n is connected to a conductor 21 k of a corresponding switching circuit, respectively, in SAR ADC switch bank 30 which includes a pair of switches S 7 k and S 8 k , where k is an index having a value between 0 and n. A first terminal of each of switches S 7 k and S 8 k of a “k”th pair has a first terminal connected to conductor 21 k . The second terminal of each switch S 7 k is connected to a suitable first reference voltage (such as supply voltage V DD ), and the second terminal of each switch S 8 k is connected to a corresponding suitable second reference voltage (such as ground or V SS ). The output of SAR DAC switch bank 30 is connected to data output bus 32 , on which digital data value DATA<11:0> (for a 12-bit SAR DAC) is produced. DATA<11:0)> represents the measured capacitance of C SENj .
Note, however, that the above mentioned “suitable” corresponding reference voltages could be set to a value higher than V DD and a value lower than ground, respectively, or alternatively they could be set to a value less than V DD and a value higher than ground, respectively, in order to “squeeze” or “expand” the usable input range of SAR ADC 17 . (Various implementations of SAR ADCs that execute the well known basic SAR algorithm are widely used, and can be readily implemented by those skilled in the art. For example, the assignee's TSC2007, TSC2005, TSC2003, TSC2046, ADS7846 all include similar SAR ADC circuits which could be used.)
The portion of passive capacitance measuring system 15 in FIG. 2A exclusive of touchscreen panel 13 A preferably is implemented on a single integrated circuit chip. Switch S 1 j and optional switch S 2 j , which are connected to measurement node 20 , are controlled by a precharge phase clock P and a measurement phase clock M, respectively. Note that divider/CDAC 23 functions in the charge redistribution operation of passive network 16 , and then functions in the SAR analog-to-digital conversion of the voltage on measurement conductor 20 into the digital output signal DATA<11:0>.
Above-mentioned FIG. 2B is a timing diagram including the digital signal P which represents the precharge phase of passive capacitance measurement system 15 , the digital signal M which represents the measurement phase, and a digital signal S which represents an SAR analog-to-digital conversion phase. Timing diagram FIG. 2B also shows a digital signal PS which is the inverse of the signal M and a digital signal PM which is the inverse of the signal S. Switch S 1 j is controlled by precharge phase signal P. Switches S 2 j and S 0 . . . Sk . . . Sn are controlled by measurement phase signal M. Switch S 6 is controlled by clock signal PM, switches S 7 k are controlled by clock signal PS, and switches S 8 k are controlled by SAR phase clock S, where k has all of the values between 0 and n. (However, note that all of the switches in FIG. 2A are illustrated in their “open” condition.)
FIG. 2C shows the configuration of the various switches of passive capacitance measurement system 15 of FIG. 2A during the above mentioned precharge phase, when clock signal P is at a high level. During the precharge phase, switches S 1 j and S 6 are closed and at least some of the n+1 switches S 7 k also are closed. The remaining switches S 2 j , S 0 . . . Sk . . . Sn, and at least some of switches S 8 k are open. In this configuration, the touchscreen capacitance C SENj (or touch button capacitance C SEN ) being measured is discharged to ground through switch S 1 j . The clock signal PM also is at a high level during the precharge phase, so switch S 6 is also closed. Top plate conductor 24 of divider/CDAC 23 therefore is maintained at V AZ before the charge redistribution between C SENj and the capacitors of divider/CDAC 23 takes place. During a normal SAR conversion this operation (or a similar operation) would occur in conjunction with a conventional auto-zeroing of SAR comparator 26 , during which SAR comparator 26 is connected to auto-zeroing voltage V AZ .
Note that there are n+1 of the switches S 7 k in SAR DAC control circuit 30 , all controlled by the PS clock signal, which is at a high level during the precharge phase (and also during the SAR conversion phase). The n+1 switches S 7 k therefore are closed during the precharge phase. Consequently, a first terminal of some or all (depending on the precharge strategy being used) of CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n in divider/CDAC circuit 23 is connected to V DD through its corresponding switch S 7 k , while the interface switches S 0 . . . Sk . . . Sn remain open, in order to precharge the corresponding bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of divider/CDAC circuit 23 . By the end of the precharge phase S, the capacitance C SEN has been discharged and the bottom plates of capacitors 25 - 0 . . . 25 - k . . . 25 - n of divider/CDAC circuit 23 all have been precharged to a suitable reference voltage level, such as V DD or even a voltage generated by a variable gain amplifier circuit or a charge pump circuit. There also are n+1 of switches S 8 k in SAR ADC switch bank 30 which are controlled in accordance with the conventional SAR conversion algorithm executed by SAR logic 28 and SAR ADC control circuit 30 .
FIG. 2D shows the configuration of the various switches of capacitance measurement system 15 of FIG. 2A during the measurement phase, while clock signal M is at its high level as indicated in FIG. 2B . During the measurement phase, switches S 2 j , S 0 . . . Sk . . . Sn, and S 6 are closed, and the remaining switches S 1 j , S 7 k , and at least some of switches S 8 k remain open (k being the above mentioned index variable having values between 0 and n). Conductor 3 - j has been released from ground since the end of precharge phase P, and M-controlled switch S 2 j is closed. Some or all of the bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of divider/CDAC 23 (depending on the precharge strategy being used) have been precharged through switches S 7 k to a suitable reference voltage, for example, V DD , and then disconnected therefrom. When the array of M-controlled switches S 0 . . . Sk . . . Sn connecting measurement conductor 20 to the precharged bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of divider/CDAC 23 are closed, the charges produced during the precharge phase on C SENj and at least some of CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n is redistributed among those capacitors. That results in a corresponding change in the voltage on measurement conductor 20 and CDAC conductors 21 - 0 . . . 21 - k . . . 21 - n . (Note that although the auto-zeroing operation continues so that at this point the voltage on the (+) input of SAR comparator 26 has not changed, the auto-zeroing of SAR comparator 26 does not necessarily have to continue during the capacitance measurement phase. Auto-zeroing is not even essential to all embodiments of the present invention.)
It should be appreciated that depending on the expected value of C SENj , it might be desirable to not connect all of the CDAC capacitors into the foregoing capacitive divider configuration during the measurement phase. For example, only the MSB CDAC capacitor might be included in the divider configuration. Alternatively, the bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n being referred to could have been set to some other suitable reference voltage between V DD and ground. For example, the CDAC bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n could have been precharged to zero and C SENj could be precharged to V DD for the measurement phase, again depending on the precharging strategy being used. This might even be necessary, depending on the ratio of the total CDAC capacitances and C SENj .)
In operation during measurement phase M, some or all of CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n are used in a capacitive divider configuration. Since C SENj is connected in series with the CDAC capacitance C CDAC of some or all of CDAC capacitors 25 - 0 . . . 25 - k . . . 25 , the charge redistribution results in a “divided” voltage which appears on measurement conductor 20 , since during the measurement phase, the voltage of top plate conductor 24 is fixed at V DD /2 (because switch S 6 is closed). The divided-voltage output on conductor 20 is equal to V DD *CDAC/(C t ). So at the conclusion of the measurement phase, it is as if a voltage sampled onto conductor 20 is, in effect, sampled onto the CDAC capacitors. Then conductor 20 is disconnected by switches S 0 . . . Sk . . . Sn, and the SAR conversion operation can then begin. (During the SAR operation, with switch S 6 open, the voltage of conductor 20 increases and/or decreases as the successive approximation algorithm is executed.)
As an extreme or limiting example, if C SENj is zero, then V DD appears on CDAC capacitance C CDAC and therefore appears as the voltage on conductor 20 , and hence also on bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of CDAC 23 . The voltage across CDAC 23 would be V DD *C CDAC /C t −V DD /2. As another example, if C SENj is equal to C CDAC , then there would be V DD /2−V DD /2=0 volts across CDAC 23 . (And the subsequent SAR conversion operation would generate a middle code 0111111111111.)
As another extreme or limiting example, if C SENj is very large, then, as above, the voltage on top plate conductor 24 is fixed, and the voltage on C SENj is sampled onto the bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n of the CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n through switches S 0 . . . Sk . . . Sn and conductor 20 , and hence the voltage sampled onto bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n would be zero, to subsequently be converted by SAR ADC 17 . Of course, the determination of the voltages on conductor 20 and hence on bottom plate conductors 25 - 0 . . . 25 - k . . . 25 - n becomes more complicated if parasitic capacitances are considered and also if subsequently described charge pump capacitor C P in FIG. 3 is included.
FIG. 2E shows the configuration of the various switches of capacitance measurement system 15 of FIG. 2A during the SAR analog-to-conversion phase, when clock signals S and PS are at a high level and clock signals P, M, and PM are at a low level as indicated in FIG. 2B . During the SAR analog-to-digital conversion phase, switch S 1 j is closed and switches S 2 j , S 0 . . . Sk . . . Sn, and S 6 remain open. Switches S 7 k and S 8 k are controlled by SAR logic 28 in accordance with the above mentioned well known SAR conversion algorithm so as to cause SAR comparator 26 to test, bit by bit, the voltages produced on top plate conductor 24 as the bottom plates of the CDAC capacitors 25 - 0 . . . 25 - k . . . 25 - n , starting with the voltage on MSB CDAC capacitor 25 - 0 , are sequentially connected to V DD by the corresponding switches S 7 k (the index variable k having the values 0-n) as the bottom plates of the other CDAC capacitors are connected to ground through their corresponding switches S 8 k . (Since the M-controlled switches S 0 . . . Sk . . . Sn are open, measurement conductor 20 may be electrically floating during the SAR conversion phase, although as a practical matter it may be set to a fixed reference voltage.)
Once measurement phase clock M is “de-asserted” to its low level, the measurement phase operation is complete and the SAR conversion phase can begin. For the 12-bit case in which n=11, switches S 0 . . . Sk . . . S 11 and switch S 6 are opened, and the sampling of C SENj by passive network 16 has been completed. SAR DAC switch bank 30 contains a total of 24 switches, in pairs. The bottom plate conductor of each CDAC capacitor, for example, the MSB CDAC capacitor 25 - 0 ) can be pulled to V DD by a corresponding one of switches S 7 k , or can be pulled to ground by a corresponding one of switches S 8 k of the same pair. (Of course, the two corresponding capacitors of a “k”th pair are never simultaneously asserted, i.e., one is never couples to V DD while the other couples to ground.) For example, during the SAR conversion phase, the MSB capacitor 25 - 0 first is pulled to V DD by switch S 7 - 0 (i.e., switch S 7 k where k=0) and then top plate conductor 24 is compared to V AZ and all of the other less significant CDAC capacitors are pulled to ground by the appropriate S 7 k switches. If testing of the resulting voltage on top plate conductor 24 by SAR comparator 26 determines that the voltage on top plate conductor 24 is too high, then the corresponding MSB capacitor (not shown) is pulled to ground by switch S 8 - 0 (i.e., switch S 8 k where k=0), and all of the other less significant CDAC capacitors are pulled to V DD by the appropriate S 7 k switches. Then the next-most-significant (MSB-1) capacitor 25 - 1 is pulled to V DD and the voltage on top plate conductor 24 is tested. Essentially the same procedure is successively repeated for all of the less significant bits.
Execution of the SAR ADC algorithm results in the digital output DATA<11:0> for the case in which n=11. DATA<11:0> indicates the amount of charge redistributed due to a person's finger touching or being in the vicinity of touch point 13 (see FIG. 1A ) of touchscreen panel 13 A. Once the SAR conversion is complete, the 12 bits of data (for this example) generated by SAR DAC control circuit 30 represent the value of the voltage on measurement conductor 20 immediately after the charge redistribution is complete. In a touchscreen controller, the digital output data DATA<11:0> can be readily used to determine the location of the particular touch point 13 on touchscreen panel 13 A that has been touched by the finger of a user.
At the end of the SAR testing process, an output voltage appears on top plate conductor 24 that is equal to V AZ , and the n+1 logical levels (i.e., 12 logic levels for the case where n=11) representing whether the various bottom plate conductors 21 - 0 , 1 . . . 11 were at “0” or “1” levels after the corresponding decisions by SAR comparator 26 provide the digital output value DATA<11:0> representing the final voltage of top plate conductor 24 .
A shortcoming of passive capacitance measurement system 15 as shown in FIG. 2A is that it has a somewhat limited range of useful values of C SENj . Another shortcoming of passive capacitance measurement system 15 is that it is subject to sensitivity degradations as C SENj or the total capacitance on measurement conductor 20 becomes too large. The embodiment of the invention generally as shown in FIG. 2A can measure a value of C SENj in the range from 0 pF (picofarads) to a value which is a function of desired system accuracy/performance, e.g., roughly 30 pF. However, it would be desirable for some applications, to provide improved a passive capacitance measurement system having greater sensitivity, i.e., greater measured capacitance per LSB of DATA<11:0> than can be achieved using the system shown in FIG. 2A .
FIG. 3 shows a modified embedded SAR based passive capacitance measurement system 15 - 1 which includes the circuitry shown in FIG. 2A and further includes a charge pump network including a pump capacitor C P having one terminal connected either directly or by a M-controlled switch (not shown) to measurement conductor 20 and another terminal connected by conductor 22 to one terminal of each of switches S 9 j and S 10 j . A P-controlled switch S 13 is coupled between measurement conductor 20 and V DD . The other terminal of M-controlled switch S 9 j is connected to V DD , and the other terminal of P-controlled switch S 10 j is connected to ground. During the previously described precharge phase P, pump capacitor C P is discharged through switch S 10 j to ground. During the previously described measurement phase, pump capacitor C P is coupled to V DD , thereby “pumping” the voltage on measurement conductor 20 to a significantly higher voltage than V DD before the previously described charge redistribution occurs.
FIG. 4A illustrates capacitance measurement sensitivity, i.e., SAR code output versus C SENj without the pump capacitor C P , as the lower curve. The upper curve in FIG. 4A indicates the higher capacitance measurement sensitivity for the embodiment of FIG. 3 , using pump capacitor C P . Using pump capacitor C P allows lower capacitance measurements to be made which result in voltage values on measurement conductor 20 that are above voltage measurement capability of the SAR converter 17 . That is, using pump capacitor C P has the effect of boosting or pumping the voltage on measurement conductor 20 to levels greater than V DD .
For small values of C SENj , is not desirable to use charge pump capacitor C P because the slope of the lower curve in FIG. 4A is adequate. As the value of C SENj increases, it may be necessary to increase the slope, which is proportional to the “sensitivity” of the passive capacitance measurement system 15 of FIG. 2A . To “broaden” the steep part of the slope for larger values of C SENj , charge pump capacitor C P is used to cause saturation of SAR ADC 17 at small values of C SENj , and also increase the overall slope magnitude in order to “recover” a bit of the foregoing higher sensitivity for larger values of C SENj .
FIG. 4B shows another way of representing essentially the same information as in FIG. 4A , but in terms of femptofarads per LSB. This better illustrates how many femptofarads which C SENj needs to change in order to cause a 1-LSB change in DATA<11:0>. The upper curve in FIG. 4B indicates capacitance measurement sensitivity of the system shown in FIG. 2A . The lower curve in FIG. 4B indicates capacitance measurement sensitivity of the system shown in FIG. 3 , including charge pump capacitor C P , and shows that the charge pump implementation of the invention improves its capacitance measurement sensitivity. If charge pump capacitor C P is used, and if C SENj is too small, then the voltage on measurement conductor 20 will go higher than V DD , causing the SAR-ADC converter 17 to become saturated to V DD . This causes the lower curve in FIG. 4B to have the vertical straight line, and also causes the upper curve in FIG. 4A to have the horizontal upper segment. (Note that it would also be possible to configure the circuitry shown in FIG. 3 in such a way that the SAR converter would be saturated to ground rather than to V DD .)
FIG. 5 shows a capacitance measurement system 15 - 2 which includes all of the circuitry 15 - 1 shown in FIG. 2A , and further includes a “negative side network” 16 A and a reference capacitor C REF . Negative side network 16 A (together with reference capacitor C REF ), constitute a network that is very similar to the network including passive network 16 and capacitance C SENj . The output 24 A of negative side network 16 A is connected to the (−) input of SAR comparator 26 . The capacitance of reference capacitor C REF is essentially the same as C SENj , and negative side network 16 A is operated simultaneously with the network including passive network 16 and SAR ADC 17 such that corresponding parasitic-based switching offset voltages are canceled, and such that the charge injection in each of the two networks is common mode and therefore is canceled.
Although negative side network 16 A can be considered to be a “dummy” network to achieve the foregoing cancellations, it also can be used to compare C SENj to C REF . For example, if one of C SENj and C REF is larger than the other, then the digital output DATA<11:0> is either larger or smaller than its midrange value. A single clock SAR operation can be performed to determine which is larger, and then the rest of the SAR ADC conversion process can be completed to determine the magnitude of the difference between C SENj and C REF .
In the above described embodiments of the invention, the capacitor C SENj is sampled, and then the decision by SAR comparator 26 is made while the touch screen panel capacitance C SENj is decoupled from SAR ADC 17 . This results in substantially improved noise performance and more accurate capacitance measurement values, which it is believed will be an important issue to potential users of the invention.
The advantages of the described embodiments of the invention include much higher speed operation than the prior art, along with reduced power dissipation and improved immunity to printed circuit board noise. The described embodiments of the invention provide consistent times to generate DATA<11:0)> for a sample capacitance measurement, in contrast to the prior art in which the amount of time required for capacitance measurement is quite dependent on the amount of the capacitance to be measured. Less noise is introduced into the described embodiments of the invention because, for example, in a 12 bit SAR ADC implementation the touch screen panel is sampled only once, for 2 μs (microseconds), during each 15 μs cycle time and then is effectively disconnected by opening switches S 0 . . . Sk . . . Sn. Only about 15 clock cycles, i.e., 50 μs at 1 MHZ, is required for a capacitance measurement, which is many fewer clock cycles than for the prior art. Since C SENj is only coupled to SAR ADC 17 for only a small fraction of the total cycle operation and then is disconnected, SAR ADC 17 is not affected as much by circuit noise as the prior art, in which the capacitance to be sampled is connected for the entire measurement cycle. The architecture is easily multiplexed for multiple channels, e.g. 8 channels per network. The described embodiments of the invention are easily reconfigurable to allow them to be used as a typical analog-to-digital converter. The capacitance measurement circuit of the present invention therefore can be utilized both as a touch-screen controller and as a fully functional analog-to-digital converter.
While the invention has been described with reference to several particular embodiments thereof, those skilled in the art will be able to make various modifications to the described embodiments of the invention without departing from its true spirit and scope. It is intended that all elements or steps which are insubstantially different from those recited in the claims but perform substantially the same functions, respectively, in substantially the same way to achieve the same result as what is claimed are within the scope of the invention. For example, the CDAC capacitors in divider/CDAC 23 do not have to be waited binarily. Furthermore, various known capacitive divider arrangements other than the one illustrated can be used, for example to provide cancellation of common mode errors due to mismatching of circuit elements and mismatching of parasitic elements. It should be appreciated that although the CDAC capacitors are binarily weighted in the described embodiments, they could be weighted in other ways, for example in accordance with a thermometer code. A “capacitively divided voltage” on measurement conductor 20 could also be achieved during the measurement phase by grounding the bottom plate conductors 21 - 0 . . . 21 - k . . . 21 - n and precharging top plate conductor 24 to an arbitrary voltage.
Having thus described the present invention by reference to certain of its preferred embodiments, it is noted that the embodiments disclosed are illustrative rather than limiting in nature and that a wide range of variations, modifications, changes, and substitutions are contemplated in the foregoing disclosure and, in some instances, some features of the present invention may be employed without a corresponding use of the other features. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention. | A capacitance measurement system precharges first terminals ( 21 - 0 . . . 21 - k . . . 21 - n ) of a plurality of capacitors ( 25 - 0 . . . 25 - k . . . 25 ), respectively, of a CDAC (capacitor digital-to-analog converter) ( 23 ) included in a SAR (successive approximation register) converter ( 17 ) to a first voltage (V DD ) and pre-charges a first terminal ( 3 - j ) of a capacitor (C SENj ) to a second voltage (GND). The first terminals are coupled to the first terminal of the capacitor to redistribute charges therebetween so as to generate a first voltage on the first terminals and the first terminal of the capacitor, the first voltage being representative of a capacitance of the first capacitor (C SENj ). A SAR converter converts the first voltage to a digital representation (DATA) of the capacitor. The capacitance can be a touch screen capacitance. | 6 |
TECHNICAL FIELD
The present invention relates generally to the field of composite pipes possessing the properties of excellent anticorrosive performance and a long lifetime, and more particularly, to employing a hot-spraying technique for preparing metal-glass glaze composite pipe for use in industrial applications in petroleum, chemical engineering, medical, and dye material applications, or for use in oil transportation, water supply, gas supply, as well as underground or submarine anticorrosive tube usage.
BACKGROUND OF THE INVENTION
At the present time, the main method for preventing tube or pipe corrosion in China makes use of hot bitumen or tar, which method was also the main method used in the major industrialized countries until recently. The lifetime of pipes treated with bitumen generally does not exceed ten years and in regions suffering from heavy corrosion conditions, the lifetime of such pipes does not exceed 5-7 years. There are many drawbacks to using such kinds of anticorrosive coating materials, e.g., the deformation rate limit is small, dripping flow occurs at elevated temperatures which damage the anticorrosive layer, the base produced at cathode protection harms the adhesion of the base painting, and microorganisms can cause erosion or damage thereon. Therefore, the weak points of the piping anticorrosive layer run the risk of being damaged at all times. This not only results in payment of large amounts of maintenance fees, but also results in a sizeable economic loss due to repairing and servicing of the pipings and interruption of the fluid transportation.
In recent years, the epoxy powder spraying method has been widely used for tube anticorrosion in many countries. In West Germany, for example, polyethylene powder coating material is employed for 90% of the anticorrosive applications with respect to gas piping as well as water supply piping. Epoxy powder coating material is widely used in western Europe and the United States. Since 1985, the Chinese Academy of Piping Research has successfully experimented with the epoxy powder spraying method for pipes and has commercialized such a method. Such steel-plastic composite pipes have a longer lifetime than those with the bitumen coating layer due to the raising of the deformation rate limit so that neither serious deformation will take place, nor will dripping cause damage. However, because epoxy powder is an organic material as is bitumen, it is susceptible to the aging problem of the coating layer. Along with the lapse of time, the rise and fall of temperature, the influence of the air humidity, as well as the acid, base, salt and water in the soil, the aging of the coating layer will accelerate. The age limit of both polyethylene and epoxy coating materials will barely exceed 20 years.
EP-0154513 (publication number) relates to glass compositions which are suitable for bonding to alloys, in particular, "Vitallium" (trademark) alloys. Its use is limited to implant tubes for use in surgical operations.
According to JP 60-273448, powdered glass spheres can be carried by a gas having a certain velocity and sprayed onto the surface of a base material, whereby these powder spheres form a molten film and adhere onto the surface of the base metal. The operational temperatures of the process are in the range of 700° C. to 800° C. and the use of the process is limited to only insulating material and fabrics.
The above art relates to glass that is sprayed onto a base material to form a composite material, as opposed to an inorganic material coating for anticorrosive purposes.
Therefore, it is necessary to provide a kind of pipe material which can eliminate the aging drawbacks of the present organic anticorrosive coating layer, to improve the anticorrosive performance of the pipings, and significantly lengthen their operational lifetime.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a metal-inorganic material composite piping to replace the existing metal-organic material composite pipe. According to the present invention, a metal-glass glaze composite pipe is prepared using a flat nozzle gun as well as a special set of equipment to hot-spray specially prepared glass glaze coating material onto the surface of standard metal piping as a glass glaze coating layer.
Other features and advantages of the invention will be apparent from the following description of the preferred embodiments, and from the claims.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of the nozzle for the hot-spray gun used to practice the present invention.
FIG. 2 is a flow chart of a schematic model of the hot-spraying method of the present invention.
FIG. 3 is a sectional view of the hot-spray operation of the spray gun.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As is well known in the art, porcelain enamel is an inorganic material with anticorrosive performance. At the present time, enamel products are all produced by calcination in furnaces, such that very long pipes are difficult to prepare.
The metal-glass glaze pipe or product provided by the method of the present invention is not prepared by calcination in specially dimensioned furnaces, but is instead formed by means of a hot-spraying process. Therefore, the process provided by the present invention can produce very long pipes which are comparable to those with porcelain enamel. Additionally, the equipment used in the present process can be moved directly to the construction site for preparing the pipes.
The present invention provides a composition for the glaze used in hot-spraying, spray guns and the other special equipment system to carry out the method of the present invention, as well as the process for hot-spraying to form the metal-glass glaze composite of the present invention.
It can be shown that MoO 3 can significantly improve formability of undeveloped glass, while tungsten and molybdenum also contribute to the chemical stability of glass. Such compounds are not only helpful for the melting of glass, but also have a positive effect on the brightness of the surface of the sprayed products. Together with base material, MoO 3 and WO 3 can readily form a molten compound molybdate or tungstate which can react to some extent with the metal pipe interface in the course of hot-spraying. For example, when barium molybdate is used as the base glaze of enamel chinaware, the adhesive force of the porcelain glaze onto metal can be improved.
MoO 3 and WO 3 are also surfactants of glass which can reduce the viscosity of glass and improve the wetting ability of glass onto metal.
The nozzles of the metal power spray guns used in prior processes are of a round shape, while the nozzles of the guns employed in the present invention are flat as shown in FIG. 1. The height H of the nozzle spray orifice (1) is smaller than the width B; the holes surrounding the nozzle spray orifice are the gas orifices (2) which inject a gaseous mixture of ethine (acetylene) and oxygen, which gives rise to flames and cause melting of the starting powdered glaze material. The outermost layer of the nozzle is the radiating fin (3).
The hot-spraying technique of the present invention is shown schematically in FIG. 2. The spraying equipment system is divided into six parts: (I) a pipe transportation system; (II) a pipe-derusting system; (III) a pipe preheating system; (IV) a pipe nitrogen protecting system; (V) a hot-spraying system; and (VI) a heating and sealing system.
The pipe (4) being sprayed during the hot-spraying operation of the present invention undergoes two simultaneous motions: a rotation about the pipe axis, and a movement along the axial direction of the pipe. Before spraying a pipe, it is necessary to use air compressor (5) and sand-blower (6) to remove any rust on the present pipe. A diesel generator (7) is used to supply power to the frequency converter and intermediate frequency generating unit (8). The pipe is preheated by the induction heating coil (10) coiled around the pipe preheating region (9) of a nitrogen protective cover (12). Nitrogen produced by a nitrogen generator (11) is introduced into the nitrogen protective cover (12) such that the preheating region and the glaze spray region on the pipe can be well protected to prevent the pipe from being oxidized at high temperatures. During spraying, a combination of ethine (acetylene) and oxygen are used as a combustion gas (13) which, together with a powdered glaze composition (14), are fed respectively to two spray guns (15). These two guns are disposed in parallel along the axial direction of the pipe to carry out two layers of spray comprising an under-glaze layer (16), and an overglaze layer (17). After the spraying is completed, the pipe enters a high frequency post-heat region (20) to allow the micropores on the glaze-sprayed face of the pipe to be well sealed to ensure the spraying quality. To carry out the final steps in the spray coating operation, the converter, a high frequency generating unit (19) and the high frequency induction heating coil (18) are used to post-heat the pipe (4) at the post-heating region (20).
The above spraying operation is suitable for the spray-coating of the outer face of the pipes The spraying of the outer surfaces of the pipes is accomplished by a spray gun utilized with the pipe rotationally inclining to a certain degree.
The preheating temperature of the pipe is generally in the range of between about 300° C. to about 750° C., and is preferably about 700° C. If intermediate frequency generation unit (8) is used for heating, an ideal temperature field for spray coating can be provided.
FIG. 3 illustrates the operation of hot-spraying glass glaze onto metal pipe. The flat nozzle spray gun as shown in FIG. 1 is used as the hot-spraying tool. Ethine (acetylene) (21) and oxygen (22), as well as a powdered glaze material (23), examples of which are listed in Table I, are fed into the gun simultaneously. The materials are ignited at gas orifice (24) and the nozzle (26) at temperatures in the range of between about 1,400° C. to about 3,000° C. The powdered glaze material is heated in a flame (25) and melted into liquid drops, which are uniformly injected towards the rotating surface of the metal pipe (27) which is also horizontally moving at the same time. A glass glaze coating layer (28) is formed comprised of an underglaze having a preferable thickness with a range of between about 0.2 mm to about 0.4 mm, and an overglaze having a preferable thickness with a range of between about 0.3 mm to about 0.6 mm.
The thickness of the underglaze on the surface of the metal pipe is generally in the range of between about 0.05 mm to about 2.0 mm, and is preferably in the range of between about 0.2 mm to about 0.4 mm; the thickness of the overglaze is generally in the range of between about 0.05 mm to about 3.0 mm, preferably in the range of about 0.3 mm to 0.6 mm. The total thickness of the two glaze layers is in the range of between about 0.10 mm to about 5.0 mm, and is preferably in the range of between about 0.5 mm to about 1.0 mm.
After spraying of the pipe is completed, the pipe is post-heated by high frequency induction coil (18) at the high frequency heating region, to a temperature which should be maintained in the range of between about 600° C. to about 850° C., and is preferably about 750° C. Such heating can eliminate the micropores on the coating and ensure the quality of the resultant composite pipe.
The test results of the physical and chemical performances of the composite pipe of the present invention are shown in Table 2, which are provided by the Chemistry Department, Qinghua University. It can be seen that the composite pipe of the present invention possesses good anticorrosive performance characteristics such as, for example, fluorion-corrosion resistance, alkali resistance, acid resistance, salt tolerance, and mechanical strength such as, for example, shock-resistance, and thermal shock resistance. Operational temperatures of the composite pipe may reach as high as 300° C., whereas the maximum operational temperature of organic coating layers is between about 60° C. and 100° C. The adhesive performance of the glaze layer of the present composite pipe is also good. For example, the glaze will not rupture or strip after being hit by a steel ball ten times, and although the overglaze will be stripped off after a hammer strike test on the glaze surface, the underglaze remains normal.
While metal pipe has high strength but low anticorrosion ability, and glass has good anticorrosion ability but low strength, these two advantages are well combined by means of the hot-spraying technique of the present invention. The composite pipe possesses the strength of metal and the anticorrosive properties of glass. Such a coating formed by glass glaze will not significantly age for about one hundred years.
The method provided by the present invention can also be used for hot-spraying the coating of various colors and various patterns onto metal substrates to manufacture metal-colored glass glaze composite products used as, for example, building signs, billboards, road signs, and street nameplates.
In order to promote the development of the piping industry and to satisfy the characteristics or demands in different countries, production capabilities have been developed in mobile factories. Also, the various required special equipment is incorporated into mobile tool cars for further production. In this way, the pipe production and the pipe application can be well integrated.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the appended claims. T2 TABLE 1-Composition of Hot-spraying glaze material? -Components? Na 2 O? Al 2 O 3? B 2 O 3? SiO 2? Co 2 O 3? MnO 2? MoO 3? WO 3? NiO 2? -Under-glaze Content 15-30 3-10 5-25 20-45 --? 0.11 10-25 1-8 1.0 - (% by weight) -Overglaze Content 15-30 3-10 5-25 15-37 0.1-5.0 0.11 15-35 1-8 --? - (% by weight)? -
TABLE 2__________________________________________________________________________Test Results of Physical & Chemical Performance of the Composite Pipe(Weight loss unit g/day · m.sup.2 (* -g/m.sup.2)) Test Results WeightPerformance Test Method appearance change loss Remarks__________________________________________________________________________Operational Determined by melting method; Operational temperaturetemperature Operational temperature is depends on operational about 0-300° C. conditions; while without corrosion contaminant, operational temperature may be set in a suitable wider range.Adhesive After a steel ball falls from Adhesion of glaze with National standard Testtest 1 meter high onto the center metal is quite good. method (shock method) of the sample, observing by The glaze of the sample naked eye decortication and does not rupture and combination between the strip, after a shock of underglaze and the metal. 10 TIMES. For a hammer strike on the glaze, the overglaze is peeled off but the underglaze remains normal.Shock using CHARPY XCJ-40 TYPE Shock resistance isresistance SHOCK MACHINE 4500 g · cmSaline Sample is immersed for 7 days Without rust and 0.00water in 5% NaCl aqueous solution at peeling off.tolerance room temperatureSaline Sample is stored in the Without rust andmist thermostat with 5% NaCl peeling off.tolerance aqueous solution at 100° C. A 15 minute continuous mist-spray is made every minutes; the test lasts 7 days, 8 hrs a day.Fluorion Sample is immersed for 7 days Without rust and 0.55resistance in 5% NaCl aqueous solution peeling off.Acid 1. Immersed for 7 days in Without rust and 1.24resistance strong phosphoric acid. peeling off. 2. Immersed for 7 days in Without gloss 1.50 HClAlkali 1. Sodium carbonate method Without rust and 1.01 National standardresistance peeling off. Test Method 2. Immersed for 7 days in 5% Without rust and 1.82 NaOH peeling off.Thermal Sample is heated in the Glaze layer is peeled ISO 2742 standardshock electric heater unit up to off at 540° C. Experimental Methodresistance 200° C. and quenched with 20° C. water; in the case of no damage, the temperature will be increased at 20° C. intervals until visible rupture or peeling off of the sample appears Sample is stored in the After repeating the thermostat of -30° C. and then test for 200 times, no immediately put into 100° C. rupture, nor peeling boiling water, repeating above off. procedures until rupture or peeling off appears.Self- A drop of refined bean oil Excellent self-cleaning ISO 2746 standardcleaning falls on the glaze of the ability Experimental Methodability sample which is baked for 1 hr at 250° C. and then the self- cleaning effect is observed.Defect Determined by international Defect concentration ISO DISdetermina- high pressure 3 gas pocket/10 cm.sup.2 8291 Experimental methodtion__________________________________________________________________________ | A process for producing a metal-glass glaze composite pipe including removing corrosion from a metal pipe, simultaneously rotating and translating the pipe through a protective cover operating under a substantially non-oxidating environment and containing an induction pre-heating device and a pair of spray guns. The pre-heating device heats the pipe to a first predetermined temperature while the first and second spray guns apply first and second layers of hot-sprayed, flame-liquefied powdered glaze material to the pipe. An induction post-heater is provided to ensure the quality of seal effected by the layers of glaze material. | 2 |
BACKGROUND
[0001] NAND flash memory has become a commonly used format for storing quantities of data on devices such as USB Flash drives, digital cameras and MP3 players. A NAND flash memory is a form of rewritable memory that derives its name from the resemblance to a NAND logic gate. NAND flash is often used for applications utilizing large files of sequential data because NAND flash provides higher density, lower cost, and faster write and erase times compared to other forms of memory such as NOR flash. NAND flash is generally fast to erase and write, but slow to read non-sequential data through its serial interface.
[0002] NAND flash memories are accessed much like block devices such as hard disks or memory cards. When executing software from NAND memories, their contents must first be paged into a memory-mapped random access memory (RAM) and executed in the RAM. This makes the presence of a memory management unit (MMU) in the system necessary. For example, when using NAND flash as program ROM, the system can include a large SRAM to store the program retrieved from the NAND flash. The program can then be executed in the SRAM.
SUMMARY
[0003] According to an aspect of the present invention, a system for executing a sequential program can include a NAND flash configured to store the sequential program and a processor configured to execute the sequential program. The system can also include a cache configured to store instructions received from the NAND flash. The cache can have a size of about twice the maximum offset of a conditional jump of the sequential program. The system can also include a cache controller configured to control the instructions stored in the cache.
[0004] Embodiments can include one or more of the following.
[0005] The cache can have a size between twice the maximum offset of a conditional jump and 2.2 times the maximum offset of a conditional jump. The cache can have a size equal to twice the maximum offset of a conditional jump. The cache controller can be configured to maintain a program counter that indicates the current location of execution of the sequential program by the processor. The cache controller can be further configured to maintain in the cache instructions with addresses within the range of the program counter minus the maximum offset of a conditional jump to the program counter plus the maximum offset of a conditional jump. The cache controller can be further configured to determine, in response to a jump command received from the processor, if a target address is stored in the cache; and if the target address is stored in the cache, change the program to the target address. The cache controller can be further configured to determine, in response to a jump command received from the processor, if the target address is not stored in the cache, clear the cache and send the target address to the NAND flash. The cache controller can be further configured to sequentially fetch additional instructions from the NAND flash if the jump command is a forward jump command and the address is stored in the cache. The cache can be a SRAM device.
[0006] According to an aspect of the present invention, a cache management unit can include a first interface configured to receive a sequential program from a NAND flash and send instructions to the NAND flash and a second interface configured to send and receive data from a processor configured to execute the sequential program. The cache management unit can also include a cache configured to store instructions received from the NAND flash The cache can have a size of about twice the maximum offset of a conditional jump of the sequential program. The cache controller can be configured to control the instructions stored in the cache.
[0007] Embodiments can include one or more of the following.
[0008] The cache can have a size between twice the maximum offset of a conditional jump and 2.2 times the maximum offset of a conditional jump. The cache can have a size equal to twice the maximum offset of a conditional jump. The cache controller can be configured to maintain a program counter that indicates the current location of execution of the sequential program by the processor. The cache controller can be further configured to maintain in the cache instructions with addresses within the range of the program counter minus the maximum offset of a conditional jump to the program counter plus the maximum offset of a conditional jump. The cache controller can be further configured to determine, in response to a jump command received from the processor, if a target address is stored in the cache; and if the target address is stored in the cache, change the program to the target address. The cache controller can be further configured to determine, in response to a jump command received from the processor, if the target address is not stored in the cache, clear the cache and send the target address to the NAND flash. The cache controller can be further configured to sequentially fetch additional instructions from the NAND flash if the jump command is a forward jump command and the address is stored in the cache. The cache can be a SRAM device.
[0009] In some embodiments, a RAM, e.g., an SRAM, is sized and configured to store data ranging from the PC+O (offset) to PC−O (offset) where O (offset) is the absolute offset of a conditional or unconditional jump. Storing addresses in the range of PC+O (offset) to PC−O (offset) can reduce the waiting time when a jump command is issued because the target address is already stored in the SRAM. Therefore, it is not necessary to send a new address to the NAND flash.
[0010] In some embodiments, using a state machine to control access to the NAND flash can reduce the waiting time.
[0011] In some embodiments, a cache controller provides methods to retrieve information from a NAND flash based on the contents of the cache. The cache controller maintains data in the cache to minimize the likelihood that a new address will need to be sent to the NAND.
[0012] In some embodiments, a cache controller allows NAND flash to be used as program ROM without a large SRAM and without an embedded controller.
[0013] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below.
DESCRIPTION OF DRAWINGS
[0014] FIG. 1 is a block diagram of a memory access system.
[0015] FIG. 2 is a block diagram of a cache.
[0016] FIG. 3 is a flow chart of a conditional forward jump process.
[0017] FIG. 4 is a flow chart of a conditional backward jump process.
[0018] FIG. 5 is a flow chart of an unconditional jump process.
[0019] FIGS. 6A-6G are block diagrams of an exemplary use of the cache to store information from the NAND.
DETAILED DESCRIPTION
[0020] Referring first to FIG. 1 , a system 10 includes a NAND flash 22 as program ROM is 20 shown. System 10 also includes a microprocessor unit 12 (MPU) and a cache management unit 14 .
[0021] In general, the MPU 12 interprets and executes instructions contained in software. The software executed by the MPU 12 is stored in the NAND flash 22 . However, the MPU 12 does not access the NAND flash 22 directly. Instead, the MPU 12 accesses the NAND flash 22 and the programs stored therein using the cache management unit 14 .
[0022] The cache management unit 14 includes a cache controller 16 , a NAND interface 18 , and an SRAM 20 . The cache controller 16 controls and manages the content stored in the SRAM 20 by controlling what programs are fetched from NAND flash 22 and caching the desired programs in the SRAM 20 . The cache controller 16 reads programs from the NAND flash 22 and stores the programs in the SRAM 20 . The MPU 12 can access the programs stored therein. The NAND interface 18 provides a communication path between the cache management unit 14 and the NAND flash 22 . The cache management unit 14 uses the NAND interface 18 to receive programs from the NAND flash 22 and to send addresses and instructions to the NAND flash 22 . The NAND interface 18 includes a single data line which is used for both transmitting addresses from the cache controller 16 to the NAND flash 22 and for receiving data from the NAND flash 22 . Since the NAND interface 18 includes a single communication line (as opposed to separate address and data lines) access to the NAND flash 22 is performed in two steps. First, the address is sent from the cache controller 16 to the NAND flash 22 . Second, in response to the received address, the NAND flash 22 sends the requested data to the cache management until 14 via the NAND interface 18 .
[0023] In some embodiments, the NAND flash 22 stores sequential programs and the SRAM 20 caches the sequential programs for execution by the MPU 12 . A sequential program is a program that includes instructions that are executed in a sequential manner. When the NAND flash 22 stores a sequential program, the program is fetched in a sequential manner and, once an initial address is received by the NAND flash 22 from the cache controller 16 , the NAND flash 22 sends data stored in subsequent memory locations of the NAND flash 22 to the cache management unit 14 in a sequential manner (e.g., A, A+1, A+2, A+3, A+4 . . . A+n). During execution of the sequential program by the MPU 12 , a conditional or unconditional jump may occur. A conditional jump is an instruction to jump to a target address and begin executing the program at the target address if a particular condition is met. An unconditional jump is an instruction to jump to a target address regardless of any conditions. The absolute offset of a conditional jump of the MPU 12 is represented herein by the variable “O (offset) .”
[0024] Referring to FIG. 2 , an exemplary block diagram of the memory locations of SRAM 20 is shown. The SRAM 20 is configured to have a minimum size of twice the absolute offset of a conditional jump (e.g., 2*O (offset) ). In general, the size of the absolute offset is between about 128 and about 32768 resulting in a cache size of about 256 to about 65536 for the SRAM. Having a cache with minimum size of 2* O (offset) allows the MPU 12 to jump forward or backward by the absolute offset of a conditional jump “O (offset) ” without requiring the cache controller 16 to send a new address to the NAND flash 22 . A new address is not necessary because the SRAM 20 stores instructions from the current value of the program counter minus the offset (i.e., PC−O (offset) ) to the current value of the program counter plus the offset (i.e., PC+O (offset) ) and thus can accommodate the jump. Storing this set of instructions in the SRAM 20 can provide the benefit of reducing the delay time when a conditional or unconditional jump is encountered by eliminating the delay associated with sending a new address and receiving data from the NAND flash 22 .
[0025] The cache controller 16 uses the SRAM 20 as a circular buffer with the current location within the buffer indicated by a program counter (PC). The cache controller 16 includes a state machine that controls the content of the SRAM 20 . The content of the SRAM 20 will vary depending on the conditions received by the cache controller 16 from the MPU 12 during execution of the sequential program (as described below).
[0026] In general, the cache controller 16 automatically fetches data from the NAND flash 22 during time periods when the SRAM 20 is not being accessed by the MPU 12 . The cache controller 16 continues to sequentially fetch data sequentially from the NAND flash 22 until the SRAM 20 is full. When the SRAM 20 is full, the cache controller 16 waits to fetch additional data from the NAND flash 22 until MPU 12 has accessed some of the data in the SRAM 20 such that a portion of the data in the SRAM 20 that is no longer within the range of plus or minus the O (offset) from the PC can be overwritten.
[0027] During execution of the program, MPU 12 can cross pages or blocks. A block is the basic unit for erase in NAND flash 22 is block and a page is the basic unit for read/write in NAND flash 22 . One block contains, for example, 32 pages or 64 pages. All pages in the same block have the same block address. When the MPU 12 crosses to a new page having the same block address as the previous page, there is no need to search out new block address. During execution of the program, when the MPU 12 crosses pages, the cache controller 16 automatically generates a read command and sends the address to the NAND flash 22 for reading the new page. If crossing blocks (for example, in a block containing 32 pages, crossing blocks means moving from page 31 in the current block to page 0 in another block), the new block address must be determined. Thus, when the MPU 12 crosses blocks, the cache controller 16 does not fetch new data from the NAND flash 22 . Instead, the cache controller 16 generates a read fault signal.
[0028] As described above, the NAND flash 22 stores a sequential program. When the MPU 12 executes the sequential program, the data needed to be retrieved from the NAND flash 22 and stored in the SRAM 20 is generally sequential nature. Thus, during sequential execution of the program by the MPU 12 , the cache controller 16 attempts to keep addresses PC−O (offset) to PC+O (offset) in SRAM 20 (i.e., the data stored at the current program counter and the data within the offset O (offset) of the program counter). The actual addresses stored in SRAM 20 at any particular time vary somewhat from the desired range of PC−O (offset) to PC+O (offset) due to the timing needed to access the SRAM 20 and to access the NAND flash 22 . For example, the cache controller 16 retrieves data from the NAND flash 22 when the SRAM 20 is not being read by the MPU 12 . This may result in a delay between the time when the instructions located at PC are read and when the instructions located at PC−O (offset) are overwritten with new data from the NAND flash 22 . However, during sequential execution the cache controller 16 attempts to maintain the addresses from PC−O (offset) to PC+O (offset) in the SRAM 20 as nearly as possible.
[0029] During the execution of the sequential program, the MPU 12 may encounter various types of instructions groups such as conditional jumps and unconditional jumps. When the MPU 12 encounters a conditional or unconditional jump, the cache controller 16 attempts to complete the jump without sending a new address to the NAND flash 22 as described below in relation to FIGS. 3-5 .
[0030] Referring to FIG. 3 , a process 50 for managing the information retrieved by the cache controller 16 from the NAND flash 22 when a conditional forward jump is encountered is shown. A conditional jump forward is encountered when the instruction executed by the MPU 12 depends on a condition. If the condition is not met, then the MPU 12 continues to execute the program sequentially. If the condition is met, then the program jumps to an instruction located at an address subsequent to the currently executing address (referred to as the target address). The maximum offset of the conditional jump forward is indicated as “+O (offset) .”
[0031] When the MPU 12 receives ( 52 ) a conditional jump forward and the condition is met, the cache controller 16 determines ( 54 ) if the target address for the conditional jump forward is in the SRAM 20 . If the target address is not in the SRAM 20 , then the cache controller 16 clears ( 56 ) the SRAM 20 and sends 60 the target address to the NAND flash 22 to fetch new programs starting at the target address. If the target address is in the SRAM 20 , then it is not necessary to send the target address to the NAND flash 22 . Rather, the cache controller 16 sets ( 58 ) the program counter (PC) to the target address. The cache controller 16 also retrieves programs from PC+1 to PC+O (offset) when the SRAM 20 is not being accessed by MPU 12 . Since the NAND flash 22 to continues to send the data to the SRAM 20 sequentially when the target address for a conditional jump forward is in the SRAM 20 and no new address is sent to the NAND flash 22 , the delay time of sending a new address to the NAND flash 22 during a conditional jump forward is eliminated.
[0032] Referring to FIG. 4 , a process 70 for managing the information retrieved by the cache controller 16 from the NAND flash 22 when a conditional jump backward is encountered is shown. A conditional jump backward is encountered when the instruction executed by the MPU 12 depends on a condition. If the condition is not met, then the MPU 12 continues to execute the program sequentially. If the condition is met, then the program jumps to an instruction located at an address prior to the currently executing address (referred to as the target address). The maximum offset of the conditional jump backward is indicated as “−O (offset) .”
[0033] When the MPU 12 receives ( 72 ) a conditional jump backward and the condition is met, the cache controller 16 determines ( 74 ) if the target address for the conditional jump backward is in the SRAM 20 . If the target address is not in the SRAM 20 , then the cache controller 16 clears ( 76 ) the SRAM 20 and sends ( 78 ) the target address to the NAND flash 22 to fetch new programs starting at the target address. If the target address is in the SRAM 20 , then it is not necessary to send the target address to the NAND flash 22 . Rather, the cache controller 16 sets ( 80 ) the program counter (PC) to the target address. The cache controller does not fetch new data from the NAND flash 22 because the programs at the requested target address are already stored in the cache and therefore, no new data is fetched from the NAND flash 22 ( 82 ). More particularly, the cache controller 16 does not immediately retrieve any additional data from the NAND flash 22 because the cache controller attempts to maintain addresses PC−O (offset) to PC+O (offset) in the SRAM 20 . Therefore, until a portion of the instructions currently stored in the SRAM 20 are executed, no new data needs to be retrieved. Since the NAND flash 22 simply delays sending additional data to the SRAM 20 (but the data is still sent sequentially) when the target address for a conditional jump backward is in the SRAM 20 , the delay time of sending a new address to the NAND flash 22 during a conditional jump backward is eliminated.
[0034] Referring to FIG. 5 , a process 100 for managing the information retrieved by the cache controller 16 from the NAND flash 22 when an unconditional jump or a call function is encountered. An unconditional jump is encountered when the instruction executed by the MPU 12 instructs the MPU 12 to begin executing at a different location within the program (referred to as the target address). When the MPU 12 receives ( 102 ) an unconditional jump, the cache controller 16 determines ( 104 ) if the target address for the jump is in the SRAM 20 . If the target address is not in the SRAM 20 , then the cache controller 16 clears ( 106 ) the SRAM 20 and sends ( 108 ) the target address to the NAND flash 22 to fetch new programs starting at the target address. If the target address is in the SRAM 20 , then it is not necessary to send the target address to the NAND flash 22 . Rather, the cache controller 16 sets ( 110 ) the program counter (PC) to the target address. The cache controller 16 then determines if the unconditional jump or call is a backward jump or call ( 112 ). If the unconditional jump or call is not a backward jump or call (e.g., it is a forward jump or call), the cache controller 16 maintains addresses from PC−O (offset) to PC+O (offset) in the SRAM 20 ( 116 ). If the offset of the jump is forward, this may require sequentially fetching additional instructions from NAND flash 22 . If the offset of the jump is backward, this may require delaying receiving additional instructions from the NAND flash 22 . In this case, the cache keeps programs from the previous PC−O (offset) to PC+O (offset) in the SRAM 20 ( 114 ).
[0035] As described above the cache controller 16 generally attempts to maintain, as nearly as possible, the addresses from the current address of the program counter minus the offset (i.e., PC−O (offset) ) to the current address of the program counter plus the offset (i.e., PC+O (offset) ). Keeping the addresses from PC−O (offset) to PC+O (offset) in SRAM 20 reduces the waiting time encountered when a jump is encountered by eliminating the need to send a new address to the NAND flash 22 . FIGS. 6A-6G provide an example of how the cache controller 16 responds to various conditions during the execution of a sequential program stored in SRAM 20 based on the processes described above. In FIGS. 6A-6G , the time as indicated by T=x does not necessarily represent a single time step or cycle of the MPU 12 .
[0036] Referring to FIG. 6A , prior to time T=0 the SRAM 20 is empty. In order to fill the SRAM 20 , at time T=0, the cache controller 16 sends an address “A” to the NAND flash 22 . In response, the NAND flash 22 will begin to send the instruction(s) at address A and the instructions will be stored in the SRAM 20 (as indicated by block 122 ). The program counter (PC) is set to the address requested, namely address A, as indicated by arrow 120 . Since the NAND flash 22 stores a sequential program, it is not necessary to send a new address to the NAND flash 22 in order to fill the SRAM 20 with additional portions of the sequential program. The cache controller 16 fills the remainder of the SRAM 20 when the SRAM 20 is not being accessed by the MPU 12 . Since the MPU 12 executes the instructions at a speed slower than the speed at which the NAND flash 22 fetches the instructions and stores the instructions in SRAM 20 , the SRAM 20 will be filled with sequential portions of the program at addresses A+1 to A+2 O (offset) −1 as indicated by portion 124 . The absolute offset of a conditional jump is represented by the variable “O (offset) ” The actual offset of any particular conditional jump can be any value smaller than O (offset) .
[0037] Referring to FIG. 6B , at time T=1, the MPU 12 has executed the instructions at addresses A to A+O (offset) . Since the MPU 12 has executed the instructions located at A to A+O (offset) , the program counter is set to A+O (offset) as shown by arrow 130 . Thus, at time T=1, the cache stores instructions from PC−O (offset) to PC+O (offset) (e.g., A to A+2O (offset) −1).
[0038] Referring to FIG. 6C , when the time increments from T=1 to T=2, the MPU 12 has executed the instruction at address A+O (offset) and the program counter is incremented from A+O (offset) to A+O (offset) +1 as indicated by arrow 132 . When the program counter is incremented to A+O (offset) +1, the cache controller attempts to maintain addresses from PC−O (offset) to PC+O (offset) in the SRAM 20 . Therefore, the cache controller 16 overwrites the cache location which had been filled with address A at time T=1 with address A+2O (offset) Thus, at time T=2, the program counter is located at A+O (offset) +1 and addresses A+1 to A+2 O (offset) are stored in SRAM 20 .
[0039] Referring to FIG. 6D , between time T=2 and T=3 a conditional jump forward in which the condition was met or an unconditional jump forward has occurred with a target address of A+2O (offset) −1. Since the address A+2O (offset) −1 is currently stored in the SRAM 20 , the cache controller does not have to send a new address to the NAND flash 22 . The cache controller 16 changes the program counter to the target address, namely A+2O (offset) −1, as indicated by arrow 134 . Since a forward jump has occurred, a portion of the cache 136 is overwritten in order to keep addresses in the range of PC−O (offset) to PC+O (offset) in the SRAM 20 (since the program counter is A+2O (offset) −1 the cache controller attempts to supply the range of A+O (offset) to A+3O (offset) −1 in SRAM 20 ). In particular, in order to keep the desired range of addresses in the SRAM 20 , the cache controller 16 overwrites a portion 136 of the SRAM 20 that previously contained addresses A+1 to A+ (offset) with addresses in the range from A+2O (offset) +1 to A+3O (offset) −1.
[0040] Referring to FIG. 6E , at time T=4 a conditional jump backward in which the condition was met or an unconditional jump backward has occurred with a target address of A+O (offset) . Since the address A+O (offset) is currently stored in the SRAM 20 , the cache controller does not have to send a new address to the NAND flash 22 . In order to complete the jump, the cache controller simply changes the program counter from A+2O (offset) −1 (i.e., the program counter at time T=3) to the target address A+O (offset) . When the program counter is changed to A+O (offset) , the addresses from A+O (offset) t to A+3O (offset) −1 will remain in the SRAM 20 . Thus, there will be a period of time during which the SRAM 20 stores instructions from PC to PC+2O (offset) rather than PC− (offset) to PC+O (offset) as desired. As shown in FIG. 6F , since the SRAM 20 includes the range of PC to PC+2O (offset) at time T=4, no new data will be received from the NAND flash 22 and stored in the SRAM 20 until the program counter is incremented from A+O (offset) to A+2O (offset) −1 such that the range of PC−O (offset) to PC+O (offset) is once again stored in SRAM 20 (e.g., A+O (offset) to A+3O (offset) −1 since the program counter is A+2O (offset) −1).
[0041] Referring to FIG. 6G , at time T=6 a conditional or unconditional jump in which the address was not in the SRAM 20 has occurred. Since the target address “B” is not in the SRAM 20 . In order to fill the SRAM 20 , at time T=6, the cache controller 16 sends the target address “B” to the NAND flash 22 . In response, the NAND flash 22 will begin to send the instruction(s) at address B and the instructions will be stored in the SRAM 20 . The program counter (PC) is set to the address requested, namely address B and the cache controller 16 fills the remainder of the SRAM 20 with addressed B+1 to B+2O (offset) −1 when the SRAM 20 is not being accessed by the MPU 12 .
[0042] Other embodiments are within the scope of the following claims: | Methods and related computer program products, systems, and devices for using a NAND flash as a program ROM are disclosed. | 6 |
This application is related to co-pending U.S. patent application Ser. No. 09/435,983, entitled: METHOD AND DEVICE FOR EXPOSING BOTH SIDES OF A SHEET, by Inventor(s): Marc Vernackt, Ronny De Loor, Anne-Marie Empsten, and Mark Ryvkin, filed: Nov. 8, 1999, Attorney/Agent's Ref. No.: BARCO-014-1, which is incorporated by reference herein for all purposes.
BACKGROUND
The present invention relates to direct image printing and more specifically to an automated method of handling and processing printed circuit board panels, printing plates, or other sensitized sheets through a direct imaging process.
It is known today that printed circuit boards may be composed of several PCB panels, each panel having two sides, one or more of which is provided with a layer forming an electrical circuit. When there is only one panel having only two layers, the board is commonly called a double-sided board, and when there are more than two layers, the board is commonly called a multi-layer board. A common way of manufacturing a multi-layer board is by fixing several panels together, each panel having a single printed circuit on one side, or a circuit on each side. “Outer” panels are those that face the outside of a multi-layer PCB, and “inner panels” are the interior panels. Typically, the inner panels have a circuit on both sides, while the outer panels have a circuit only on one, the outer side. Each inner panel resembles a thin double-sided PCB in that the panel is comprised of an insulating substrate which is clad on both sides with metallic foil, typically copper foil. A printed circuit is formed on any circuit side of an inner panel by that side's metal cladding having a light-sensitive layer laid on top of the metal. The light-sensitive layer is exposed to light (typically ultra-violet (UV) radiation) at selected locations, then processed by a photographic process that removes the layer at selected locations. An etching process is then applied to remove those parts of the layer of metal not necessary for forming the actual circuit. Once all the double-sided inner panels are produced, they are fused (pressed) together by placing an insulating binding material, typically a partially cured epoxy-resin material called prepreg, between the panels. Unexposed outer foils are placed on the outside of the double-sided inner panels, again with prepreg in between. All the layers are now laminated by applying heat and pressure that causes the prepreg to flow and bond to the surfaces of the inner panels and the outer foils. Holes are now drilled on the laminated multi-layer board, including holes for mounting electrical components inserted into the board (“mounting holes”), and holes for making contacts from one layer to one or more other layers (feed-throughs, also called vias or conductive vias). The holes typically are plated through. Each side of the multi-layer panel now is sensitized, then exposed and processed to form the two outer printed circuits in exactly the same manner as forming circuits on the inner panels. New technology for making PCB panels like SBU (sequential build up) or direct ablation of the copper can be used with direct imaging technology. Since a multi-layer panel is exposed in the same way as an inner PCB panel, the words “PCB panel” or simply panel will mean either a complete PCB board, an inner PCB panel, or a post-lamination multi-layer panel.
One difficulty in producing multi-layered printed circuit boards is the strict requirement for accuracy in positioning the different PCB panels together to ensure that the different circuits are positioned very accurately relative to each other. In particular, the mounting holes and vias need to be very accurately placed on each layer's circuits. For a particular tolerance for the placement of a circuit, it is clear that any deviations in the specified location of the circuits on each of the layers may be additive, so that at any one location, there could be large deviations. For the case of double-sided panels, including the multi-layer panel after lamination, it is even more difficult to position the circuits accurately enough relative to each other.
Also for the new technology such as the SBU, where each new layer is directly added to the previous stack of layers as an additive process, the relationship between imaging process and the registration process becomes very critical. The relationship between imaging process and the registration process becomes increasingly critical as increased geometrical accuracy and increased PCB layout density is desired.
A common method for producing printed circuit boards is to first produce artwork, which is an accurately scaled configuration used to produce a master pattern of a printed circuit, and is generally prepared at an enlarged scale using various width tapes and special shapes to represent conductors. The items of artwork, once reduced, for example, by a camera onto film to the correct final size, are referred to as phototools and are used as masks for exposing the sensitized layers. Because the photographic reduction is never 100 percent accurate, more accurate phototools are produced nowadays using photoplotters rather than photographic reduction. However produced, physical phototools are susceptible to damage. In addition, whenever any amendments need to be made to any circuit, new phototools need to be produced. Furthermore phototools, sometimes in the form of photographic negatives, are difficult to store. They also may not be stable; their characteristics might change with temperature and humidity changes and can suffer degraded quality over time.
There thus are advantages to directly imaging the required circuit patterns onto PCB panels, for example PCB panels that include a light-sensitive layer on one or both sides. The same advantage also is applicable to directly imaging printing plates that include a UV, visible light, or thermally-sensitive layer. Often such sensitive sheets as used for PCBs or thermal printing plates are rigid, so that the scanning apparatus for exposing such sheets for direct imaging (e.g., directly exposing printing plates or directly exposing PCB panels) is of the flat-bed type in which the sheet is disposed on a horizontal table for exposure by the light energy (e.g., UV light or infrared) produced by the scanner. Such scanning apparatuses are typically quite bulky because of the horizontal table. Also, such direct imaging systems expose one side at a time, and there are problems accurately aligning the two sides for double-sided exposure.
Direct imaging addresses some of the production issues such as the difficulties associated with photoplotters, phototools, and the image transfer process. Direct imaging, however, does not ensure proper alignment of the PCB panel to be processed, especially with outer layers where the image has to match the drilled holes pattern. Further, direct imaging, alone, does not address the handling of the PCB panels. Modern PCB panel can be large scales such as up to 24 inches in width and up to 36 inches in length (609.6 mm×914.4 mm) or even larger PCB panels are know to be used.
The manufacturing difficulties of precise alignment and handling described above are further amplified as the overall physical size of the PCB panel increases. In many specialized applications the PCB panel can be large scale PCB panels as large as 24 inches in width and 36 inches in length (609.6 mm×914.4 mm) or even larger. The large scale sizes are more difficult to handle and accurately align for processing than more typical, smaller PCB panels. The result is a very slow, complicated and expensive production process that typically results in inconsistent product quality.
Thus there is a need for an automated method for precisely handling, aligning, for example, a drilled holes pattern, and direct imaging both sides of large scale PCB panels to produce a consistently high quality product for a low cost and at a high rate of production. Further, such a process should include the capability of handling large as well as small size PCB panels. Also, mixing panels of varying sizes and thicknesses to be imaged can happen dynamically and automatically without operator input or introducing unnecessary delays and provides the operator with total production flexibility.
SUMMARY OF THE INVENTION
The present invention provides an automated, flow-through, dual side, laser direct imaging process and apparatus. This provides the capability to simultaneously image both sides of a substrate in a continuous flow-through process. The present invention provides efficiency and flexibility improvements over the prior art on several levels. First, the prior art is a batch-based process in which substrates are imaged one (or a batch) at a time in contrast where the present invention is a continuous, flow through, sequential process whereby a first substrate is followed into the apparatus by a second substrate which is, in turn followed by a third and so forth and the second substrate begins the process through the apparatus before the first substrate completes the process through the apparatus, substantially reducing or even eliminating handling process time. Second, the process time per substrate is reduced as compared to the prior art. Third, different panel sizes and thickness can be mixed according operator needs without introducing additional handling process time which provides the operator with total production flexibility.
The present invention discloses a method for automated direct imaging of a sensitized panel. First, a panel is loaded to a registration station and registering the panel. Then imaging at least one of a front surface and a back surface of the panel utilizing a direct imaging station. Then unloading the panel. The process occurs automatically in sequence without operator intervention. Additional panels can be handled and processed automatically.
The present invention describes an apparatus for automated direct imaging of a sensitized panel. The apparatus includes a loading station mounted on a floor surface, a registering station which is detachably docked to a loading station and an imaging station, and an unloading station mounted on a floor surface. A sensitized panel can be loaded in said loading station, and then moved to said registering station, and then registered in said registering station, and then imaged in said imaging station, and then unloaded at said unloading station.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 illustrates a modular view of one embodiment of the present invention 100 .
FIG. 2 illustrates the parallel processing 200 of multiple panels through the one embodiment of the present invention.
FIG. 3 illustrates the sequentially processing 300 of multiple panels through the one embodiment of the present invention.
FIG. 4A illustrates an isometric view of one embodiment 400 of the present invention.
FIG. 4B illustrates a front view of one embodiment 400 of the present invention.
FIG. 4C illustrates a top view of one embodiment 400 of the present invention.
FIG. 4D illustrates a side view of one embodiment 400 of the present invention.
FIGS. 5A-5B illustrate one embodiment of the panel flipper 500 in accordance with the present invention.
FIGS. 6A-6E illustrate another embodiment of the panel flipper 600 in accordance with the present invention.
FIG. 7 illustrates the six directions necessary to register a panel 702 .
FIG. 8A illustrates one embodiment of the registration station, in accordance with the present invention.
FIG. 8B illustrates one embodiment of the registration station, in accordance with the present invention.
FIGS. 9A-9B illustrates one embodiment of the exposing carriage carrying a panel through the dual side imager, in accordance with the present invention and shows the unload system.
FIG. 10 illustrates one embodiment of a dual side direct imager 1000 in accordance with the present invention.
FIGS. 11A-11B illustrates one embodiment of the panel unload section 1100 in accordance with the present invention.
FIG. 12 illustrates an embodiment of a local area network (LAN) 1200 in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a modular view of one embodiment of the present invention 100 . The modules include a loading module 110 , a registration module 120 , an exposing or imaging module 130 and an unloading module 140 . Both the process and apparatus of each respective module will be more fully described below. An overview of the process of the present invention includes first loading a sensitized panel or substrate, then aligning or registering the panel in the system, then imaging or exposing the panel, and finally unloading the panel from the present invention.
The process through the first embodiment begins with loading a first panel. The loading zone 110 includes different actions and phases with multi-tasking capabilities. The main function is to accept a panel and to move the panel to the next zone, in this case a registration zone 120 . In an alternative embodiment, the panel is pre-registered in the loading zone. In a preferred embodiment, the complete loading zone 110 can be removed or separated from the other portions of the present invention to ease shipment, installation and service.
The interface to between the outside world and the loading zone 110 can be fully automated or manual. In an automated embodiment, the connection with the previous process is accomplished using a conveyor, a robot or other equivalent automated methods. In an alternative automated embodiment, simple electrical signals such as input ready, input busy or input jam can be linked to the previous process making the system to work in a closed loop. Other control and status data can also be communicated to other previous processes, subsequent processes and remote monitoring and or control systems. In a manual embodiment an operator manually places the panel in the loading zone. In an alternative embodiment, the present invention can accept panels input from at least two directions: i.e. from the side or from the front of the loading zone. Other directions such as vertically loaded panels or from the rear of the apparatus can also be accommodated in still other embodiments. Accepting input from multiple directions provides increased flexibility and compatibility with the prior processes. In one embodiment, one input direction could be automated and provide the other inputs available for manual operation. The preferred embodiment can also include sensors to automatically detect which direction a panel is input from. In such an embodiment, the sensors can be utilized to disable any other input direction when the first input direction is utilized. Such sensors may be infra red or other light sensors or may also be weight or motion sensors.
In an alternative embodiment, a panel cleaning device can be added immediately preceding the loading zone. Panel cleaning devices are utilized to remove contamination such as dust, grit, fibers, hair, machinery debris, insects, etc that are larger than 1 micron or even smaller. Such panel cleaning devices are widely available such as the Clean Machine from Teknek Electronics Ltd. River Drive, Inchinnan Business Park, Renfrewshire, PA4 9RT, Scotland, UK or similar cleaning devices. In still another alternative embodiment, the cleaning devices could be located in other locations in the process and apparatus as long as they are used before the imaging process.
In yet another embodiment, the entire process apparatus may be contained within a controlled environment such as a Class 1000 environment or better. As is well known to those skilled in the art, a Class 1000 environment controls the amount of contamination in the ambient air surrounding the process. A cleaner, controlled environment results in a more accurate, repeatable imaging process as any contaminants can interfere with the imaging process. Different methods to enclose the process and apparatus in a Class 1000 or better clean environment include housing the process apparatus in a Class 1000 clean-room or in a self-contained micro-environment. Such micro-environments are widely available from various sources. Examples include various products and systems from Clean Air Technology of Canton, Mich., USA or Clean Air Products of Minneapolis, Minn.
In yet another embodiment, additional modules can be placed in front of the input slot. One such device can read bar codes. If the panel s to be exposed are labeled with a bar code, this bar code reader device could get information about size and material properties of the panel to be exposed. This could than be used to automatically retrieve the correct image data from a server such as a raster imaging processor (RIP). Such an embodiment reduces errors such as size mismatches between image data size and panel size which can happen easily when processing various panel sizes. Also, such a bar code reader can reduce the operator effort to operate the machine since the operator now must only observe the panel supply towards the processing apparatus.
Optionally, the panel can next be pre-registered. In pre-registering, the panel is mechanically aligned to a reference point on the loading table. Pre-registration accuracy in the range of 1 mm can be achieved easily in a very short cycle time. The panel is moved mechanically such as by sliding across the loading table or by tilting the loading table, toward the zero position. The panel is aligned by three pins using the sides of the panel. A zero position detector will check if the panel is pre-registered correctly or not. The big advantage in doing a pre-registration is that less time is required during the final, fine registration process because the positional error is already substantially reduced. Pre-registration can thereby decrease the total throughput time.
Next, the panel is picked-up and rotated from a horizontal position to a vertical position. This is accomplished by rotating a pick-up mechanism to near t he panel level. One embodiment of the pick-up includes a set of grippers to hold the panel at the edges. Other methods such as vacuum caps or a vacuum table may also be utilized to hold the panel during rotation. See for example, U.S. patent application Ser. No. 09/447,184 to Vernackt filed Nov. 22, 1999, entitled AUTOMATICALLY ADAPTING VACUUM HOLDER, and assigned to the assignee of the present invention, for an example of a vacuum table that may be used in the present invention. An advantage of using grippers is that the chance of dropping the panel during rotation and moving is significantly reduced. Also when the panel is transferred to the registration system, the panel must be gripped by a second gripper system or a vacuum table. Grippers use only a small portion of the panel. After closing the grippers, the pick-up mechanism and the panel are rotated from a horizontal to a vertical position. The bottom load plate can also rotate to help the panel being rotated to avoid being bent. The panel then hangs vertically. The bottom plate then returns to the horizontal position. The loading zone 110 is then free and both inputs are cleared, ready to accept the next panel. As the first panel is moved to the registration zone 120 or section, a second panel can be loaded in the load zone 110 . Each of the different portions of the loading process, happen fully independently and thus in parallel with other actions of the present invention. Approximately 20 seconds are required to complete the load/pre-registration process on the panel.
Now that the first panel is in the registration zone 120 , the panel must be registered. Registration is a multi-step process. First, the panel is rotated slightly so that the vertical line between two reference points at top and bottom of the panel are parallel to the scan line. Typically, three reference points or targets are used to determine the X-Y scale factor and the delta theta rotation error. Delta theta rotation error is the change in rotation required to cause the two reference points forming a vertical line on the panel to be parallel to the scan line of the imaging section. The delta theta rotation error correction can be accomplished mechanically by rotating the vacuum plate or grippers holding the panel using a motor with a gearbox or eccentric systems or using piezo devices in the grippers to achieve highly accurate positions. During this rotation, a vision system checks the position of at least two targets on the panel and forms a closed loop with the driver or controller of the motor. Next, the two scale factors in X and Y direction are searched using at least three targets. The three targets are typically located in a L-shape along the long and short side of the panel. Using a grid system and a dynamic range vision system, the registration phase can happen very quickly and gives total location freedom of the targets to be inspected.
Also the number of targets in this case to be checked does not matter for the system. In an alternative embodiment, both surfaces of the panel can be registered as described above. If both surfaces are registered then any alignment error existing between the two surfaces can be determined and appropriate correction data can be sent to the imaging section so that the alignment errors are corrected for during the imaging process.
Next, the panel is attached to the exposing carriage using grippers or an equivalent holding device such as a vacuum or other holding devices. Once the grippers of the exposing carriage have closed on the panel, the registration zone 120 is reset to accept the next panel for registration. At this point the relative position of the panel to the grippers of the exposing carriage is known. This relative position information can be utilized in the imaging process to correct or adjust the imaging process.
The exposing carriage then transports the panel through the imaging zone 130 or section. In the imaging zone 130 , a dual sided, laser, direct imager exposes both sides of the panel simultaneously as the exposing carriage moves the panel very accurately using a high resolution linear encoder or other similar devices known in the art. The direct imaging or scanning process is the dominating process and depends on many variables such as available laser power, resolution, resist sensitivity, etc. Before the scanning begins, the optical scanning heads are brought in close proximity to the panel. The panel hangs vertically, so that the panel's weight helps maintain the straight, vertical orientation of the panel. A pair of guides below the optical heads, establish an air bearing on either side of the panel. The guides and resulting air bearing enable a very precise vertical position of the panel. The scanning begins at the front edge of the panel and continues in a vertical line as the panel progresses horizontally. In short, the imager scans up and down and the panel movement provides the horizontal movement necessary to scan or image the entire surfaces of the panel. See above mentioned U.S. patent application Ser. No. 09/435,983 for a description of one embodiment of an imaging apparatus and process suitable for the present invention. In alternative embodiments of the present invention, other dual side direct imaging processes can also be utilized.
When the last scan line is set onto the panel, the grippers mounted on the exposing carriage will open. The panel then falls downwards in a controlled manner to be picked up by the unloading section 140 or zone. Similar to the loading section 110 or zone, the unloading section 140 or zone can include sensors to sense the presence of a panel. The unloading section 140 can also be automatic or manual in interface with any subsequent processes. Also similar to the loading zone 110 , the unloading zone 140 can include the capability for unloading to subsequent processes in a plurality of directions. Also similar to the loading zone 110 , one exit slot can be automated while the others can be used for manual uses. Also similar to the loading zone 110 , the complete unloading zone 140 can be removed or separated from the other portions of the present invention to ease shipment, installation and service.
During operation in continuous full, flow through mode, i.e. most efficient manner, three panels are in process at any one time. Each panel will have a different action. Each of the sub processes: loading, registering, imaging and unloading are operating fully independent and that the overall system is in multi-tasking mode. In the preferred embodiment, the logic is controlled via an embedded computer (PC), running control software. In other alternative embodiments other types of controllers such as sequential logic controllers, PLCs and other controllers may also be used.
One embodiment of the present invention may be operated in three types of integration of this principle: fully automated, semi-automated and manual. Fully automated means that automated input and output via a conveyor or robots or equivalents thereof and panels are delivered to the input in an automated manner and the panels output are removed from the unload section in an automated manner. Semi-automated means that the panels are delivered manually for input and removed from the unload section manually, but inside the process the panel handling is accomplished fully automatically, using the loading and unloading sections. Manual operation means operation without the loading and unloading sections. In manual operation, panels are manually “loaded” directly into the registration section and removed from the output of the imaging section.
FIG. 2 illustrates the parallel processing 200 of multiple panels through the one embodiment of the present invention. FIG. 2 is divided by lines 1 to 14 . Lines 1 to 14 are divided into four columns designated by their respective headings: Load Zone, Registration Zone, Expose Zone and Unload Zone. FIG. 2 also includes timing points of the process designated T 0 , T 1 , T 2 , T 3 and T 4 , respectively. T 0 represents the start time of the process on a first panel 210 . T 1 represents the completion time of loading the first panel 210 . T 2 represents the completion time of registering the first panel 210 . T 3 represents the completion time of exposing or imaging the first panel 210 . T 4 represents the completion time of unloading the first panel 210 . The present invention is capable of handling various sizes of panels through the process. Examples of some of the various panel sizes and the timing, expressed in seconds, in processing the panels through one embodiment of the present invention are included in Table 1.
TABLE 1
Timing
36 Inch
18 Inch
32 Inch
Point
Panel*
Panel*
Panel*
T 0
0
0
0
T 1
10
10
10
T 2
20
20
20
T 3
65
45
61
T 4
75
55
71
*Time expressed in seconds
FIG. 2 also illustrates at least a portion of the processing of subsequent panels 220 , 230 and 240 through the present invention. In one embodiment, the present invention can process panels ranging in dimensions within the range of 9 inches to 24 inches in width and 12 inches to 32 inches in length and 50 μm to 6 mm in thickness.
FIG. 3 illustrates another embodiment 300 of the present invention where the panels 310 , 320 , 330 , 340 are processed sequentially rather than parallel as shown in FIG. 2 . Sequential processing may be preferred for certain applications but results in a somewhat slower process time for the subsequent panels 320 , 330 , 340 . As is clearly shown panel 340 is not loaded until line 14 in sequential processing, FIG. 3 as compared to panel 240 loaded at line 12 in parallel processing, FIG. 2 .
FIG. 4A illustrates an isometric view of one embodiment 400 of the present invention. The loading zone 410 is shown in the foreground and includes the loading table 401 and the panel flipper 404 . The registration section 420 , is not shown but the location is as shown. The imaging section 430 is shown in the center of the FIG. 4 A. The unloading section 490 includes an unloading table 492 . The foundation slab 432 and the foundation slab forklift openings 434 of the image section 430 are also shown.
FIG. 4B illustrates a front view of one embodiment 400 of the present invention. The exposing carriage 436 , vertical supports 438 , imager 440 , foundation slab 432 and top rail 442 are shown. The foundation slab 432 , vertical supports 438 and top rail 442 are manufactured from a very stable material. The registration section 420 is not shown in FIG. 4 B. FIG. 4C illustrates a top view of one embodiment 400 of the present invention. The exposing carriage grippers or clamps 444 , 446 , 448 imager 440 and top rail 442 are shown. The registration section 420 is not shown in FIG. 4 C.
FIG. 4D illustrates a side view of one embodiment of the present invention showing the registration section 420 , which includes the registration sub frame 450 , tapered guide pins 452 , 454 and guide pin sockets 453 , 455 which are mounted to the registration mount 460 which is securely fastened to the foundation slab 432 . Between the registration sub frame 450 and foundation slab 432 , vibration isolators 462 , 464 are installed. The isolators can be air bellows or other viscous couplings capable of isolating the registration sub frame 450 from the foundation slab 432 . Such viscous couplings can include oil or water filled couplings or combinations thereof or any equivalents thereof. Additional vibration isolators 466 , 468 are installed between the foundation slab 432 and the base 470 . The base 470 is mounted via legs 474 , 478 to the floor surface 472 . The isolators 466 , 468 are operable to isolate the from the foundation slab 432 from vibrations in the floor surface 472 or other portions of the outside world such as the loading 410 and unloading 490 sections. Isolating the foundation slab 432 and thereby isolating the imager 440 installed on the foundation slab 432 is extremely critical toward maintaining accuracy of the scanning and imaging. The foundation slab 432 , vertical supports 438 and top rail 442 can be manufactured from any large, stiff and massive material. Examples include granite, steel or other equivalently massive and stiff material. In a preferred embodiment, the foundation slab 432 is at least 3000 kg. This heavy weight ensures us a very stable construction where the impact of external vibrations is reduced to a minimum. A lighter foundation slab 432 would be more susceptible to external vibrations and there fore less preferred.
FIG. 5A illustrates one embodiment of the panel flipper 500 in accordance with the present invention. The panel flipper is utilized to rotate the panel to be exposed from horizontal to vertical orientation. The panel flipper 500 includes a frame 501 and a suction cap system 502 for securely holding the panel 504 . A vacuum ejector 520 for generating the vacuum in the suction caps system 502 and thereby holding the panel 504 . A rotary actuator 510 is also shown. The rotary actuator 510 can also include internal detectors and speed controllers. A counterweight 512 is also included to balance the frame 501 and ease in the movement of the frame 501 . The suction caps system 502 can include a plurality of suction caps 524 configured to allow the panel flipper 500 to engage and securely move a plurality panel sizes. A vacuum table system as mentioned in U.S. patent application Ser. No. 09/447,184 can be used in one embodiment. FIG. 5B illustrates the plurality of suction caps 524 arranged in an array configuration. Other arrangements may also be utilized to cover a sufficient portion of the panel 504 to be handled. The vacuum is operable to hold the panel 504 during rotation and so that the panel 504 hangs vertically during movement toward the registration zone.
FIG. 6A illustrates a load section 600 in accordance with one embodiment of the present invention. Table 602 , panel 603 , edge reference pins 662 , 664 , 666 , zero point detector 660 , input rollers 656 and transfer ramp 658 . The edge of panel 603 is positioned against the three reference pins 662 , 664 , 666 . The zero point detector 660 then checks the panel is properly positioned and touching the reference pins 662 , 664 , 666 . In an alternative embodiment, the reference pins 662 , 664 , 666 can be a straight zero point edge 661 such as shown in FIG. 6 B. FIG. 6B illustrates one embodiment of the loading section 600 and a loading table 602 in accordance with the present invention. The panel flipper 605 includes a plurality of grippers 604 attached to the end of the panel flipper frame 606 . A pivot 608 , counterweight 610 and actuator 612 are also included. The loading table 602 also includes cylinders 652 , 654 , input rollers 656 and transfer ramp 658 , a zero point edge 661 and a damper 662 . Cylinders 652 , 654 and two others, which are not shown in this view, are operable to tilt the loading table 602 . The surface of the loading table 602 is made from a very low friction material and could also be equipped with a plurality of air jets so that the panel 603 (not shown) slides in a controlled way towards the zero point edge 661 .
The process of loading a panel is illustrated in FIGS. 6B through 6E. In FIG. 6B a panel enters the loading table 602 through input rollers 656 , down the transfer ramp 658 to the loading table 602 surface. Of course other input directions can be used and is not drawn here. The cylinders 652 , 654 can then be selectively manipulated to cause the panel to move towards the zero point edge 661 . Then, as shown in FIG. 6C, the panel flipper frame 606 rotates around the pivot 608 via the actuator 612 , towards the panel 603 (not shown). When the panel flipper frame 606 is in close proximity to the edge of the panel it depresses the transfer ramp 658 to expose the edge of the panel. The grippers 604 are then actuated to securely grab the panel 603 (not shown) and loading table 602 . Then, as shown in FIG. 6D, the panel flipper frame 606 rotates around the pivot 608 via the actuator 612 , toward the vertical. When the panel flipper frame 606 is rotated vertically, the loading table 602 rotates with the panel flipper frame 606 . Rotating the loading table 602 with the panel flipper frame 606 helps the panel during rotation and thereby substantially avoiding bending the panel 603 . In FIG. 6E, the loading table 602 rotates back to horizontal orientation. The panel 603 (not shown) can then be transferred to the next process in the vertical orientation. After the loading table 602 is rotated to horizontal the entire loading process can begin for a subsequent panel.
FIG. 7 illustrates the six directions necessary to register a panel 702 . Those directions are also very important to get a perfect image quality on the panel. The +In-Scan direction is moving the panel vertically up. The −In-Scan direction is moving the panel vertically down. The +In-Scan and the −In-Scan are along the Y axis of the panel. The +Slow Scan direction is moving the panel horizontally, parallel with the plane of the panel and further towards the unloading section of the present invention. The −Slow Scan direction is moving the panel horizontally, parallel with the plane of the panel and back towards the loading section of the present invention. The +Slow Scan and the −Slow Scan are along the X-axis of the panel. The Front Focal direction is moving the panel horizontally, perpendicular to the panel, towards the front of the present invention. The Back Focal direction is moving the panel horizontally, perpendicular to the panel, towards the back of the present invention. A +rotation and −rotation directions move the panel in order to reduce the delta theta error.
FIG. 8A illustrates one embodiment of the registration section 800 in accordance with the present invention. The registration section 800 includes a foundation slab 802 which is shared by the image section (not shown). The vibration isolators 804 , 806 are mounted to the foundation slab 802 and are operable to isolate the registration sub frame 810 from the foundation slab 802 . Isolating the registration sub frame 810 from the foundation slab 802 substantially eliminates the transmission of vibrations from the registration section 800 to the image section. The isolators 804 , 806 can be air bellows or other viscous couplings capable of isolating the registration sub frame 810 from the foundation slab 802 . Such viscous couplings can also include oil or water filled couplings or combinations thereof or any equivalents thereof. Docking or guide pins 812 , 814 are mounted on the registration sub frame 810 . Pin recesses or guide pin sockets 813 , 815 are mounted to a portion 818 of the frame for the image section. The use of a combination of self-centering docking pins 812 , 814 and pin recesses 813 , 815 are but one embodiment. Other embodiments include precision channels and grooves or other equivalent mechanical, self-centering devices and a docking surface with a corresponding mating surface in lieu of the docking pins 812 , 814 and pin recesses 813 , 815 . The registration sub frame 810 is docked to the portion 818 of the frame for the image section by raising or otherwise inflating the isolators 804 , 806 so as to cause the entire registration sub frame 810 to move upwards. At a certain level, where the docking pins 812 , 814 engage the pin recesses 813 , 815 , the registration sub frame 810 will enter into a repeatably accurate position. In an alternative embodiment, the registration sub frame 810 does not move to undock or disengage from the imaging section. The vibration isolators 804 , 806 can also be optional in alternative embodiments although such alternative embodiments would likely be slower so as to not load a panel 824 into the registration system 800 at the same time another panel is being imaged. Such an alternative embodiment would therefore be substantially slower than the having some method of isolation between the registration section 800 and the imaging section but provides the benefit of a simpler apparatus.
A vacuum table 820 is attached to the registration sub frame 810 via a pivot 822 . See for example, U.S. patent application Ser. No. 09/447,184 to Vernackt filed Nov. 22, 1999, entitled AUTOMATICALLY ADAPTING VACUUM HOLDER, and assigned to the assignee of the present invention, for an example of a vacuum table that may be used in the present invention. A panel 824 is shown being held by the vacuum table 820 . A transparent panel 830 is attached to the registration sub frame 810 via a plurality of extenders 832 , 834 . A plurality of cameras 836 (only one shown) are attached to the transparent panel 830 . A portion of the vertical support 850 and top rail 852 for the image section are also shown. The exposing carriage 854 is slideably attached to the top rail 852 . A plurality of panel grippers 856 , 858 are attached to the exposing carriage 854 via a plurality of lateral adjusters 860 .
In one embodiment, the transparent panel 830 has a grid mask on it and a plurality of cameras 836 to accurately and quickly measure the position of a plurality of targets which are located on the panel 824 . In an alternative embodiment, only one camera 836 is mounted in an X-Y coordinate frame such that the camera 836 is moved from one target location to second or other subsequent target locations using a high resolution encoder. An embodiment using one camera 836 in combination with an X-Y coordinate frame would require additional registration time and further, require targets be more specifically located on the panel.
Before the transfer of the panel 824 from the loading section to the registration section, the registration section is checked to ensure the registration section is ready to accept a new panel i.e. does not have a panel currently in the registration section. In another embodiment, before the panel flipper returns to “home” position in the load zone, the push plate (not shown) is retracted. Retracting the push plate provides the possibility to move the panel flipper backwards, with the panel hanging vertically on the vacuum table 820 . In an alternative embodiment, the push plate can be part of the panel flipper. If the push plate is part of the panel flipper, the transparent plate 830 is not needed. In still another embodiment where the loading section includes a first vacuum table, the same first vacuum table can serve as the push plate, which is thus part of the panel flipper. The use of such a first vacuum table has the advantage that the panel 824 is flattened during the load process and a flat panel 824 is presented to the vacuum table 820 in the registration section.
Also after the panel is brought in front of the vacuum table 820 , first compressed air is applied to create an air flow escaping from both the vacuum table 820 and the plate 830 . The air flow creates an air cushion when the plate 830 comes towards the vacuum table 820 . In this method the panel 824 is sandwiched between the vacuum table 820 and the plate 830 . The low friction of the air cushion assists in flattening the panel 824 without damaging the panel 824 during the sandwich operation. Next, the airflow in the vacuum table 820 is stopped and vacuum is applied. For a short period of time, compressed air is escaping from the plate 830 . The vacuum causes the panel 824 to be fixed onto the vacuum table 820 . Next, the grippers of the panel flipper release the panel. In an embodiment where the plate 830 is part of the camera section, the plate 830 is retracted. Then the panel flipper can then return to the loading section to pick-up the next panel.
When a panel 824 is loaded into the registration section 800 , the vacuum table 820 applies a vacuum to the panel 824 to securely hold the panel 824 . Next, the transparent plate 830 is pressed against the panel 824 via the extenders 832 , 834 . Pressing the panel 824 against the vacuum table 820 with the transparent plate 830 results in a very tight sandwich-type structure. The sandwich-type structure flattens and smoothes the panel 824 so as to further reduce potential registration errors. Next, the cameras 836 determine the location of the targets on the panel 824 . The targets may be any type of marking, or a hole, or, on multi-layered panels, may be a point located on an earlier layer that is detectable by the cameras 836 . Determining the location of a plurality of targets determines the delta theta rotation error. Next the delta theta rotation error is substantially eliminated by first very slightly retracting the transparent plate 830 via the extenders 832 , 834 and then rotating the vacuum table 820 via the pivot 822 . The pivot 822 can include a motor with a gearbox. The gear box provides a highly accurate position resolution. The vacuum table 820 can mechanically rotate over a very small angle to substantially remove the delta theta error in the panel 824 . Next, the two scale factors in X and Y direction are searched using at least three targets. Using a grid system and a dynamic range vision system, the registration process occurs very quickly. After the last scan line is applied to the previous panel i.e. the imaging section has completed the imaging process on any previous panel, the registration sub frame 810 is raised to cause the docking pins 812 , 814 to engage the portion 818 of the frame for the image section. In one embodiment, the registration sub frame 810 is raised by increasing the pressure of or otherwise causing the isolators 804 , 806 to extend. In an alternative embodiment the registration sub frame 810 is raised by other methods separate from the isolators 804 , 806 such as a mechanical lifting device such as a hydraulic or air cylinder, a screw or geared lifting device. Next the grippers 856 , 858 grip the panel 824 . Optionally, next the cameras 836 check the location of the targets once again. If any additional delta theta errors are detected, then the grippers 856 , 858 release the panel and the vacuum table 820 readjusts to further substantially eliminate the delta theta error as described above. Then the transparent plate 830 is retracted away from the panel 824 and the vacuum is released from the vacuum table 820 . Optionally, to assist in releasing the panel from the vacuum table 820 , pressurized air or some other gas or combination of gases can be applied to the vacuum table 820 . Then, the vacuum table 820 is lowered to its original position.
In yet another embodiment, two registration systems can be utilized, one system for each side of the panel 824 . Each registration system will be equipped with a transparent plate 830 and cameras 836 . Both registration systems move toward each other and sandwich the panel 824 to hold it in place. Such a dual sided registration system can provide highly detailed registration information for each side of the panel 824 . In such and embodiment, each side of the panel 824 is treated individually and the correct delta theta error correction information for each side is transmitted to the corresponding imaging head in the imaging section. Such a dual sided registration system can be of great benefit when, for example, a panel 824 is drilled with a small diameter drill and the resulting hole is not precisely straight due to drill run out or some other tolerance or machine wear or operator error. The holes on either side of the panel 824 can be located differently. The error from one side of the panel 824 to the other side could be as great as 15 microns and the imaging section can correct and compensate for such an error.
Next, the panel is rotated so that the vertical line between two reference points at top and bottom of the panel are parallel to the scan line. This can be accomplished mechanically by rotating the vacuum plate using a motor with a gearbox. The gear box provides a highly accurate position resolution. During this rotation, the vision system checks the position of the two targets and forms a closed loop with the driver or controller of the motor.
FIG. 8B illustrates another embodiment of the registration section 870 . The registration section 870 includes a foundation slab 872 which is shared by the image section 874 . A registration sub frame 876 and a registration control system 878 are included in the registration section 870 .
FIGS. 9A and 9B illustrates a panel 910 being carried via the exposing carriage 905 through the dual side imager 915 . In an alternative embodiment, a plurality of exposing carriages 905 may be included. A plurality of exposing carriages 905 can further reduce the cycle time of the imaging process. A second or subsequent exposing carriage 905 could pick up a subsequent panel from the registration section and begin moving it toward the imaging section before the previous exposing carriage 905 returned to home position. In an embodiment having a plurality of exposing carriages 905 panels are effectively placed next to each other at the scan line position. This simulates a panel having an endless length. The process throughput time would then be substantially determined by the imaging speed and additional handling time would not be needed. This embodiment creates the optimum arrangement and use with the highest production efficiency.
When the last scan line is set onto the previous panel, the grippers mounted on the exposing carriage 905 will open. The previous panel will fall downwards in a controlled manner and will be picked up by the unloading section. At that time the registration section is raised to dock to the image section. The exposing carriage 905 then returns to its home position at a relative high speed. The home position of the exposing carriage 905 is in the registration section to pick-up the next panel 910 .
During the return of the exposing carriage 905 , the grippers are in an open state and will glide over the top edge of the panel 910 being held in the registration section. Once in position, the grippers close on the panel 910 . Until the grippers close on the panel 910 , the registration system can continuously check if the panel is still in registration.
Next, the vacuum in the vacuum table in the registration section is released and compressed air is applied. The push plate then retracts so that the push plate-panel-vacuum table sandwich is disassembled. The exposing carriage 905 then moves forward at a relative high speed to the beginning of the scan line is reached. In the same time a synchronization between the speed of the exposing carriage and the speed of the polygon motor is established, where the polygon motor speed determines the vertical span of the laser direct imager. Upon entering the panel between the optical heads, the optical heads are set at a wider range from each other. Before the scanning begins, the optical scanning heads are brought in close proximity to the panel. The panel hangs vertically, so that the panel's weight helps maintain the straight, vertical orientation of the panel. A pair of guides below the optical heads, establish an air bearing on either side of the panel. The guides and resulting air bearing enable a very precise vertical position of the panel.
Next, the scanning begins. Simultaneously, the registration sub frame is lowered so that the registration sub frame disengages from the imaging section and returns to a lowered position, ready to accept the next panel for registration. The scanning process is the dominating process and depends on many variables such as available laser power, resolution, resist sensitivity, etc.
FIG. 10 illustrates one embodiment of a dual side direct imager 1000 in accordance with the present invention. The dual side direct imager 1010 is mounted on the foundation slab 1020 . The exposing carriage 1030 and the grippers 1040 are shown gripping a panel 1045 . The registration section is not shown for clarity. Any dual side direct imager is suitable for use in the present invention. One embodiment of the dual side direct imager suitable for the present invention is disclosed in co-pending U.S. patent application Ser. No. 09/435,983, entitled: METHOD AND DEVICE FOR EXPOSING BOTH SIDES OF A SHEET, by Inventor(s): Marc Vernackt, Ronny De Loor, Anne-Marie Empsten, and Mark Ryvkin, filed: Nov. 8, 1999, Attorney/Agent's Ref. No.: BARCO-014-1, which is incorporated by reference herein for all purposes.
FIGS. 11A and 11B illustrate one embodiment of the panel unload section 1100 in accordance with the present invention. The front plate 1112 and rear plate 1114 ensure panel maintains vertical position during movement of the panel 1102 and protects the panel 1102 . The panel 1102 is carried on the exposure carriage 1104 until the panel clears the scan lines in the imaging section 1106 . The panel 1102 is then released and falls to the shock absorbing ramp 1120 . The shock absorbing ramp 1120 , the front holder 1124 and the rear holder 1126 are included in the unload system 1140 . The unload system 1140 moves towards the unload section, holding and thus moving the panel 1102 toward the unload table 1132 . In FIG. 11B the front plate actuator 1118 is then retracted to cause the front plate 1112 open and allow the panel 1102 to move down the shock absorbing ramp 1120 . The front holder 1124 is then released and the panel pusher 1130 is actuated causing the panel 1102 to move down the shock absorbing ramp 1120 toward the unload table 1132 . The unload table 1132 can also include rollers or robot arms or other mechanical methods to pull or cause the panel 1102 to continue moving the panel 1102 away from the unload section 1100 . In an alternative embodiment, the unload pick-up system 1140 is raised prior to the panel 1102 being released from the exposure carriage 1104 . Raising the unload pick-up system 1140 reduces the distance the panel 1102 falls and therefore the falling speed.
In the preferred embodiment, each section, i.e.: load section, registration section, image section and unload section, are automatically controlled by a controller or a plurality of individual controllers in communication with each other. The controller utilizes a control logic to operate the individual sections. Each section can be operated independently but in coordination with the other sections to rapidly process panels in parallel. The controller can be an embedded PC, running control software. In other alternative embodiments other types of controllers well known to one skilled in the art such as sequential logic controllers, PLCs and other controllers may also be used.
FIG. 12 illustrates an embodiment of a local area network (LAN) 1200 in accordance with the present invention. The LAN 1200 includes interconnections between the of the controller 1202 of an automated, flow-through, dual side, laser direct imaging apparatus and the extranet 1204 . Also connected to the LAN 1200 are the raster imaging bank (RIP) bank 1208 a main file server to the LDI 1210 and a work station 1220 . Other work stations and peripheral connections may also be connected to the LAN 1200. The extranet 1204 can include the internet.
While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of a preferred embodiment should not be limited by any of the above described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. | A system and method is disclosed that provides an automated, flow-through, dual side, laser direct imaging process and apparatus. This provides the capability to simultaneously register and image both sides of a substrate in a continuous flow-through process. The present invention provides efficiency improvements over the prior art on several levels. First, the prior art is batch process in which substrates are imaged one (or a batch) at a time in contrast with the present invention is a continuous, flow through, sequential process whereby a first substrate is followed into the apparatus by a second substrate which is, in turn followed by a third and so forth and the second substrate begins the process through the apparatus before the first substrate completes the process through the apparatus. Second, the process time per substrate is reduced as compared to the prior art. | 7 |
1. FIELD OF THE INVENTION
[0001] The present invention relates to a semiconductor biosensor which is used for healthcare chip and a control method of the semiconductor biosensor.
2. DESCRIPTION OF THE RELATED ART
[0002] In recent years, it has become significant to suppress the drastic increase of medical expense since the society is aging in developed countries. It may be possible to early find diseases and thereby reduce the medical expense if we can inspect and detect little amount of chemical substance contained in a sample with high precision. It is expected that such an inspect method can be achieved by utilizing microelectronics technologies. (See K. Koike, et al., Jpn. J. Appl. Phys., vol. 53, 05FF04 (2014).)
[0003] However, the inspection equipment with high precision is not only expensive but also large in size. Thus, the inspection can only be carried out in large hospitals or medical facilities. This makes the inspection expensive, and the inspection period is often more than several days.
[0004] In other words, small inspection equipment with high precision may enable small-scale medical institute to perform cheap inspection. The inspection period shall be substantially reduced with simplified process of inspection, then substantially reducing the cost and improving the convenience of the inspection. Therefore, in order to cut the cost of the inspection, it is necessary to substantially reduce the size of inspection equipment while keeping the precision by utilizing the combined technologies of semiconductor micro-devices and biosensors.
[0005] FIG. 1 is an exemplary illustration of basic device structure of a conventional semiconductor biosensor (See K. Koike, et al., Jpn. J. Appl. Phys., vol. 53, 05FF04 (2014).). An oxide film 1 , a source electrode 2 and a drain electrode 3 are layout on a semiconductor substrate 4 . Those electrodes are covered by a resist film 100 so as to be protected from a solution (e.g.: specimen such as blood, urine, sweat, and so forth) in which inspection target is dissociated. This conventional semiconductor biosensor is exposed into the solution during inspection.
[0006] Referring to FIG. 10 , in the solution, a target 7 and a receptor 8 are attached to the surface of the oxide film 1 to produce a chemical reaction. The chemical reaction normally has a dissociation constant 300 (K) for determining the equilibrium state thereof. When the dissociation constant 300 is larger, the decoupling prevails in the chemical reaction. To the contrary, when the dissociation constant 300 is smaller, the coupling prevails in the chemical reaction, and thus a composite body 5 is made on the surface of the oxide film 1 , as illustrated FIGS. 2 , 3 , and 4 .
[0007] The composite body 5 has charge carried by the target 7 . The charge will modulate surface electric field of the semiconductor substrate 4 . It may capable of detecting whether the target 7 is contained in the solution by reading the change in electric current flowing between the source electrode 2 and the drain electrode 3 .
[0008] There are many composite bodies 5 on the surface of the oxide film 1 , as illustrated in FIG. 2 , as long as the dissociation constant 300 is small. If the dissociation constant 300 is larger, the density of the composite bodies 5 is decreased, as illustrated in FIGS. 3 , and 4 .
[0009] Besides, if the number of target 7 is more in solution, then more composite bodies 5 are attached to the surface of the oxide film 1 , as illustrated in FIG. 2 . If the number of target 7 is less in solution, then, as illustrated in FIGS. 3 , and 4 , the number of composite bodies 5 attached to the surface of the oxide film 1 becomes less.
[0010] The dissociation constant 300 is sensitive to the density of target 7 in the solution and temperature.
[0011] In FIGS. 3 , and 4 , those charges of the composite bodies 5 are sparse on the surface of the oxide film 1 and then work as point charges. In this regard, electrons flowing from the source electrode 2 to the drain electrode 3 can easily circumvent around the composite bodies 5 , as shown in FIG. 6 . Thereby, if the electrons flowing from the source electrode 2 to the drain electrode 3 along a roundabout route, those composite bodies 5 exhibit no impact on the electric current characteristics of the conventional semiconductor biosensor.
[0012] Therefore, referring to FIG. 7 , another conventional semiconductor biosensor replaces the semiconductor substrate 4 with wide gate width with a semiconductor conducting wire 6 with narrow gate width. Since electrons cannot circumvent around a composite body 5 while flowing through the semiconductor conducting wire 6 , there is no roundabout route for the electrons flowing from the source electrode 2 to the drain electrode 3 . Thus, the transport speed of those electrons is reduced in average and the electric current is suppressed. In theory, it may be possible to detect a sole target 7 as long as we can sense this change in the electric current.
[0013] In general, the change in electric current (ΔI ds ) flowing on the semiconductor surface of transistors is sensed as change in threshold voltage shift (ΔV t ). Depicting the trunsconductance g m , the surface density of total charge carried by target 7 Q x , the gate capacitance of transistor C, the surface density of receptors 8 [Y], the density of target 7 in solution [X], formula 1 is obtained with the cut-off to the background noise:
[0000]
Δ
I
ds
g
m
=
Δ
V
t
=
Q
X
C
[
Y
]
×
[
X
]
[
X
]
+
K
+
(
cut
-
off
)
[
Formula
1
]
[0014] The cut-off is predetermined for veiling the noise not related to biosensors and must be much smaller than any noise attributable to the biosensors.
[0015] According to Formula 1, the limit of detection (LOD) is obtained as formula 2, where I noise is the absolute value of the electric current caused by the noise attributable to the biosensors. (See M. A. Reed, IEEE IEDM13, pp. 208-211 (2013).)
[0000]
LOD
=
K
(
Q
X
[
Y
]
/
C
I
noise
/
g
m
-
(
cut
-
off
)
)
[
Formula
2
]
[0016] According to Formula 2, it is found that LOD is made small as long as I noise becomes small and is equal to the cut-off.
[0017] As mentioned above, I noise can be made small by using semiconductor conducting wires 6 to replace the semiconductor substrate 4 . Specifically, referring to FIG. 5 , there are a plurality of conducting wires 6 in parallel between a common source 2 and a common drain 3 . As example, there are three conducting wires 6 , each of which can detect a sole composite body 5 on the surface of the oxide film 1 . Then, it appears that the LOD is made small.
[0018] However, all of the conducting wires 6 are connected to the common drain 3 , which indicates that the current signals from the conducting wires 6 are added. Once the signals are added up, it is impossible to distinguish signals from different conducting wires 6 . Therefore, the LOD is not improved significantly.
SUMMARY OF THE INVENTION
[0019] An objective of the present disclosure is to provide a semiconductor biosensor and a control method thereof with improved limit of detection.
[0020] An embodiment of the semiconductor biosensors related to the present invention comprises a central reaction unit of a highly-precise very small inspection equipment, with the central reaction unit being able to be embedded into a semiconductor chip; and with the central reaction unit comprising: a plurality of semiconductor conducting wires; a common source, wherein one end of each conducting wire is connected to the common source; a plurality of non-volatile memory type transistors respectively connected to another end of each conducting wire; a plurality of sense-amplifiers respectively connected to the said non-volatile memory type transistors; a bit line controller analyzing signals sensed by the said sense-amplifiers and managing the operation of the said non-volatile memory type transistors; an oxide film wrapping or covering the said conducting wires, and a plurality of receptors fixed on a surface of the said oxide film.
[0021] A control method of the semiconductor biosensor comprises: initializing the semiconductor biosensor by sensing output signals from the plurality of conducting wires by the plurality of sense-amplifiers, and then testing for conducting wires having wire-errors, wherein conducting wires with anomalous high resistance or snapped conducting wires are regards as conducting wires having said wire-errors; data-thinning the semiconductor biosensor by selectively programming non-volatile type memory transistor connected to the conducting wires having said wire-errors; and exposing the semiconductor biosensor into a solution. In addition, the control method of the semiconductor biosensor, further comprising selectively tuning threshold voltages of the non-volatile memory type transistor connected to the conducting wires without said wire-errors after said data-thinning but before exposing the semiconductor biosensor into the solution.
[0022] In accordance to the above structure and method, it is made capable of producing a central reaction unit as a key device of the semiconductor biosensor to achieve highly-precise and very small inspection equipment.
[0023] Embodiments according to the present invention will be explained below with reference to the drawings. These embodiments are not intended to limit the present invention. The drawings schematically show practical devices and are not made to scale.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The illustrative embodiments may best be described by reference to the accompanying drawings where:
[0025] FIG. 1 is a view illustrating a basic device structure of prior art biosensor.
[0026] FIG. 2 is a view illustrating a basic device structure of prior art biosensor.
[0027] FIG. 3 is a view illustrating a basic device structure of prior art biosensor.
[0028] FIG. 4 is a view illustrating a basic device structure of prior art biosensor.
[0029] FIG. 5 is a view illustrating a basic device structure of prior art biosensor;
[0030] FIG. 6 is a view illustrating that electrons flow around charge in prior art biosensor;
[0031] FIG. 7 is a view illustrating that electrons cannot flow around charge in prior art biosensor;
[0032] FIG. 8 is a view illustrating that receptors are attached on oxide surface and then targets moving in solution are caught by those receptors and immobilized;
[0033] FIG. 9 is a view illustrating a basic component related to an embodiment of the present invention;
[0034] FIG. 10 is a view illustrating a reaction of receptors and targets, which is related to an embodiment of the present invention;
[0035] FIG. 11 is a view illustrating fabrication method of biosensor related to an embodiment of the present invention;
[0036] FIG. 12 is a view illustrating fabrication method of biosensor related to an embodiment of the present invention;
[0037] FIG. 13 is a view illustrating fabrication method of biosensor related to an embodiment of the present invention;
[0038] FIG. 14 is a view illustrating equivalent circuit related to an embodiment of the present invention;
[0039] FIG. 15 is a view illustrating that those receptors catch targets in equivalent circuit of biosensor related to an embodiment of the present invention;
[0040] FIG. 16 is a view illustrating that signal electric current is modulated with regard to charge carried by those targets in biosensor related to an embodiment of the present invention;
[0041] FIG. 17 is a view illustrating simulation result of operation of biosensor related to an embodiment of the present invention;
[0042] FIG. 18 is a view illustrating a method for correcting error modes of biosensor related to an embodiment of the present invention;
[0043] FIG. 19 is a view illustrating a method for correcting error modes of biosensor related to an embodiment of the present invention;
[0044] FIG. 20 is a view illustrating a method for correcting error modes of biosensor related to an embodiment of the present invention;
[0045] FIG. 21 is a view illustrating fluctuation of diameter of semiconductor conducting wires;
[0046] FIG. 22 is a view illustrating a method for correcting offset of biosensor related to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0047] Referring to FIG. 8 , an embodiment of the semiconductor biosensor related to the present invention is constituted of a central reaction unit 200 comprising semiconductor conducting wires 6 , an oxide film 1 and receptors 8 , and the peripheral unit described below. The semiconductor conducting wires 6 can be thin conducting wires. Moreover, the semiconductor conducting wires 6 can be nanowires.
[0048] The central reaction unit 200 is fabricated on the semiconductor substrate. The central reaction unit 200 is exposed into a solution dissociating targets 7 . The targets 7 having charge moves in the solution and then couples with receptors 8 attached to the surface of the oxide film 1 subject to the formula shown in FIG. 10 . The dissociation constant 300 determines the equilibrium state of the chemical reaction of the targets 7 and the receptors 8 . When K is large, then receptors 8 and targets 7 are decoupled. When K is small, then the receptors 8 and the targets 7 are coupled to form immobilized composite bodies 5 .
[0049] Referring to FIG. 9 , the central reaction unit 200 further comprises a plurality of sense-amplifier 9 (S/A). One end of each conducting wire 6 is connected to a common source 2 and another end of each conducting wire 6 is connected to each sense-amplifier 9 . The number of the sense-amplifier (M) is same with the number of the conducting wires 6 and the sense-amplifiers 9 are labeled from 0 to M−1, respectively.
[0050] In this figure, there are three conducting wires 6 , each of which can detect a sole composite body 5 on the surface of the oxide film 1 . The sense-amplifiers 9 corresponding to those conducting wires 6 can detect the reduction of current signal thanks to charges of those composite bodies 5 . The difference between the embodiment of the semiconductor biosensor related to the present invention and the conventional semiconductor biosensor shown in FIG. 5 is that the common drain 3 was replaced with a plurality of the sense-amplifiers 9 each of which is connected to one of the conducting wires 6 independently. By such arrangement, it is theoretically made possible to distinguish change in electric current from one of the conducting wires 6 attributable to a sole composite body 5 , by not adding signals from every conducting wire 6 up.
[0051] Next, the method for distinguishing signal from noise is described. There are M conducting wires 6 and M sense-amplifiers 9 . The M sense-amplifiers 9 and the common source 2 are connected at the opposite side of the M conducting wires 6 as shown in FIG. 9 . It is supposed that m conducting wires 6 of M ones can detect sole composite body 5 on the surface of the oxide film 1 in a similar way. (In the example of FIG. 9 , m=3.)
[0052] If one conducting wire 6 does not detect any sole composite body 5 on the surface of the oxide film 1 , the electric current that flows from the common source 2 to the sense-amplifier 9 that is connected to said wire 6 is denoted as I 0 . On the other hand, if one conducting wire 6 detects a sole composite body 5 on the surface of the oxide film 1 , the electric current that flows from the common source 2 to the sense-amplifier 9 that is connected to said wire 6 is denoted as I 1 . The electric current I 1 can be expressed as the sum of electric current I 0 and a difference AI between currents I 0 and I 1 . Namely, I 1 =I 0 +ΔI. In this regard, if the conventional semiconductor biosensor is used for inspection, the common drain 3 will receive an electric current from each conducting wire 6 that has a magnitude of I 0 +(m/M)×ΔI in average. On the other hand, the sense-amplifier 9 of the biosensor in this embodiment, that is connected to the conducting wire 6 detecting the sole composite body 5 on the surface of the oxide film 1 , is able to receive the electric current of I 0 +ΔI. In other words, the sense-amplifier 9 in the embodiment is able to determine whether the conducting wire 6 detects the sole composite body 5 based on the electric current of I 0 +ΔI. In contrast, the common drain 3 of the conventional biosensor can only determine whether a single conducting wire 6 detects the sole composite body 5 based on the electric current of I 0 +(m/M)×ΔI. The sense-amplifier 9 of the application receives an extra amount of current of ΔI×(1−m/M) in addition to the average current received by the conventional common drain 3 . As such, the value of (1−m/M) can serve as a standard for evaluating the level of improvement to the Limit of Detection (LOD) in the embodiment.
[0053] The improving factor of LOD is given by Formula 3.
[0000]
ɛ
≅
1
-
m
M
[
Formula
3
]
[0054] Accidental current change on the conducting wires 6 is a noise, which misleading the conducting wires 6 without composite body 5 to be considered as having one. Assuming the number of the conducting wires 6 with noise is δ. The noise is made ignorable as long as m is large enough compared with δ. The total number of conducting wires 6 (M) should be made larger, in order to enlarge m while not degrading the limit of detection. Thereby, the improved LOD by the present invention, Formula 4, is obtained.
[0000]
Improved
LOD
=
(
1
-
ɛ
)
×
LOD
=
m
M
×
LOD
[
Formula
4
]
[0055] In the example where the gate width of biosensor (i.e., the width of central reaction unit 200 ) is 2.4 mm, the width of the conducting wire is 3 nm in average, and the space between adjoining conducting wires 6 is 57 nm in average, there are 40,000 conducting wires 6 . When the improving factor ∈ (Formula 3) is 99.9%, m is 40. Indeed, there may be conducting wires 6 in which electric current is accidentally decreased. Namely, the possibility of the presence of the conducting wires 6 with noise is non-zero. However, the number of those conducting wires (δ) may be less than 40. When the improving factor is 99%, m is 400 which may further larger than δ. When the improving factor is 90%, m is 4000, which may much larger than δ. Even for a 90% improving factor, the improving ratio (m/M) may be large enough.
[0056] The total number of the conducting wires 6 (M) is predetermined in the step of device design, which will be described below with an example of a fabrication method of the central reaction unit 200 .
[0057] In FIG. 11 , there is a SOI (Silicon-On-Insulator) film 10 with the thickness being 20 nm as an example. This SOI film 10 is cut out to line 11 and space 12 in the lithography process, as illustrated in FIG. 12 . The width of the line 11 (L) and the width of the space 12 (S) are 30 nm. The lines 11 correspond to semiconductor wires. By this way, a plurality of semiconductor wires 11 with cross-section being (30 nm, 30 nm, 20 nm) in average are made.
[0058] Next, an oxide film is compensated to the spaces 12 , and then slim the semiconductor wires 11 by subsequent thermal processes (sliming process).
[0059] As a result, conducting wires 6 with diameter being 3 nm in average and spaces 12 with width being 57 nm in average are layout, as illustrated in FIG. 13 . Subsequently, CMP (Chemical and Mechanical Process) and oxidization are preceded. A thin oxide film 1 is formed after planarization to perform as gate oxide. Furthermore, receptors 8 are fixed on the surface of the oxide film 1 , and then central reaction unit 200 is made in FIG. 8 .
[0060] FIG. 14 illustrates an equivalent circuit of the embodiment of the semiconductor biosensor related to the present invention. An end of conducting wire 6 is connected to a common source line (CSL) via a source select gate 20 (SGS). The other end is connected to the sense-amplifier 9 via a drain select gate 21 (SGD). The signal from each sense-amplifier 9 is analyzed by a bit line decoder 22 .
[0061] FIG. 15 is an illustration obtained by picking up a sole conducting wire 6 from the equivalent circuit and hiding the others in FIG. 14 . This is for paying attention to the operation of the conducting wire 6 related to the present invention. As an example, the source select gate 20 is an nMOSFET and the drain select gate 21 is a pMOSFET. In general, the four combinations of SGS 20 and SGD 21 are possible; for example, (nMOSFET and nMOSFET), (nMOSFET and pMOSFET), (pMOSFET and nMOSFET), and (pMOSFET and pMOSFET).
[0062] While both of the source select gate 20 and the drain select gate 21 are turned on, electron current is made flow from n-type diffusion layer of the source select gate 20 to the conducting wire 6 by applying drain voltage via the sense-amplifier 9 . It is noted that the conducting wires 6 generally exhibit low thermal conductivity if the diameter is very small, so the heating dissipation is made difficult for the conducting wires 6 , which leads to self-heating effect. Thus, in order to cool the conducting wires 6 down, it is preferable to dissipate the heat to p-type diffusion layer of the drain select gate 21 if the diameter is very small. Therefore, the drain select gate 21 can be a pMOSFET.
[0063] The electric current flowing through conducting wire 6 is made of electrons flowing therein. If the charge stored by composite bodies 5 is negative, the signal sensed by sense-amplifier 9 is reduced by the charge. Otherwise, the signal is increased by the charge.
[0064] FIG. 16 is an illustration of the drain current (current sensed by the sense-amplifiers 9 ) with no composite body 5 attached on the conducting wire 6 (N=0) and with the composite bodies 5 having two electrons attached on the conducting wire 6 (N=2). To sense the difference in current is to detect the existence of target 7 .
[0065] The result of device simulation with a different amount of composite bodies 5 attached to the conducting wire 6 is shown in FIG. 17 . The ratio of the current to that with no composite body 5 ; which is neutral (N=0), is plotted with respect to the number of electrons (n) stored in the composite body 5 . As the number of electrons increasing, the ratio of the current is reduce to about half at n=3, or about 20% at n=4. It is able to detect the current change with this level of reduction with standard sense-amplifier.
[0066] The EOT is the Equivalent Oxide Thickness of some dielectric film between the target 7 and the conducting wire 6 , to which the thickness of the dielectric film is converted. The sensitivity is improved as EOT is decreased. It is preferable that EOT is less than 2 nm from this simulation result.
[0067] As illustrated in FIG. 13 , the production tolerance is not negligible in actually fabricated line-and-space structures. The resistivity of the conducting wire 6 is increased as the diameter of the conducting wire 6 becomes smaller; and is decreased as it becomes larger. This fluctuation of the diameter of the conducting wire 6 induces the noise contaminated into signals sensed by the sense-amplifiers 9 .
[0068] Referring to FIGS. 18 and 19 , the resistance of conducting wires with diameter being too small 32 is high enough to make the signal undistinguishable from noise. On the other hand, there may also be snapped conducting wire 30 . The snapped conducting wire 30 cannot conduct current, and thus the signal from which is also undistinguishable from noise.
[0069] FIGS. 18 and 19 illustrate a control method of the semiconductor biosensor related to the present invention for dealing with the production tolerance. In FIG. 18 , the drain select gate 21 is replaced with non-volatile memory type transistor 31 . On the other hand, in FIG. 19 , non-volatile memory type transistor 31 is put between the drain select gate 21 and the sense-amplifier 9 .
[0070] Firstly, as illustrated in FIG. 20 , the electric current is sensed by the sense-amplifier 9 while the central reaction 200 unit is exposed into a solution without target 7 or not exposed into any solution. This is the step of Initialization. Conducting wires 6 with no sensible current are regarded as conducting wires with diameter being too small 32 or as snapped conducting wires 30 . Then, non-volatile memory type transistor 31 related to those conducting wires 6 is programmed. Since the programmed non-volatile memory type transistors 31 are turned off, the data of those conducting wires 6 are not transferred to sense-amplifier 90 . This is the step of Data Thinning. After excluding the conducting wires with diameter being too small 32 and snapped conducting wires 30 , the left-behind conducting wires 6 are utilized for testing by sensing the electric current via the sense-amplifiers 9 . This is the step of Inspection.
[0071] In general, the operation of transistor composed of conducting wire 6 is more influenced by surface states than the conventional MOSFET is. It is because the surface to the volume is larger in conducting wire 6 than in a substrate constituting the conventional MOSFET. Thereby, more noise is contaminated to the signal through conducting wire 6 than the signal on the surface of the substrate. The cut-off shown in Formula 2 is determined with respect to the maximum amplitude of the noise.
[0072] The amplitude of noise though conducting wire 6 is sensitive to the diameter of conducting wire 6 . As long as the cut-off is adequate, the amplitude of the noise is less than the limitation of control. Of course, the conducting wires with diameter being too small 32 or with anomalously high resistance may induce noise with amplitude out of the limitation, so the conducting wires with diameter being too small 32 should be excluded.
[0073] It is necessary to take the fluctuation (increase and the decrease) in the amplitude of the noise into consideration for adequately determining the cut-off.
[0074] In addition, as illustrated in FIG. 21 , there is fluctuation in diameter even within a sole conducting wire 60 , which is a characteristic of the conducting wire 6 . It is also necessary to take the fluctuation in the diameter into consideration for adequately determining the cut-off.
[0075] Since it is impossible to grasp fluctuation in the amplitude of the noise or the fluctuation in the diameter when designing biosensor, it is necessary to tune the cut-off to suppress the impact of those fluctuations.
[0076] In concrete, the system with non-volatile memory type transistor 31 , constituting an exemplary embodiment related to the present invention and illustrated in FIGS. 18 and 19 , is capable of adequately determining the cut-off.
[0077] In another embodiment of the control method of the semiconductor biosensor related to the present invention, as illustrated in FIG. 22 , the step of Offset Tuning 530 is appended next to the step of Data Thinning 410 in the flow chart illustrated in FIG. 20 . In this step, the resistance of non-volatile memory type transistor 31 is tuned by arranging threshold voltage of the non-volatile memory type transistor 31 , and thereby, suppressing the impact of fluctuation in the amplitude of the noise or the diameter
[0078] The method to arrange threshold voltage of non-volatile memory type transistor 31 is well-known as verify programming, in which program-erase is repeated with small step (short pulse). (See T. Tanaka, et al., 1990 Symposium on VLSI circuits, pp. 105-106 (1990).)
[0079] By the embodiments of present invention, the limit of detection of biosensor is substantially improved, which result in the significant enhancement of performance of semiconductor biosensor and the drastic price reduction of medical healthcare chip. This enables early detection of disease, which has been impossible with the conventional biosensors, and then substantially reduces medical cost.
[0080] 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. | A semiconductor biosensor and a control method thereof are disclosed for enhancing performance of semiconductor biosensor and the reducing price of medical healthcare chip. An embodiment of the semiconductor biosensor includes a central reaction unit. The central reaction unit comprises a plurality of semiconductor conducting wires; a common source, wherein one end of each conducting wire is connected to the common source; a plurality of non-volatile memory type transistors respectively connected to another end of each conducting wire; a plurality of sense-amplifiers respectively connected to the said non-volatile memory type transistors; a bit line controller analyzing signals sensed by the said sense-amplifiers and managing the operation of the said non-volatile memory type transistors; an oxide film wrapping or covering the said conducting wires, and a plurality of receptors fixed on a surface of the said oxide film. | 6 |
BACKGROUND
[0001] 1.Technical field
[0002] The embodiments herein generally relate to hubble-bubble device used in smoking and particularly relate to a heading section of the hubble-bubble device. The embodiments herein more particularly relate to the heading section provided with arrangements for quick tobacco replacement and adjusting a distance between the charcoal and the tobacco.
[0003] 2. Description of the Related Art
[0004] Application history of the tobacco returns to many years ago and smoking plants for medical purposes and use of plants holding a tranquilizer or weak poisons was common. In this among, the use of hubble-bubble, with a small water reservoir in a lower section and tobacco in an upper section within a ceramic container placed over the hubble-bubble, has antiquity of hundreds years. In the hubble-bubble, suction imposes negative pressure and creates an airflow starting from the upper section of tobacco. The airflow passes through the blazing charcoal over the head of the hubble-bubble. The stroke of hot air with tobacco pieces placed underneath the charcoal results in a quick rise in the temperature of the tobacco pieces and the temperature increase accompanies an evaporation of the materials existing in the tobacco. The vapor enters into the water in the form of a white smoke through a pipe of the hubble-bubble and then to the upper section of the water container and comes out of the hubble-bubble with next suctions. The use of water in the lower section of the hubble-bubble reduces the temperature of the outgoing gases and the positive pressure imposed on the air coming out through the pipe gives a much pleasure to the smoker.
[0005] One of the existing techniques includes a closed end metal cylinder with small furrows, surrounded by the tobacco placed over the head of the hubble-bubble. The head of the hubble-bubble device is surrounded by charcoal pieces and/or using element placed around it to control temperature and avoid burning of tobacco. Another technique includes a special chamber for tobacco which preserves the space between the charcoal and the tobacco and avoids a burning of tobacco or a temperature increase. In another technique, the tobacco is placed within a piece of aluminum foil thereby creating an aluminum capsule. During a smoking process, the aluminum capsule is perforated and is placed over the heading section of the hubble-bubble to provide temperature required for smoking
[0006] There are several disadvantages that exist with the conventional heating techniques. Aluminum is known to produce gases when heated that are harmful to the lungs. Additionally, the charcoal produces ashes that fall through the holes in the aluminum, which gets mixed with the tobacco thereby changing the flavor. Another disadvantage is that the charcoal is located on top of the tobacco, causing the tobacco to burn quickly resulting in a harsh smoke, and the heat often does not transfer to the tobacco on the bottom of the bowl. Still another disadvantage to the heating technique is the chance of bumping the hubble-bubble, causing the hot coals to fall on the floor or the user. Still yet another disadvantage is that the charcoal moves about the top of the foil due to vibration of the hubble-bubble during heating, which necessitates a constant repositioning of the charcoal. Yet another disadvantage is that stirring and/or replenishing of the tobacco within the bowl is difficult as one must remove the charcoal and foil from the top of the bowl in order to access the contents therein.
[0007] Furthermore, another problem of traditional hubble-bubble is the undue and uncontrollable increase of temperature and consequent burning of the used tobacco resulting in the sense of stinging in the respiratory duct of the smoker. The prevailing problems further include the impossibility of replacing the tobacco without replacing the charcoals over the heading section, and lack of access to the tobacco for checking the quantity and the quality of the remaining tobacco.
[0008] Hence, there is a need for an improved hubble-bubble device that eliminates the problem of temperature rise in hubble-bubble device. There also exists a need to provide a hubble-bubble device with facilitates a replacement of a tobacco without replacing the charcoals over the heading section. Furthermore, there exists a need for a hubble-bubble device which provides an access to the tobacco for checking the quantity and the quality of the tobacco remaining in a tobacco holder.
[0009] The abovementioned shortcomings, disadvantages and problems are addressed herein and which will be understood by reading and studying the following specification.
OBJECTS OF THE EMBODIMENTS
[0010] The primary object of the embodiments herein is to provide an improved hubble-bubble device which prevents a burning of the tobacco while smoking.
[0011] Another object of the embodiments herein is to provide a hubble-bubble device which controls a rate of temperature around a tobacco holder.
[0012] Yet another object of the embodiments herein is to provide a hubble-bubble device which facilitates a quick replacement of the charcoal and the tobacco when the tobacco is burned or it is not per palate of user.
[0013] Yet another object of the embodiments herein is to provide a hubble-bubble device which facilitates to vary the distance of the charcoal from the tobacco for controlling the heat around the tobacco.
[0014] Yet another object of the embodiments herein is to provide a hubble-bubble device which avoids a scattering of the ash of a flamed charcoal.
[0015] These and other objects and advantages of the embodiments herein will become readily apparent from the following detailed description taken in conjunction with the accompanying drawings.
SUMMARY
[0016] A hubble-bubble device for a smoking apparatus comprises a holder, a charcoal container arranged on top of the holder and a tobacco tray arranged on a bottom section of the holder. The charcoal container further includes at least two knobs arranged on opposite sides of the charcoal container and the tobacco tray includes at least one knob for an insertion and a withdrawal of the tobacco tray from the holder. The holder is provided with the threads on at least one of an outer surface and an inner surface for receiving the charcoal container. The holder and the charcoal container of the hubble-bubble device are made of ceramic and the tobacco tray is made of ceramic or metal.
[0017] According to one embodiment herein, the hubble-bubble device further comprises a container base and a re-movable charcoal container. The re-movable charcoal container is adapted to be inserted into the container base provided with a casing. The container base includes the inclined trenches so that the trenches are arranged on the opposite sides of the casing of the container base to vary the distance of the re-movable charcoal container from the tobacco for adjusting the distance between the charcoal and the tobacco. The design of the inclined trenches can be in furrow form or a straight form. The hubble-bubble device further comprises a plurality of pins to plug the movable charcoal container and the container base into the hubble-bubble device.
[0018] The charcoal container further includes two knobs arranged on the opposite sides of the charcoal container. The knobs are adapted to engage with the grooves provided along the casing of the container base to provide a tight fit of the charcoal container on the container base and also to slide the charcoal container along the inclined trenches to adjust the distance between the charcoal and the tobacco.
[0019] According to one embodiment herein, the hubble-bubble device further comprises a holder, a charcoal container, a handle provided on at least one end of the charcoal container, a tobacco tray arranged on a bottom section the holder. The casing of the holder is provided with a plurality of furrows to receive and hold the handle of the charcoal container so as to adjust the distance of the charcoal container from the tobacco tray to prevent burning of the tobacco during smoking The plurality of furrows is defined in at least one of a staircase form and thread form.
[0020] The tobacco tray includes at least one knob for an insertion and a withdrawal of the tobacco tray from the holder. Further the charcoal container includes a corkscrew to facilitate the placement of the charcoal container inside the holder of the hubble-bubble device. The corkscrews/knob on the charcoal container regulates the distance from the charcoal container to the tobacco tray. The charcoal container is rotated and moved along the furrows on the casing of the holder to regulate the distance between the charcoal and tobacco. The hubble-bubble device further comprises a lid in the bottom section of the holder to prevent the scattering of an ash of a flamed charcoal.
[0021] These and other aspects of the embodiments herein 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 descriptions, while indicating preferred embodiments and numerous specific details thereof, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The other objects, features and advantages will occur to those skilled in the art from the following description of the preferred embodiment and the accompanying drawings in which:
[0023] FIG. 1 illustrates a front view of the heading section of the hubble-bubble device according to an embodiment of the present disclosure.
[0024] FIG. 2 illustrates an exploded view of the heading section of the hubble-bubble device according to an embodiment of the present disclosure.
[0025] FIG. 3 illustrates a front view of the heading section of the hubble-bubble device with the ceramic container placed inside the ceramic cylinder according to another embodiment of the present disclosure.
[0026] FIG. 4 illustrates an exploded view of the heading section of the hubble-bubble device according to another embodiment of the present disclosure.
[0027] FIG. 5 illustrates a perspective view of a charcoal container of the hubble-bubble device according to another embodiment of the present disclosure.
[0028] FIG. 6 illustrates the exploded view of the charcoal container of the hubble-bubble device according to another embodiment of the present disclosure.
[0029] FIG. 7 illustrates the perspective view of the charcoal container with an inclined trench according to another embodiment of the present disclosure.
[0030] FIG. 8 illustrates an exploded view of the charcoal container with an inclined trench for a hubble-bubble device according to one embodiment of the present disclosure.
[0031] FIG. 9 illustrates a front view of the heading section of the hubble-bubble device with the ceramic container placed inside the ceramic cylinder having a furrow extending along a casing according to an embodiment of the present disclosure.
[0032] FIG. 10 illustrates an exploded view of the heading section of the hubble-bubble device showing the ceramic container, the ceramic cylinder with furrow extending along a casing and a tray according to an embodiment of the present disclosure.
[0033] FIG. 11 illustrates a front view of the heading section of the hubble-bubble device with the ceramic container placed inside the ceramic cylinder having a plurality of furrows along a casing according to an embodiment of the present disclosure.
[0034] FIG. 12 illustrates an exploded view of the heading section of the hubble-bubble device showing the ceramic container, the ceramic cylinder with a plurality of furrows along a casing and the tray according to an embodiment of the present disclosure.
[0035] Although the specific features of the embodiments herein are shown in some drawings and not in others, this is done for convenience only as each feature may be combined with any or all of the other features in accordance with the embodiments herein.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0036] In the following detailed description, a reference is made to the accompanying drawings that form a part hereof, and in which the specific embodiments that may be practiced is shown by way of illustration. These embodiments are described in sufficient detail to enable those skilled in the art to practice the embodiments and it is to be understood that the logical, mechanical and other changes may be made without departing from the scope of the embodiments. The following detailed description is therefore not to be taken in a limiting sense.
[0037] The various embodiments herein provide a hubble-bubble used in a smoking apparatus and particularly to a heading section of the hubble-bubble device. FIG. 1 illustrates a front view of the heading section of the hubble-bubble device according to an embodiment of the present disclosure and FIG. 2 illustrates an exploded view of the hubble-bubble device. The charcoal container 101 is arranged on top of a holder and a tobacco tray is arranged on a bottom section of the holder. The charcoal container 101 is provided with two knobs 105 a and 105 b placed on opposite sides of the casing of the holder. The charcoal container is provided with threads 107 on the inner wall for screwing the charcoal container 101 to the holder. The holder 102 is provided with the threads 107 and/or staircase or any other form as shown in FIG. 2 on the outside wall for screwing/fixing the charcoal container 101 on the holder 102 of the hubble-bubble device. The charcoal is placed inside the charcoal container 101 and the tobacco is placed inside the tray 103 provided at the bottom section of the hubble-bubble device as shown in FIG. 1 and FIG. 2 . Knob 106 is provided on the tray 103 to insert and remove tray 103 from the hubble-bubble device. The tobacco tray 103 is made of metal or ceramic for placing a tobacco. The arrangement facilitates a placement of the charcoal container 101 inside the head of hubble-bubble and regulation of the distance of the charcoal container 101 from the surface of the tobacco tray 103 . The lower section 104 of a heading section 100 is connected to the body of the hubble-bubble device 100 to complete the assembly of the hubble-bubble device 100 .
[0038] FIG. 3 illustrates a front view of the heading section of the hubble-bubble device showing the charcoal container, the holder and the tray according to an embodiment of the present disclosure. The charcoal container 101 is provided with two knobs 105 a and 105 b placed on opposite sides on the casing and the said charcoal container 101 is placed inside the holder 102 as shown in FIG. 3 . The charcoal is placed inside the charcoal container 101 and the tobacco is placed inside the tray 103 provided at the bottom section of the heading section 100 of the hubble-bubble device as shown in FIG. 3 . A handle 106 is provided on the tray 103 to insert and remove the tray 103 from the heading section 100 of the hubble-bubble device. The lower section 104 of the heading section 100 is connected to the body of the hubble-bubble device to complete the assembly of the hubble-bubble device.
[0039] FIG. 4 illustrates an exploded view of the heading section of the hubble-bubble device showing the charcoal container, the holder and the tray according to an embodiment of the present disclosure. The charcoal container 101 is provided with two knobs 105 a and 105 b placed on opposite sides on the casing and the threads 107 are formed on the outer wall of the charcoal container 101 for screwing. The holder 102 is provided with the threads 107 and/or staircase or any other form as shown in FIG. 4 on the inner wall for screwing/fixing the charcoal container 101 inside the holder 102 of the hubble-bubble device. The charcoal is placed inside the charcoal container 101 and the tobacco is placed inside the tray 103 provided at the bottom section of the heading section 100 of the hubble-bubble device as shown in FIG. 3 and FIG. 4 . A handle 106 is provided on the tray 103 to insert and remove the tray 103 from the heading section 100 of the hubble-bubble device. The tray 103 is made of metal or ceramic for placing the tobacco. The arrangement facilitates a placement of the charcoal container 101 inside the head of hubble-bubble and to regulate the distance of the charcoal container 101 from the surface of the tobacco tray 103 . The lower section 104 of the heading section 100 is connected to the body of the hubble-bubble device to complete the assembly of the hubble-bubble device.
[0040] FIG. 5 illustrates the perspective view of a charcoal container arranged inside a hubble-bubble device with furrows according to an embodiment of the present disclosure. The hubble-bubble device comprises a container base 502 and the re-movable charcoal container 501 . The re-movable charcoal container 501 is adapted to be inserted into the container base 502 . The re-movable charcoal container 501 is provided with corkscrews/knob 503 a and 503 b and/or special protrusions that facilitate placement of re-movable charcoal container 501 inside the container base 502 as shown in FIG. 5 . The container base 502 is further provided with inclined furrows 504 on the opposite sides of the casing to regulate the distance from the surface of the tobacco tray 103 . The container pins 505 a and 505 b are provided to plug the container base 502 along with the re-movable charcoal container 501 in the heading section 100 of a device housing in the hubble-bubble device.
[0041] FIG. 6 illustrates the exploded view of a charcoal container (with furrows) for a hubble-bubble device according to an embodiment of the present disclosure. With respect to FIG. 6 , the hubble-bubble device comprises a container base 502 and the re-movable charcoal container 501 . The re-movable charcoal container 501 is adapted to be inserted into the container base 502 . The re-movable charcoal container 501 is provided with corkscrews/knob 503 a and 503 b and/or special protrusions that facilitate placement of re-movable charcoal container 501 inside the container base 502 as shown in FIG. 5 and FIG. 6 . The container base is provided with longitudinally extending grooves along the sides of the casing to facilitate the placement of re-movable charcoal container 501 inside the container base 502 of the hubble-bubble device. The container base 502 is further provided with inclined furrows 504 on the opposite sides of the casing to regulate the distance of the charcoal container from the surface of the tobacco tray 103 . The inclined furrows 504 provided on the container base 502 helps in the adjustment of distance between the re-movable charcoal container 501 from the tray 103 provided in the bottom section of the heading section 100 of the hubble-bubble device. The container pins 505 a and 505 b are provided to plug the container base 502 along with the re-movable charcoal container 501 in the heading section 100 of a device housing in the hubble-bubble device.
[0042] FIG. 7 illustrates a perspective view of a charcoal container (with an inclined trench) for a hubble-bubble device according to one embodiment of the present disclosure. With respect to FIG. 7 , the re-movable charcoal container 501 is provided with corkscrews/knob 503 a and 503 b and/or special protrusions that facilitate the placement of the re-movable charcoal container 501 inside the container base 502 . The container base 502 is provided with the inclined trench 504 on the opposite sides of the casing to facilitate the placement of re-movable charcoal container 501 inside the container base 502 of the hubble-bubble device. The container pins 505 a and 505 b are provided to plug the container base 502 along with the re-movable charcoal container 501 in the heading section 100 of a device housing in the hubble-bubble device.
[0043] FIG. 8 illustrates an exploded view of a charcoal container (with an inclined trench) for the hubble-bubble device according to one embodiment of the present disclosure. The re-movable charcoal container 501 is provided with corkscrews/knob 503 a and 503 b and/or special protrusions that facilitate the placement of the re-movable charcoal container 501 inside the container base 502 as shown in FIG. 7 and FIG. 8 . The container base 502 is provided with the inclined trench 504 on the opposite sides of the casing to facilitate the placement of re-movable charcoal container 501 inside the container base 502 of the hubble-bubble device and to regulate the distance of the container 501 from the surface of the tobacco tray 103 . The inclined trench 504 provided on the container base 502 helps in the adjustment of a distance between the re-movable charcoal container 501 from the tray 103 provided in the bottom section of the heading section 100 of the hubble-bubble device. The container pins 505 a and 505 b are provided to plug the container base 502 along with the re-movable charcoal container 501 in the heading section 100 of the hubble-bubble device.
[0044] FIG. 9 illustrates the front view of the heading section of the hubble-bubble device with the charcoal container placed inside the holder having furrow extending along a casing according to an embodiment of the present disclosure. The charcoal container 901 is provided with the corkscrew/knob 905 and/or special protrusions that facilitate a placement of the charcoal container 901 inside the holder 902 of the heading section 100 of the hubble-bubble device. The holder 902 is provided with the furrows 906 that are in the form of thread and/or staircase or any other form which is extended along the casing as shown in FIG. 9 . With the placement of tobacco over the tobacco tray 903 and with the placement of the tobacco tray 903 in its place, the replacement of the tobacco tray 903 and the tobacco is possible at every time.
[0045] FIG. 10 illustrates an exploded view of the heading section of the hubble-bubble device with the charcoal container placed inside the holder having furrow extending along a casing according to an embodiment of the present disclosure. The charcoal container 901 is provided with the corkscrew/knob 905 and/or special protrusions that facilitate the placement of charcoal container 901 inside the holder 902 of the heading section 100 of the hubble-bubble device. The charcoal container 901 in its flooring section include a circular piece 908 made of metal that is used as the board for placing a charcoal. The holder 902 is provided with the furrows 906 that are in the form of thread and/or staircase or any other form and are extended along the casing as shown in FIG. 9 and FIG. 10 . With the placement of the tobacco over the tobacco tray 903 and with the placement of tobacco tray 903 in its place, the replacement of tray 903 and tobacco is possible in each time of use.
[0046] The tray 903 is provided with the knob 907 to pull-out and push-in the tray 903 containing tobacco in the hubble-bubble device. With the placement of a charcoal in the charcoal container 901 , depending on the form of the piece, the distance from flamed charcoals up to the placement site of the tobacco can be adjusted. This avoids the burning of the tobacco during a smoking by rotating the piece and moving it over the furrows 906 existing inside the heading section 100 of the hubble-bubble. The charcoal container is provided with a lid (not shown) to avoid a scattering of the ash of the flamed charcoal. The lower section 904 of the heading section 100 is connected to the body of the hubble-bubble device.
[0047] FIG. 11 illustrates a front view of the heading section of the hubble-bubble device with the charcoal container placed inside the holder having a set of furrows (placed opposite to each other) along a casing according to an embodiment of the present disclosure. The charcoal container 901 is provided with the corkscrews/knob 905 a and 905 b and/or special protrusions that facilitate the placement of the charcoal container 901 inside the holder 902 of the heading section 100 of the hubble-bubble device. The holder 902 is provided with the set of furrows 906 placed on the opposite sides on the holder 902 casing as shown in FIG. 11 . The charcoal container 901 in its flooring section holds a circular piece 908 made of metal that is used as the board for placing charcoal. With the placement of the tobacco over the tray 903 and with the placement of the tobacco tray 903 in its place, the replacement of the tobacco tray 903 and the tobacco is possible in each time of use.
[0048] FIG. 12 illustrates an exploded view of the heading section of the hubble-bubble device with the charcoal container placed inside the holder having a set of furrows (placed opposite to each other) along a casing according to an embodiment of the present disclosure. The charcoal container 901 is provided with the corkscrews/knob 905 a and 905 b and/or special protrusions that facilitate placement of the charcoal container 901 inside the holder 902 of the heading section 100 of the hubble-bubble device. The holder 902 is provided with the set of furrows 906 placed on the opposite sides on the holder 902 casing in the form of thread and/or staircase or any other form that is extended along the casing as shown in FIG. 11 and FIG. 12 . Charcoal container 901 in its flooring section may hold a circular piece 908 made of metal that is used as the board for placing the charcoal. With the placement of the tobacco over the tray 903 and with the placement of tobacco tray 903 in its place, the replacement of tray 903 and the tobacco is possible in each time of use.
[0049] The tray 903 is provided with the knob 907 to pull-out and push-in the tray 903 containing a tobacco in to the hubble-bubble device. With the placement of a charcoal in the charcoal container 901 , depending on the form of the piece, one can adjust the distance from flamed charcoals up to the placement site of the tobacco and avoid the burning of the tobacco during the smoking by rotating the charcoal container 901 and moving it over the furrows 906 existing on the casing of the holder in the heading section 100 of the hubble-bubble device. The charcoal container is provided with a lid (not shown) to avoid the scattering of the ash of flamed charcoal. The lower section 904 of the heading section 100 is connected to the body of the hubble-bubble device.
[0050] One of the advantages of the proposed heading section of the hubble-bubble device is a quick replacement of a tobacco and easy regulation of the distance between the charcoal and the tobacco. The distance regulation mechanism provided in the heading section prevents a burning of the tobacco due to an excess heat from the charcoal. The rate of the temperature required for the effective functioning of the smoking apparatus is controlled through the proposed design and mechanism. Also it permits the increase of a heat for increasing the density of smoke of hubble-bubble in the case of coal shortage. The embodiment herein provides for an easy replacement of any part in case of damage of the part. The drawer type design for the tobacco tray provides for checking the quantity and quality of the tobacco present in the tobacco tray during the smoking process. The embodiment disclosed herein is suitable for any climate.
[0051] The foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the appended claims.
[0052] Although the embodiments herein are described with various specific embodiments, it will be obvious for a person skilled in the art to practice the invention with modifications. However, all such modifications are deemed to be within the scope of the claims.
[0053] It is also to be understood that the following claims are intended to cover all of the generic and specific features of the embodiments described herein and all the statements of the scope of the embodiments which as a matter of language might be said to fall there between. | The various embodiments herein provide an efficient head for hubble-bubble device used in smoking and using tobacco with the capability of immediate tobacco replacement and easy regulation of the distance between charcoal and tobacco. A hubble-bubble device comprises the holder, the charcoal container arranged on top of the holder and the tobacco tray arranged on a bottom section of the holder. The tobacco tray is in the form of a drawer which provides for insertion and removal of the tobacco tray from the holder thereby facilitating quick replacement of the tobacco. | 0 |
BACKGROUND OF THE INVENTION
The right ventricle receives blood from the right atrium through the tricuspid valve and pumps the blood through the pulmonic valve to the pulmonary artery. In pumping blood, the right ventricle expands during diastole to take in blood through the tricuspid valve and contracts during systole to discharge blood through the pulmonic valve into the pulmonary artery.
It is sometimes necessary or desirable to determine the effectiveness of the right ventricle in pumping blood to the pulmonary artery, and for this purpose, right heart ejection fraction is determined. Ejection fraction is determined by comparing the expanded volume or end diastolic volume (EDV) of the right ventricle with the contracted volume or end systolic volume (ESV) of the right ventricle. Mathematically, ejection fraction (EF) can be expressed as follows: ##EQU1##
Ejection fraction is calculated from thermodilution curves by hand computation. Thermodilution is typically carried out by injecting a cold indicator into the right ventricle or right atrium and allowing the indicator to be diluted with blood. As this cold mixture is pumped through the right ventricle into the pulmonary artery, the temperature of the fluid in the pulmonary artery falls and then rises. The temperatures of the fluid in the pulmonary artery are measured during the time that the temperature is rising and compared with a prebolus baseline temperature of blood in the pulmonary artery to establish temperature differentials. The temperature differentials are then used to determine ejection fraction. Ejection fraction calculation is widely discussed in the literature, such as
1. Journal of Surgical Research, "Measurement of Ejection Fraction by Thermal Dilution Techniques", H. R. Kay et al, Vol. 34, 337-346 (1983).
2. The Journal of Trauma, "Thermodilution Right Ventricular Volume: A Novel and Better Predictor of Volume Replacement in Acute Thermal Injury", J. A. J. Martyn et al, Vol. 21, No. 8, 619-626 (1981).
3. ASA, "Ejection Fraction By Thermodilution" (Abstract), G. G. Maruschak et al, Vol. 55, No. 3, September 1981.
Hand calculation of ejection fraction is typically performed using the plateau method which can be mathematically stated as follows: ##EQU2## where, T i is the temperature at any of the plateaus on the downslope (i.e. during the time the temperature in the pulmonary artery is rising) of the thermodilution curve, T i+1 is the temperature at the immediately following plateau, and T B is the baseline temperature. Hand calculation of ejection fraction using the plateau method is, of course, slow and, as shown by equation 2, utilizes only two points in the cardiac cycle, see American Journal of Cardiology, "Usefulness and Limitations of Thermal Washout Techniques in Ventricular Volume Measurement", E. Rapaport, Vol. 18, 226-234, August 1966.
In addition, calculation of ejection fraction using the plateau method is consistently lower than ejection fraction as calculated using radionuclear techniques. Accordingly, it is desirable to refine the ejection fraction determinations so that more accurate results are obtained.
SUMMARY OF THE INVENTION
This invention automates EF determinations and provides other important advantages. This invention is based, in part, upon the recognition that some of the assumptions underlying the calculation of ejection fraction using equation 2 are erroneous. For example, one such assumption is that the baseline temperature T B of the blood entering the right ventricle does not change from a time just before injection of the bolus through the times that the temperature is measured in the pulmonary artery for the purpose of determining EF. This is not true if atrial injection is utilized. Because injection of the cold indicator is carried out over several heart beats, some indicator is pooled in the atrium, and this changes the baseline temperature T B of the blood entering the right ventricle from the prebolus baseline temperature prior to injection. This is one reason why ejection fraction calculations made by the plateau method tend to be low.
This invention compensates for the baseline temperature drift without adding another temperature sensor to the catheter used in taking the temperature measurements. This is accomplished by establishing a temperature versus time relationship or curve using at least some of the measured temperatures in the pulmonary artery when the temperature of fluid in the pulmonary artery is rising. This curve projects temperatures between the measured temperatures and beyond the highest measured temperature used to establish the curve. A temperature established by the curve which is below the last measured temperature is then used to establish the post bolus baseline temperature.
For the best results, the curve preferably is or approximates a first order exponential curve. This curve can be used in various different ways to approximate a post bolus baseline temperature T B2 which produces more accurate results than the prebolus baseline temperature which is the blood temperature entering the right ventricle prior to injection of the cold indicator into the atrium. In any event, the post bolus baseline temperature will be lower than the prebolus baseline temperature due to the various cooling factors identified above.
A preferred technique for establishing the post bolus baseline temperature is to use as the post bolus baseline temperature, the temperature identified by the first order exponential curve as the curve approaches its asymptote. Although the use of this curve to establish a post bolus baseline temperature is particularly adapted for injection of the indicator upstream of the right ventricle, such as in the atrium, it may also be used for ventricular injection.
The plateau method as determined by equation 2 also assumes that the temperatures sensed in the pulmonary artery accurately represent the temperature of the fluid in the pulmonary artery. However, testing has shown that the response time of the catheter mounted temperature sensor is not adequate to monitor 100 percent of the temperature change within a given heartbeat interval. Numerical modeling provides a means by which the response time can be compensated for when the heartbeat or R--R interval is known. This enables more accurate computer measurement of the temperature changes in the pulmonary artery.
This can be accomplished, for example, by determining the response time for a group of the catheter-mounted sensors which are to be utilized. A correction factor can then be applied to the calculated EF.
Another assumption underlying the use of equation 2 is that there is no arrhythmic heart activity during the time that the temperatures in the pulmonary artery are being measured to determine ejection fraction. This invention recognizes the possibility of such arrhythmic heart activity and provides for arrhythmia detection. If arrhythmic heart activity is detected during the time of interest, an alarm is activated to advise of the arrhythmic heart activity.
The invention, together with additional features and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying illustrative drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view through the right heart showing one form of catheter which can be used in the determination of ejection fraction.
FIG. 2 is an idealized, illustrative plot of temperature of the fluid in the pulmonary artery versus time and of the corresponding "R" waves and detected "R" waves.
FIG. 3 is a flow chart showing the basic steps in the determination of ejection fraction.
FIG. 4 is a plot of temperature versus time illustrating how the post bolus baseline temperature is established.
FIG. 5 is a plot of percent response versus time for one catheter-mounted thermistor that may be used in carrying out this invention.
FIG. 6 is a block diagram showing one apparatus embodying the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 illustrates one form of catheter 11 inserted into a human heart 13 for the purpose of carrying out the present invention. Although the catheter 11 may be of various different constructions and be just a temperature probe, in this embodiment, the catheter includes an elongated flexible tube 15 having an injectate port 17, a balloon 19 closely adjacent the distal end of the tube and a temperature sensor in the form of a thermistor 21 proximal of the balloon but adjacent the distal end of the tube. A more complete description of the catheter 11 can be obtained from Webler et al application Ser. No. 570,631 filed Jan. 13, 1984, now U.S. Pat. No. 4,632,125, which is incorporated by reference herein.
The catheter 11 is inserted into the heart 13 using conventional medical techniques to place the balloon 19 and the thermistor 21 in pulmonary artery 23 and to place the injectate port 17 in right atrium 25. Thus, the catheter extends through tricuspid valve 27, right ventricle 29 and the pulmonic valve 31 to the pulmonary artery 23.
To determine right heart ejection fraction or cardiac output, a bolus of cold indicator, such as saline solution, is rapidly injected over several heart beats through a lumen of the tube 15 and the injectate port 17 into the right atrium 25. In the illustrated embodiment, the injectate is directed generally toward inferior vena cava 32 counter current to the blood flow from the inferior vena cava so as to provide good mixing with the blood. During diastole, the right ventricle 29 expands, and the tricuspid valve 27 opens to allow some of the blood-indicator mixture to enter the right ventricle. During systole, the right ventricle 29 contracts to force or pump the blood-indicator mixture through the pulmonic valve 31, into the pulmonary artery 23 and across the thermistor 21. Because the injection of the cold indicator takes place over multiple heart beats, the temperature of the fluid in the pulmonary artery 23 reduces from a prebolus baseline temperature T B1 (FIG. 2) in multiple increments to a lowermost temperature or temperature peak T PK and then increases in increments such that the temperature curve asymptotically approaches the prebolus baseline temperature T B1 . As shown in FIG. 2, each temperature step or plateau of the thermodilution (TD) curve 33 immediately follows an "R" wave or right ventricle 29 contraction or heart beat. It should be noted that the TD curve 33 is inverted in that the prebolus baseline temperature T B1 is a higher temperature than the temperature peak T PK . Using the TD curve 33 and equation 2, it is possible to calculate ejection fraction as more fully described in, for example, Webler et al application Ser. No. 570,631 now U.S. Pat. No. 4,632,125 referred to above.
The present invention provides for the automated determination of ejection fraction, although hand computation utilizing the principles of this invention is also possible. This invention can be implemented with the catheter 11 and a suitable instrument 34 (FIG. 1) which may include suitable electronic hardware, software and a microcomputer or a combination of the two. A software implementation is preferred to carry out the steps shown in FIG. 3, and in that connection, it is only necessary to make certain modifications to a program known as COM-1 used by equipment available from American Edwards Laboratories of Santa Ana, Calif., for the purpose of computing cardiac output.
With the catheter 11 in the heart 13 as shown in FIG. 1, the thermistor 21 provides continuous temperature information concerning the temperature of the fluid, i.e., blood or blood-indicator mixture in the pulmonary artery 21 to the instrument 34. In a digital system, this temperature information is sampled periodically, such as every 71 milliseconds by a sampler in the instrument 34. With reference to FIG. 3, and excluding the usual preliminaries of the type used in the COM-1 program, such as noisy baseline identification and thermodrift detection, the first step is prebolus baseline determination, i.e., determining the prebolus baseline temperature T B1 . To accomplish this, the temperature samples are averaged in any suitable manner, such as by calculating a running average of the samples. Although TB1 is actually measured in the pulmonary artery, it can be safely assumed that, prior to injection of the cold indicator, the temperature of the blood entering the right ventricle is the same as in the pulmonary artery.
With T B1 determined, the operator can initiate a start command, and a bolus of cold indicator is injected through the injectate port 17 into the right atrium 25 with such injection taking place over multiple heart beats. The indicator cools the blood and forms a blood-indicator mixture which is pumped through the right ventricle 29 to the pulmonary artery to provide the TD curve 33 shown in FIG. 2. The start command also brings about the storage of raw dT values and the associated detected "R" waves 35 (FIG. 2) as, for example, a twelve-bit word. The dT values are the difference between the temperature defined by the TD curve 33 and the prebolus baseline temperature T B1 as shown in FIG. 2. The dT samples are taken periodically, such as every 71 milliseconds, and the buffer for storing such samples may be, for example, 1024 words in length for approximately 73 seconds of storage. Every "R" wave is stored in the "R" wave buffer in the instrument 34 and is stored as a detected "R" wave 35. The "R"-wave buffer and the buffer for the dT values are synchronized in time so that, for each dT value, the presence or absence of an "R" wave during the associated dT sample time is stored as a "1" or "0" in the "R"-wave buffer. This buffer synchronization facilitates correlation between heart electrical activity and fluid movement by the heart as manifested in temperature changes, i.e., dT values. Although the dT values can be manipulated in various different ways, it is preferred to store all of the dT values. In addition, a real time running average of recent dT values is maintained, as represented by the half-second window storage. For example, every 7 dT samples may be averaged and stored as a 0.5 second average. Thus, the first 7 dT values are averaged, then dT values 2 through 8 are averaged and so on.
Next, the peak temperature T PK , or lowest temperature, is determined. This can be accomplished, for example, by identifying the largest stored 0.5 second dT average as the peak temperature T PK . T PK and the time when it occurs are stored.
Next, the deviation 80% and 30% values are calculated by multiplying 0.8 and 0.3, respectively, times the peak temperature T PK . These calculated values are stored.
Using the stored 0.5 second dT averages, the 80 percent deviation determination is located on the TD curve 33. Specifically, the first of such average dT values following T PK that is equal to, or less than 0.8 times T PK is stored as T D1 . The time at which the temperature T D1 occurs is also stored.
Similarly, the 30 percent of deviation determination is also located. The first of the stored average dT values following T PK that is equal to or less than 0.3 times the temperature T PK is identified as T D2 and is stored along with its reference time.
Establishing T D1 and T D2 as approximately equal to 0.8 times T PK and 0.3 times T PK , respectively, is desirable but not critical. However, other points on the downslope of the TD curve 33 between about 0.95 times T PK and 0.15 times T PK can be used, if desired.
The evaluation interval is then determined as the first step of post processing. To enhance repeatability and allow for a good curve fit, it is desired to consistently locate the evaluation interval in accordance with a particular program. Generally, this can be accomplished by determining the "R" waves occurring closest to T D1 and T D2 and their respective times of occurrence. Various programs for choosing such "R" waves can be used. For example, if T D1 occurs between "R" waves, the first of such "R" waves, i.e., the "R" wave nearer T PK , is used to establish the upper limit temperature T u if such "R" wave's corresponding temperature amplitude is within 12.5 percent of the temperature T D1 and is less than 90 percent of the peak temperature T PK . Also, this "R" wave must occur after the occurrence of the peak temperature T PK . If these synchronization conditions are met for such first "R" wave, then the temperature corresponding to the time of occurrence of such " R" wave will be used as the upper limit temperature T u . If these synchronization conditions cannot be achieved for such first "R" wave, then the temperature corresponding to the time of occurrence of the "R" wave immediately following the occurrence of the temperature T D1 will be used as the upper limit temperature T u .
The "R" wave nearest the temperature T D2 must be at least two R--R intervals beyond the upper "R" wave. If the "R" wave which is two R--R intervals forward down the TD curve 33 is from 15 to 30 percent of T PK , then this point is used as T L as shown in FIG. 2. If this "R" wave is above 30 percent of T PK , then the temperature that corresponds to the "R" wave that is closest to 30 percent of T PK is used. If the temperature along the TD curve 33 at the end of the second R--R interval is less than 15 percent of T PK , then the temperature at the end of the first R--R interval is used for T L . If the temperature at the first R--R interval is still less than 15 percent of T PK , an error message is given.
The respective upper and lower limit temperature values T u and T L are stored and each is preferably an average, such as a 3-point average, of the data on each side of the associated "R" wave. For example, if T 2 corresponds to the lower "R" wave synchronization point, the actual temperature used for T L would be as follows: ##EQU3## where, T 1 and T 3 are stored temperatures dT on opposite sides of T 2 .
The temperatures T L and T u which also constitute evaluation limits always coincide with "R" wave events as shown in FIG. 2.
Next a post bolus baseline temperature T B2 is determined utilizing T u and T L and force fitting a first order exponential curve to these two points as shown in FIG. 4. This calculation is made using the prebolus baseline temperature T B1 as follows: ##EQU4## where, TD is the value on the curve 41
Δ is the temperature T u
t is time and ##EQU5## where, t L is the time at which T L occurs and
t u is the time at which T u occurs.
Thus, by implementing equation 4, the curve 41 of FIG. 4 can be plotted and extrapolated beyond T L . Because the curve 41 is or approximates a first order exponential curve, it asymptotically approaches the prebolus baseline temperature T B1 .
This invention establishes as the post bolus baseline temperature T B2 the temperature which exists near the time when the curve 41 closely approaches T B1 . Although various levels can be employed, a preferred approach is to utilize a threshold of 0.01 to 0.05 of T PK with 0.03 to T PK being optimum. The time t f at which this threshold temperature occurs can be obtained by solving for "t" in equation 4 which yields t a , which is the difference between t F and t u . The time t F can be found from the equation t F =t u +t a . Next, the raw temperature data that corresponds to the time t F is located, and this is established as the post bolus baseline temperature T B2 . Preferably, an average, such as a 70-point average of the temperature data beginning at t F is used to establish the post bolus baseline T B2 , i.e., an average of the temperatures occurring in the pulmonary artery in the next 2.5 to 5 seconds may be used to establish T B2 .
The post bolus baseline temperature T B2 is subtracted from the curve 41 to provide a new upper limit temperature T nu and a new lower limit temperature T nL . A new curve 43 can then be force fit to the new upper and lower limit temperatures T nu and T nL as shown in dashed lines in FIG. 4. The curve 43 asymptotically approaches the post bolus baseline temperature T B2 . The number of "R" waves occurring during the evaluation interval, i.e., between t u and t L are determined, and the duration of the evaluation interval is calculated. From this, preliminary ejection fraction can be calculated from the following equation: ##EQU6## n=the number of "R" waves occurring during the evaluation interval.
The preliminary ejection fraction calculation is then corrected based upon the response time of the catheter mounted thermistor 21. For this purpose, the response of the catheter mounted thermistor 21 is plotted as a function of time using any suitable technique, and one such plot for the thermistor 21 as mounted on the catheter 11 is shown in FIG. 5.
Although various techniques can be utilized to determine the response, to plot FIG. 5, a group of the catheters 11 having the thermistor 21 thereon were tested for response time data at the 63 percent, 90 percent and 95 percent responses. The average of these data points at these responses are shown by the points D, E, F on the response curve 51. Beyond the point F, the curve 51 approaches an asymptote A which represents the maximum percent response for the catheter-mounted thermistor. For a catheter mounted thermistor, a second order exponential curve 51 is a good approximation of the percent response as a function of time, with the curve 51 being influenced primarily by the first order component from the origin to a division response or point G, which, in this example, is beyond the point D and at about 70 percent response, and with the curve 51 being primarily influenced by the second order component above, response G. By placing a time delay before the second order component, its effect on the first order component is delayed; hence the shape of the curve between the points G and E. The functional form of the equation for the second order exponential curve 51 is: ##EQU7## where, A is the % response at the asymptote,
B and C are the first and second order slope coefficients, and
t is time.
The best curve fit using this form is achieved with A equal to 97, B equal to 12 and C equal to 1.8.
As shown by FIG. 2, the temperature during the downslope of the curve 33 changes with each heart beat. Accordingly, the time for the thermistor 21 to react to a temperature change is equal to the R--R interval. The model shown by way of example in FIG. 5 shows the known approximate percent response to temperature change as a function of time, i.e., about how rapidly the catheter-mounted thermistor 21 responds during any given time interval. Although this could be used to correct every temperature value, this would be quite complex, and it has been found that a good approximation for correcting the ejection fraction can be determined as follows: ##EQU8## To utilize equation 7, the length of the R--R interval or the average length of such intervals between t u and t L determine the time in seconds, and from this the actual percent response can be determined from the curve 51. Thus, R--R interval of one second would provide an 80 percent actual response which in turn would provide a correction factor of 1.25 which should be multiplied by the preliminary EF to obtain the corrected ejection fraction.
Of course, the ejection fraction can be calculated multiple times from multiple injections of cold indicator, if desired. The mathematical functions and the steps described above can be readily implemented with software.
An optional, but important, feature of the invention is the setting of a flag or the providing of an alarm if any arrhythmic heart activity occurs during the evaluation interval. This can be accomplished by appropriate monitoring of the "R" wave data stored in the "R" wave buffer. Although this can be accomplished in different ways, the present invention provides a 4-beat running average of the "R" wave intervals with all abnormal beats and the beat following any abnormal beat not being used in the average; i.e., with each new beat, a new average of the 4 most recent normal beats is taken. Although various factors could be monitored, this invention considers heart activity which is out of range, premature, or delayed to be abnormal or arrhythmic in nature. For example, individual heart beats and the preceeding R--R interval which are equivalent to heart rates below 35 per minute or over 180 per minute are considered out of range. Delayed beats are those which are separated by more than one-and-one-half times the current 4-beat average, and a premature beat is any beat which has its preceding R--R interval 20 beats per minute faster than the current 4-beat average. Thus, the present invention provides an alarm if any out of range, delayed or premature beats occur during the evaluation interval by monitoring the stored R-wave data.
FIG. 6 shows by way of example a block diagram of the components of the instrument 34. Analog temperature data from the catheter 11 is fed through an isolation amplifier 101 to an A/D converter which samples the raw temperature data periodically, such as every 71 milliseconds, to provide dT temperature samples or values to a microcomputer 105. Similarly, "R"-wave information is fed through an isolation amplifier 107 to an "R"-wave detector 109 which provides the detected "R" waves 35 to the microcomputer 105. The microcomputer 105 has the storage capability to store the temperature samples dT and the detected "R" waves 35 and to perform the other functions discussed above. A display 111 may be provided to display, for example, the calculated ejection fraction.
As used herein, the term "catheter" refers to any probe or catheter. The injection and temperature-measuring functions of the catheter can be carried out by separate catheters, if desired.
Although an exemplary embodiment of the invention has been shown and described, many changes, modifications and substitutions may be made by one having ordinary skill in the art without necessarily departing from the spirit and scope of this invention. | A method and apparatus for determining right heart ejection fraction by injecting a cold indicator into the right ventricle or locations in the heart upstream thereof during an injection period and allowing the indicator to be diluted with blood and flow to the pulmonary artery whereby the temperature of the fluid in the pulmonary artery falls and then rises, measuring the temperature of the fluid in the pulmonary artery at least during the time that the temperature in the pulmonary artery is rising, measuring a prebolus temperature of the blood in the pulmonary artery prior to the time that the cold indicator reaches the pulmonary artery, establishing a post bolus baseline temperature which is lower than said prebolus baseline temperature, comparing at least some of the measured temperatures during the time that the temperatures of the fluid in the pulmonary artery are rising to the post bolus baseline temperature to establish temperature differentials, and using at least some of the temperature differentials to determine ejection fraction. | 0 |
The present application claims priority to Provisional Application Serial No. 60/303,643, filed Jul. 9, 2001, herein incorporated by reference.
FIELD OF THE INVENTION
The present invention relates generally to multifunctional devices for performing suction, irrigation, and manipulation at an internal site in a subject, and more particularly to enlargeable multifunctional devices for performing such functions while avoiding obstruction during conventional and endoscopic surgery.
BACKGROUND OF THE INVENTION
There are two fundamental types of surgery, conventional and endoscopic surgery. Conventional surgery generally involves a relatively large incision with direct visualization (e.g. the “naked eye”) of the area being operated upon. Examples of conventional surgery include heart and bowel surgeries. Endoscopic surgery involves indirect visualization of the operative field with a small camera. Endoscopic surgery is generally done by way of multiple small incisions through which a camera and instruments are inserted. The instruments perform their functions inside the body but are operated by use of their handles outside the body. Examples of endoscopic surgery include endoscopic appendix or gallbladder removal. Endoscopic surgery can also be done through existing, natural orifices (e.g. certain prostate surgeries).
A surgeon uses mechanical devices to assist in performing a variety of interventions within the surgical field during an operation. Three functions generally performed by such mechanical devices include direct tissue manipulation, irrigation, and suction. Direct tissue manipulation may include, but is not limited to, cutting, stitching, cauterizing, injecting, and scraping. Irrigation may include washing the surgical area with fluids (often directed with a tube and/or nozzle). Irrigation is employed as the area of interest within the operative field can become contaminated or can be obscured from visualization by blood or debris. Suction is employed as irrigation fluids and bodily fluids collect in the operative field and need to be removed. There are various devices that currently fulfill these functions. Their use is sometimes impeded, however, when malleable tissue such as fat or intestine surrounds the area of interest and obstructs visualization and/or operation of the device. Below are examples of the limitations of currently used devices.
Currently utilized direct tissue manipulation devices come in many different designs. These devices do not have a feature to intrinsically hold malleable tissue away from the tip of the instrument. This function is served by an assistant's hands or a separate device. This can make surgery particularly difficult during small incision conventional surgery or any endoscopic surgery.
Currently utilized suction devices contain a tube of fixed diameter (see, e.g., FIG. 1 ). These devices have an opening and/or perforations on the sides of the barrel through which fluid flows and is removed from the operative field. However, during endoscopic surgery (or other types of surgery), the ability to retract tissue out of the operative field is constrained by the limited number of introducer ports through which extra instruments can be placed. Thus, suction devices are frequently operated in close proximity to malleable tissue such as fat or intestine. This leads to frequent obstructions of the suction ports which require the surgeon to disengage the tissue from the device in order to resume suctioning of fluid. Disengaging the tissue from the suction device uses valuable operating room time and distracts from the primary tasks of the operation.
Currently utilized irrigation devices simply have a tube through which fluid is expelled into the operative field for cleansing or visualization purposes. Like the other two examples, malleable tissue can obstruct the end of the instrument.
What is needed are multifunctional devices capable of performing functions at an internal site in a subject (e.g. suction, irrigation, tissue manipulation) while avoiding obstruction from malleable tissue.
SUMMARY OF THE INVENTION
The present invention relates generally to multifunctional devices for performing suction, irrigation, and manipulation at an internal site in a subject, and more particularly to enlargeable multifunctional devices for performing such functions while avoiding obstruction during conventional and endoscopic surgery.
In some embodiments, the present invention provides multifunctional devices (e.g. for performing at least one function at an internal site in a subject), comprising; an elongate member with a plurality of openings defining an enlargeable section, wherein the enlargeable section comprises a plurality of walls, and wherein the enlargeable section is movable between a non-enlarged position, and an enlarged position. In preferred embodiments, the enlarged position creates a chamber in the elongate member. In particular embodiments, the enlarged position is any position of the enlargeable section that has a cross-sectional dimension greater than the enlarged section when in the non-enlarged position. In certain embodiments, the enlargeable section, when moved from the non-enlarged position to the enlarged position, is capable of pushing bodily tissue outward (e.g. the walls of the enlargeable section are capable of pushing bodily tissue away from the elongate member axis).
In other embodiments, the present invention provides multifunctional devices (e.g. for performing at least one function at an internal site in a subject comprising; an elongate member with a plurality of openings defining an enlargeable section, wherein the enlargeable section comprises a plurality of walls, and wherein the enlargeable section is movable between a non-enlarged position, and an enlarged position, wherein the enlarged position forms a chamber in the elongate member, and b) a sleeve member enclosing at least a portion of the elongate member, the sleeve member being moveable between a first position along the elongate member that fully encloses the enlargeable section, and a second position along the elongate member that at most partially encloses the enlargeable section. In particular embodiments, the sleeve member enclosing at least a portion of the elongate member may be pushed distally around the enlargeable section to transfer the location of maximal suction and/or irrigation forces toward the distal end of the device.
In certain embodiments, the present invention provides methods for constructing a multifunctional device, comprising; a) providing an elongate member, and b) generating a plurality of openings in the elongate member such that an enlargeable section is formed in the elongate member, the enlargeable section comprising a plurality of walls and being moveable between a non-enlarged position and an enlarged position. In preferred embodiments, the enlarged position creates a chamber in the elongate member.
In other embodiments, the present invention provides methods for constructing a multifunctional device, comprising; a) providing; i) an elongate member, and ii) a sleeve member configured for enclosing at least a portion of the elongate member; and b) generating a plurality of openings in the elongate member such that an enlargeable section is formed in the elongate member, the enlargeable section comprising a plurality of walls and being moveable between a non-enlarged position and an enlarged position, wherein the enlarged position creates a chamber in the elongate member; and c) inserting the elongate member into the sleeve member such that the sleeve member is moveable between a first position along the elongate member that fully encloses the enlargeable section, and a second position along the elongate member that at most partially encloses the enlargeable section.
In some embodiments, the present invention provides methods for performing at least one function at an internal site in a subject, comprising; a) providing; i) a multifunctional device comprising an elongate member with a plurality of openings defining an enlargeable section, wherein the enlargeable section comprises a plurality of walls, and wherein the enlargeable section is movable between a non-enlarged position, and an enlarged position, wherein the enlarged position creates a chamber in the elongate member, and ii) a subject comprising a body opening; and b) inserting the multifunctional device through the body opening into an internal site in the subject with the enlargeable section in the non-enlarged position. In preferred embodiments, the method further comprises step c) moving the enlargeable section from the non-enlarged position to the enlarged position. In certain embodiments, the methods of the present invention are part of an endoscopic surgery or endoscopic procedure. In some embodiments, the moving step is accomplished by pushing the distal end of the device against a solid surface in the subject (e.g. against tissue in the subject).
In other embodiments, the device further comprises a sleeve member, and the moving step is accomplished by moving the sleeve member to a position such that it does not enclose the enlargeable section. In other embodiments, the body opening is an incision in the body of the subject. In some embodiments, the body opening is a natural orifice in the body of the subject. In particular embodiments, the sleeve member enclosing at least a portion of the elongate member may be pushed downward around the enlargeable section to transfer the location of maximal suction and/or irrigation forces toward the proximal end of the device.
In certain embodiments, the elongate member is configured for transmitting fluid (e.g. into and/or out of a surgical site). In some embodiments of the present invention, the elongate member is configured for suctioning. In other embodiments, the elongate member is configured for irrigation.
In particular embodiments, the elongate member comprises a tube (e.g. a cylindrical, hollow member with openings at both ends). In some embodiments, the tube comprises plastic (e.g., polyethylene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyacetal, polyphenylene oxide, polytetrafluoethylene, polyethylene teraphthalate, polybutylene terephthalate, phenolic urea formaldehyde, melamine formaldehyde, polyester, and combinations thereof). In some embodiments, the elongate member is at least 1 centimeter in length (e.g. at least 1 centimeter, or at least 2 centimeters, or at least 3 centimeters). In certain embodiments, the elongate member is at least 5 centimeters in length (e.g. at least 5 centimeters, or at least 10 centimeters). In other embodiments, the elongate member is at least 12, or at least 15, or at least 18, or at least 20 centimeters in length. In particular embodiments, the elongate member is no more than 5 centimeters in length (e.g. no more than 5 centimeters, or no more than 3 centimeters, or no more than 2 centimeters).
In some embodiments, the elongate member has a primary cross-sectional dimension (e.g., a cross-sectional dimension that is present throughout at least 50 percent of the length of the elongate member). In certain embodiments, the primary cross-sectional dimension is present throughout at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent, or at least 95 percent, or at least 99 percent of the elongate member. In preferred embodiments, the cross-sectional dimension of the elongate member is uniform throughout its length. In certain embodiments, the primary cross-sectional dimension is a diameter value ranging between 2 millimeters and 15 millimeters (e.g., approximately 2 mm, 3 mm, 8 mm, 12 mm, or 14 mm). In other embodiments, the primary cross-sectional dimension is a diameter value ranging between 4 millimeters and 10 millimeters (e.g. approximately 4 mm, 6 mm, 8 mm or 10 mm).
In particular embodiments, the elongate member comprises a distal tip. In further embodiments, the enlargeable section of the elongate member has a bulging midsection shape. In other embodiments, the elongate member has a distal end and a proximal end. In certain embodiments, distal end of the elongate member is configured to be inserted in a body opening of a subject (e.g. during endoscopic surgery). In some embodiments, the proximal end of the elongate member is configured to remain outside the body (e.g., during endoscopic surgery such that the device may be manipulated by a user, such as a surgeon). In other embodiments, the enlargeable section is located in the distal end of the elongate member. In still other embodiments, the multifunctional device further comprises a handle. In particular embodiments, the handle is located in, or attached to, the proximal end of the elongate member.
In certain embodiments, the plurality of walls are separated by at least one of the plurality of openings (e.g. at least 1, 2, 3, 4, 5, 6, 7, 8, or 9 of the plurality of openings). In other embodiments, at least one of the plurality of walls is at least 1 millimeter in length (e.g., at least 1, 2, 3, 4, 5, or 6 millimeters in length).
In some embodiments, at least one of the plurality of openings in the elongate member is a longitudinal opening. In further embodiments, the at least one longitudinal opening is at least 1 millimeter in length (e.g. at least 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, or 6 mm in length). In certain embodiments, the plurality of openings comprises at least three separate openings (e.g. at least 4, or 5, or 6, or 7, or 8, or 9, or 15, or 20 separate openings). The plurality of openings of the present invention may be of any shape or size. In some embodiments, the openings are longitudinal, diamond, zig-zag shape, regular or irregularly shaped, and allow adjustment of the chamber shape and/or volume.
In certain embodiments, the enlargeable section, when in the enlarged position, has a cross-sectional dimension at least 1.5 times larger than the enlarged section when in the non-enlarged position (e.g. at least 1.5 times larger, or at least 2 times larger, or at least 3 times larger, or at least 4 times larger). In some embodiments, the chamber has a volume of at least 5 cubic centimeters (e.g., at least 6 cc, 7 cc, 8 cc, 9 cc, or at least 10 cc).
In preferred embodiments, at least a portion of the enlargeable section is enclosed by media (e.g., an expandable membrane, such as GORE-TEX ePTFE membranes, made by W. L. Gore & Associates, Inc., Elkton, Md.). In particularly preferred embodiments, the media is biocompatible. In other preferred embodiments, the media further comprises a therapeutic agent, including, but not limited to, antibiotics, anticoagulants, steroids, and combinations thereof. In some embodiments, the media is permeable to liquid. In other embodiments, the media (e.g. latex) is impermeable to liquid. In still other embodiments, the media is partially permeable to liquids. In other embodiments, the media comprises perforations (e.g. that allow fluid to pass).
In certain embodiments, the multifunctional device further comprises an adjustment device. In other embodiments, at least a portion of the adjustment device is within the elongate member. In some embodiments, the adjustment device is configured for changing the shape of the chamber. In preferred embodiments, the adjustment device is configured for moving the enlargeable section from the non-enlarged position to the enlarged position, or vice-versa. In other embodiments, the adjustment device comprises a handle component (e.g. such that user can operate the adjustment device from outside the body of a patient).
In some embodiments, the multifunctional devices of the present invention further comprise an inner utility member. In particular embodiments, the inner utility member comprises a rod or rod-like member. In certain embodiments, the inner utility member is configured for transmitting fluid (e.g. irrigation or suction, or both). In other embodiments, the inner utility member is configured for attachment to a tissue manipulator tip (or the distal end of the inner utility member forms a tissue manipulator tip). In some embodiments, the multifunctional device further comprises a tissue manipulator tip (e.g. connected to the inner utility member).
In certain embodiments, the enlargeable section of the elongate member comprises a spring member. In some embodiments, the spring member is configured to move the enlargeable section to the enlarged position. In other embodiments, the spring member is configured to move the enlargeable section to the non-enlarged position. In other embodiments, the enlargeable section has passive spring action (e.g. will move to the enlarged position unless constrained). In some embodiments, the plurality of walls of the enlargeable section have passive spring action (e.g. will move to the enlarged position unless constrained).
In some embodiments, the multifunctional devices of the present invention comprise a sleeve member. In certain embodiments, the sleeve member encloses at least a portion of the elongate member. In other embodiments, the sleeve member is moveable (e.g. adjustable) between a first position along the elongate member that fully encloses the enlargeable section, and a second position along the elongate member that at most partially encloses the enlargeable section (e.g. at most encloses 95%, 75%, 50%, 25%, 10% or 5% of the enlargeable section). In other embodiments, the enlargeable section is in the non-enlarged position when the sleeve member is in the first position. In particular embodiments, the enlargeable section is in an enlarged position when the sleeve member is in the second position.
In certain embodiments, the sleeve member comprises plastic (e.g., polyethylene, polypropylene, polystyrene, polyvinyl chloride, nylon, polyacetal, polyphenylene oxide, polytetrafluoethylene, polyethylene teraphthalate, polybutylene terephthalate, phenolic urea formaldehyde, melamine formaldehyde, polyester, and combinations thereof).
In other embodiments, the sleeve member is configured to be moved (e.g. adjusted) from outside of a subject's body (e.g. during endoscopic surgery). In some embodiments, the sleeve member comprises a proximal end, and the proximal end is connected to a handle.
In some embodiments, the present invention provides methods for constructing a multifunctional device, comprising; a) providing an elongate member, and b) generating a plurality of openings in the elongate member such that an enlargeable section is formed in the elongate member, wherein the enlargeable section comprises a plurality of walls. In other embodiments, after step b), the elongate member comprises a distal tip. In particular embodiments, the enlargeable section is moveable between a non-enlarged position and an enlarged position, wherein the enlarged position creates a chamber in the elongate member. In particular embodiments, the enlarged position is any position of the enlargeable section that has a cross-sectional dimension greater than the enlarged section when in the non-enlarged position. In certain embodiments, the generating comprises cutting a plurality of holes (e.g. slits) in the elongate member. In some embodiments, the present invention provides methods for constructing a multifunctional device, comprising; generating an elongate member that has a plurality of openings, wherein the plurality of openings form an enlargeable section comprising a plurality of walls. In some embodiments, the generating comprises blow-molding, or otherwise forming, the elongate member such that a plurality of openings are formed therein.
In other embodiments, the present invention provides kits, comprising an elongate member with a plurality of openings defining an enlargeable section, wherein the enlargeable section comprises a plurality of walls, and wherein the enlargeable section is movable between a non-enlarged position, and an enlarged position, wherein the enlarged position forms a chamber in the elongate member, and b) a sleeve member configured for enclosing at least a portion of the elongate member, the sleeve member being moveable between a first position along the elongate member that fully encloses the enlargeable section, and a second position along the elongate member that at most partially encloses the enlargeable section. In other embodiments, the kits of the present invention further comprise any of the additional components of the multifunctional devices mentioned above (e.g. media, inner utility member, adjustment device, elongate member with or without a distal tip, etc.). In certain embodiments, the kits of the present invention further comprise instructions for assembling and/or using the multifunctional devices of the present invention.
In other embodiments, the present invention provides systems, comprising an elongate member with a plurality of openings defining an enlargeable section, wherein the enlargeable section comprises a plurality of walls, and wherein the enlargeable section is movable between a non-enlarged position, and an enlarged position, wherein the enlarged position forms a chamber in the elongate member, and b) a sleeve member configured for enclosing at least a portion of the elongate member, the sleeve member being moveable between a first position along the elongate member that fully encloses the enlargeable section, and a second position along the elongate member that at most partially encloses the enlargeable section. In other embodiments, the systems of the present invention further comprise any of the additional components of the multifunctional devices mentioned above (e.g. media, inner utility member, adjustment device, elongate member with or without a distal tip, etc.). In certain embodiments, the systems of the present invention further comprise instructions for assembling and/or using the multifunctional devices of the present invention.
In other embodiments, the present invention provides multifunctional devices that permit the removal of bodily and irrigation fluids, the injection of irrigation fluids, or the manipulation of tissue (e.g. cautery, cutting, scraping, etc.), comprising an elongate member (e.g. suction and/or irrigation tube) that is connected to, or preferably integral with, an enlargeable section that is configured to provide access down into a surgical field (e.g. for removal or injection of fluids), the enlargeable section defining a chamber volume having an area measured across the elongate member axis similar to the cross-sectional area of the elongate member when the enlarged section is non-deployed (e.g. in a non-enlarged position), and having an area measured across the elongate member axis greater than the cross-sectional area of the elongate member, and thereby an increased chamber volume, when the enlargeable section is deployed (e.g. in an enlarged position).
In some embodiments, the enlargeable section comprises walls. In further embodiments, the wall are perforated. In certain embodiments, the wall of the enlargeable section, when deployed, are capable of pushing bodily tissue outward from the elongate member axis to form an enlarged chamber volume free of bodily tissue (e.g. such that fluids may be collected for removal).
In certain embodiments, the elongate member has a plurality of openings that form the enlargeable area. The openings may be of any shape or size. In some embodiments, the openings are longitudinal, diamond, zig-zag shape, regular, or irregular in shape, and allow adjustment of the chamber shape and volume.
In particular embodiments, the walls of the enlargeable section have passive spring action that opens the enlargeable section to its deployed shape and size. In other embodiments, the walls of the enlargeable section have passive spring action that returns the enlargeable section to its non-deployed (e.g. non-enlarged) shape and size when deployment forces are released or counteracted, whereby the chamber length can be reduced and the chamber width and volume can be increased by pushing on the tube and enlargeable section.
In some embodiments, the multifunctional device further comprises a tissue manipulation tip (including, but not limited to, a cautery tip, scalpel tip, scissors tip, scraping tip, and stitching tip) which can operate both within the enlargeable section and beyond the tip of the enlargeable section.
In further embodiments, the multifunctional device further comprises an adjustment device that connects to the enlargeable section and is operable from the top of the elongate member. In certain embodiments, the adjustment device may be used to change the change length, width and volume (e.g., change the enlargeable section from a non-enlarged position to an enlarged position, or vice versa).
In some embodiments, the multifunctional device of the present invention further comprises a sleeve member around the elongate member, through which the elongate member (e.g. tube) and enlargeable section can move. In certain embodiments, the sleeve member may be used to insert into or withdraw from the surgical area the elongate member (e.g. suction/irrigation tube), with the enlargeable section in a non-deployed (e.g. non-enlarged), or partially deployed condition. In particular embodiments, the sleeve member enclosing at least a portion of the elongate member may be pushed downward around the enlargeable section to transfer the location of maximal suction and/or irrigation forces toward the proximal end of the device.
In certain embodiments, the walls of the enlargeable section comprise tynes. In some embodiments, when the tynes are spread apart form openings between them for fluid movement. In particular embodiments, the tynes have outward or inward passive spring action to create deployment or non-deployment forces.
In some embodiments, the multifunctional device of the present invention comprises flexible media material surrounding and/or conforming to at least a portion of the enlargeable section. In certain embodiments, the flexible media serves to control movement of materials into the chamber. In other embodiments, the media is fluid permeable or impermeable, or perforated, in specific areas, thus restricting bodily tissue from entering the chamber.
In additional embodiments, the multifunctional device further comprises an inner utility member (e.g. suction and/or irrigation tube) inside of the elongate member. The inner suction/irrigation tube may be employed to additionally remove bodily or irrigation fluids or inject irrigation fluids. In other embodiments, the insertion depth of the inner suction/irrigation tube determines the zone from which fluids are removed or to which fluids are injected within the chamber.
DESCRIPTION OF THE FIGURES
FIG. 1 shows a cutaway perspective view of a prior art endoscopic surgery suction device.
FIG. 2 shows one embodiment of the multifunctional device of the present invention.
FIG. 3 shows another embodiment of the multifunctional device of the present invention.
FIG. 4 shows an additional embodiment of the multifunctional device of the present invention.
FIG. 5 shows a further embodiment of the multifunctional device of the present invention.
DEFINITIONS
To facilitate an understanding of the invention, a number of terms are defined below.
As used herein, the terms “subject” and “patient” refer to any animal, such as a mammal like livestock, pets, and preferably a human. Specific examples of “subjects” and “patients” include, but are not limited to, individuals requiring surgery, and in particular, requiring endoscopic surgery for diagnostic or therapeutic purposes.
As used herein, the terms “endoscopic surgery” and “endoscopic procedures”, and like terms, refer to what is generally known as laproscopic or endoscopic surgery, which generally involves indirect visualization of the operative field with a small camera (e.g. specialized fiberoptic telescopes measuring less than a half inch in diameter that are attached to high resolution television cameras). Endoscopic surgery is generally done by way of multiple small incisions through which a camera and instruments are inserted. The instruments perform their functions inside the body but are operated by use of their handles outside the body. Examples of endoscopic surgery include endoscopic appendix or gallbladder removal.
As used herein, the term “primary cross-sectional dimension” when used in reference to the elongate member, refers the cross sectional dimension (i.e. area of the internal opening) in the elongate member that is present throughout at least 50% of the length of elongate member (i.e. at least 50% of the length of the elongate member has a cross-sectional dimension that is the same value, referred herein as the primary cross-sectional dimension). In some embodiments, the primary cross-sectional dimension is present throughout at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95% of the elongate member. In preferred embodiments, the primary cross-sectional dimension is present throughout about 100% of the elongate member (e.g. a tube of approximately uniform diameter is employed).
As used herein, the term “distal tip” when used in reference to a portion of the elongate member, refers to the area of the elongate member that is distal of the enlargeable section of the elongate member. In some embodiments, the distal tip has approximately the same cross-sectional dimension as the primary cross-sectional dimension of the elongate member. In other embodiments, the distal tip is non-enlargeable.
GENERAL DESCRIPTION OF THE INVENTION
The present invention relates generally to multifunctional devices for performing suction, irrigation, and manipulation at an internal site in a subject, and more particularly to enlargeable multifunctional devices for performing such functions while avoiding obstruction during conventional and endoscopic surgery.
The present invention eliminates many of the problems associated with malleable tissue obstruction or impeding suction catheters, irrigation catheters, and other surgical instruments. The present invention permits conventional utilization of suction, irrigation, and other functions, but also provides the ability to deploy and retract a guard (e.g. enlargeable section) to create an area (e.g. chamber) free of tissue interference. The tissue guard (enlargeable section) may be activated (e.g. go from non-enlarged position to an enlarged position), for example, by direct pressure of the device tip against tissue (or other firm surface). The tissue guard (enlargeable section) may also be activated, for example, by a mechanism on the device handle or passive spring action. When the enlargeable section is deployed (e.g. in an enlarged position), it forms a barrier preventing tissue from coming into direct contact with any functioning portion of the device (e.g. suction, irrigation, or tissue manipulation part of the device).
In preferred embodiments, the multifunctional devices of the present invention comprise an elongate member (e.g. a hollow tube) with longitudinal slits or other perforations/openings that run to nearly the end of the elongate member (e.g. a plurality of openings are formed near the distal end of the elongate member forming an enlargeable section adjacent to the distal tip of the elongate member). In other embodiments, the multifunctional devices of the present invention comprise an elongate member (e.g. hollow tube) with longitudinal or other perforations/opening that run to the end of the elongate member (e.g. a plurality of openings are formed at the distal end of the elongate member forming an enlargeable section at the end of the elongate member).
Also in preferred embodiments, when the tip (e.g. very end) of the elongate member is forced against an object or is pulled proximally toward the top of the elongate member (e.g. toward the handle), the openings (e.g. slits, perforations, etc) allow the sides of the elongate member (e.g. the walls of the enlargeable section of the elongate member) to bow out. This creates a cavity (e.g. chamber) that is protected from tissue encroachment by the bowed-out walls. In certain embodiments, the multifunctional devices have a suctioning function, and the formation of the chamber (e.g. when the enlargeable section is in the enlarged position) causes the suction interface to shift from the area just beyond the distal tip of the elongate member, to the an area within the enlargeable section, or just above the enlargeable section.
Since the multifunctional devices of the present invention may be moved between a non-enlarged position and an enlarged position (e.g. the enlargeable section of the elongate member may be in enlarged and non-enlarged positions), the device may be inserted through openings otherwise too small to accommodate a device with bowed out chambers. In this regard, the devices of the present invention may be used in a conventional manner, or passed through introducer ports (e.g. for endoscopic type surgery), by reversing the bowing process, thus causing the cross-sectional dimension of the enlargeable section to return to “normal” (e.g., return to a position such that the enlargeable section has approximately the same cross-sectional dimension as the primary cross-sectional dimension of the elongate member).
DETAILED DESCRIPTION OF THE INVENTION
The multifunction devices of the present invention have advantages over previous prior art devices. FIG. 1 shows a prior art suction device, and FIGS. 2-5 show various preferred embodiments of the multifunctional devices of the present invention.
Referring to FIG. 1, a prior art suction device 10 penetrates the body wall 11 of a subject through an introducer 12 down to the surgical field 13 where bodily and irrigation fluids 14 accumulate. Tube 20 transmits fluids during surgery through hole 21 (not shown, and not always present) in the tube 20 end, and holes 22 in the tube 20 sides from the surgical area inside the body 14 to outside the body 23 .
Referring generally to FIGS. 2, 3 , 4 , and 5 , elongate member 20 (e.g. suction/irrigation tube) is connected to, or preferably integral with, an enlargeable section 30 (i.e. elongate member 20 has an enlargeable section 30 ). Elongate member 20 allows removal of bodily fluids and irrigation fluids during surgical operations inside the bodies of subjects (e.g. humans and other animals, such as cows, pigs, horses, dogs, cats, and other mammals). The enlargeable section 30 may be in a non-enlarged (non-deployed) position or an enlarged (deployed) position. FIGS. 2, 3 , 4 and 5 show the enlargeable section 30 in an enlarged position. Generally, the enlargeable section 30 , when in the non-deployed position, is of similar cross-sectional dimension 31 as elongate member 20 , but when in a deployed position, is of a cross-sectional dimension, such as 32 , that is larger than the cross-sectional dimension 31 of elongate member 20 .
In particularly preferred embodiments, the walls 35 of deployed enlargeable section 30 are capable of pushing bodily tissue 36 (e.g. malleable tissue) outward away from the elongate member 20 axis 37 , and form a chamber 38 . In certain embodiments, the enlargeable section contains a plurality of openings 39 . FIGS. 2 and 5 show “slit” type openings 39 a , between walls 35 . In some embodiments, the slit openings are longitudinal (e.g. 39 a ), horizontal, angled, or combinations thereof. FIGS. 2 and 5 also show an alternative embodiments with openings 39 b (e.g. perforations) cut in a zig-zag pattern (e.g. to form an expanding mesh). In certain embodiments with perforations 39 b , the perforations may be any type of opening, including, but not limited to, longitudinal, diamond, regular or irregular shaped openings. Openings 39 (e.g. 39 a and 39 b ) may allow adjustment of the chamber shape and volume.
The chamber 38 shape and volume may be varied by adjusting its length 40 and width 32 . The chamber 38 length 40 can be decreased and the chamber 38 width 32 can be increased, for example, by pushing elongate member 20 downward against the surgical field 13 . This motion may also act to bring the point of maximum suction 47 closer to the surgical field 13 .
The walls 35 , in some embodiments, have inward passive spring action that returns the enlargeable section 30 to its non-deployed (non-enlarged) shape and size when deployment forces are released or counteracted. In alternative embodiments, the plurality of walls 35 have outward passive spring action that opens the enlargeable section 30 to its deployed shape and size of variable length 40 and width 32 .
Adjustment device 45 , which connects to the bottom of enlargeable section 30 and is operable from the top of elongate member 20 , can be used to change the chamber 38 length 40 and width 32 . Adjustment device 45 can be used to increase or decrease the volume of chamber 38 .
Sleeve member 46 , which surrounds elongate member 20 , can be used for many purposes. For example, for device insertion purposes, with enlargeable section 30 non-deployed and retracted within sleeve member 46 , the enlargeable section 30 and elongate member 20 can be inserted into the surgical area. After insertion, sleeve member 46 can be partially pulled back such that walls 35 , when including outward passive spring action, will open to form enlarged chamber dimension 32 . In another example of employing sleeve member 46 , for device removal purposes, sleeve member 46 can be used to reduce the enlargeable section 30 width 32 to the same cross-sectional area 31 of elongate member 20 for removal of enlargeable section 30 and elongate member 20 through sleeve 46 . In a further example, for controlled suction and irrigation purposes, sleeve member 46 can be pushed toward the surgical field 13 . Through this downward movement, sleeve member 46 compresses the walls 35 inward from the larger dimension 32 to the smaller dimension 31 , blocks increasing percentages of the openings 39 , and thereby transfers the location of maximal suction or irrigation forces 47 downward toward the surgical field 13 .
Media 48 may surround part or all of enlargeable section 30 to control movement of materials into chamber 38 . Media 48 is flexible to conform to the variable shape of walls 35 . Specific areas of media 48 may be permeable or impermeable to fluids, and may further contain perforations. Media 48 restricts bodily tissue from entering chamber 38 (e.g. restricts bodily tissue from entering openings 39 ).
Inner utility member 49 (e.g. suction/irrigation tube or tissue manipulation support), inserts into elongate member 20 and chamber 38 as an additional or alternative means for removal of bodily and irrigation fluids, or as a tissue manipulation support (e.g. for attaching a tissue manipulator tip). The depth of insertion determines the zone from which fluids are removed. As insertion depth increases and dimension 50 therefore decreases, fluid levels are lowered closer to surgical field 13 . Tissue manipulator tip 62 may be attached to, or integral with, inner utility member 49 (e.g. in order to perform surgical maneuvers, such as cutting, cauterizing, knot tying, scraping, and stitching).
Referring now to FIGS. 2 and 3 specifically, both of these figures show the enlargeable section 30 in an enlarged position such that a ‘bulging midsection’ is formed (i.e. enlargeable section 30 is narrower at either end, and larger in the middle). In preferred embodiments, the cross-sectional dimension adjacent to both ends of the enlargeable section 30 is approximately the same (e.g. approximately the same cross-sectional dimension as the primary cross-sectional dimension of the elongate member 20 ). FIG. 2 specifically shows a distal tip 51 of elongate member 20 adjacent to the enlargeable section 30 that has approximately the same cross-sectional dimension as elongate member 20 . FIG. 2 also shows a tissue manipulation tip 62 at the end of inner utility member 49 .
Referring now to FIGS. 4 and 5 specifically, both of these figures show the enlargeable section 30 in an enlarged position such that a ‘cone configuration’ is formed (i.e. enlargeable section 30 is narrower at one end (approximately the same cross sectional dimension as elongate member 20 ), and the other end is the widest part of the enlargeable section 30 . FIG. 5 also shows a tissue manipulation tip 62 at the end of inner utility member 49 .
The multifunctional devices of the present invention have many advantages. For example, in certain embodiments, the enlargeable section may be constructed by cutting holes (e.g. longitudinal slits) in an existing elongate member, instead of attaching a separate enlargeable member to an elongate member. In this regard, the devices of the present invention are reliable (e.g. few parts) and easy to produce (e.g. no extra steps to create and attach a separate enlargeable member). Another advantage of the devices of the present invention is that, in many embodiments, there are no tynes (or other potentially dangerous protuberances) that stick out that could damage tissue (e.g. embodiments with a “bulging midsection” do not have tynes sticking out that might damage tissue). Furthermore, in some embodiments, the walls of the enlargeable section and/or the media (membrane) surrounding the enlargeable section, prevents tissue from being blocking the ability of the multifunctional devices to provide a suction, irrigation, or tissue manipulation function.
The enlargeable section of the present invention can be continuously enlarged to different sizes or can have various predetermined sizes in the deployed (expanded position). The walls of the enlargeable section can have various predetermined or preformed configurations or shapes in the expanded position in accordance with procedural use including various shapes for holding back or manipulating tissue and defining or circumscribing various working or operating spaces. Some configurations for the enlargeable section that are particularly advantageous include, but are not limited to, “bulging midsection” configurations, “cone-shaped” configurations”, triangular, oval, single or multiple ball-shaped, etc. Any shape that that creates space during surgery, or allows irrigation or suction to occur without blockage are useful in the present invention.
The multifunctional devices of the present invention are useful for performing conventional surgery. Examples of conventional surgery include, but are not limited to, abdominal surgeries, urologic surgeries, gynecologic surgeries, thoracic surgeries, cardiac surgeries, and vascular surgeries. The multifunctional devices are also useful for conventional microsurgeries (e.g. of the hand), peripheral vascular surgeries, neurosurgery (e.g. peripheral, spinal cord, and intracranial), and otolaryngological (ENT) surgeries.
The multifunctional devices of the present invention are particularly useful for endoscopic type procedures. Examples of procedures in which the devices of the present invention may be employed include, but are not limited to, laparoscopic cholecystectomy, laparoscopic treatment of gastroesophageal reflux and hiatal hernia, laparoscopic cardiomyotomy (Heller Myotomy), laparoscopic gastrostomy, laparoscopic vagotomy, laparoscopic plication of perforated ulcer, gastric resections, laparoscopic bariatris surgery, small bowel resections, enterolysis, enteroenterostomy, placement of jejunostomy tube, laparoscopic appendectomy, laparoscopic colostomy, laporoscopic segmental colectomies, anterior resections, abdominopereneal resection, laparoscopic-assisted proctocolectomy, distal pancreatectomy, laparoscopic cholecystojejunostomy, laporoscopic gastrojejunostomy, laporoscopic splenectomy, lymph node biopsy, laparoscopic adrenalectomy, laproscopic inguinal hernia repair, laproscopic repair of ventral hernia, upper gastrointestinal endoscopy, small bowel enteroscopy, endoscopic retrograde cholangiopancreatography, choledochostomy, flexible sigmoidoscopy, colonoscopy, and pediatric endoscopy. These and other techniques and methods suitable for use with the multifunctional devices of the present invention are described in “The Sages Manual, Fundamentals of Laparoscopy and GI Endoscopy”, edited by Carol E. H. Scott-Conner, Spinger Pub., 1999, herein specifically incorporated by reference.
All publications and patents mentioned in the above specification are herein incorporated by reference. Various modifications and variations of the described devices, compositions, methods, systems, and kits of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in art are intended to be within the scope of the following claims. | The present invention relates generally to multifunctional devices for performing suction, irrigation, and manipulation at an internal site in a subject, and more particularly to enlargeable multifunctional devices for performing such functions while avoiding obstruction during conventional and endoscopic surgery. The present invention eliminates many of the problems associated with malleable tissue obstruction during surgery by providing the ability to deploy and retract a guard (e.g. enlargeable section) to create an area free of tissue interference. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This is a divisional of application 09/026,446 filed Feb. 19, 1998, now U.S. Pat. No. 6,093,293, which claims priority on Swiss application 2897/97, filed Dec. 17, 1997.
SUMMARY OF THE INVENTION
This invention relates to a magnetron sputtering source, a vacuum chamber with such a source, a vacuum coating system with such a chamber, and in addition a process technique for such a system, as well as its utilization.
In essence the present invention is based on the need for depositing on large-surface, in particular rectangular substrates with an area of at least 900 cm 2 , a film having a homogenous thickness distribution, by means of sputter coating, in particular also reactive sputter coating. Such substrates are in particular used in the manufacture of flat panels, normally on glass substrates thinner than 1 mm, such as for TFT panels or plasma display panels (PDP).
When magnetron sputter coating large surfaces, even larger sputter surfaces and consequently larger targets are normally required unless the sputtering source and the substrate are moved relative to each other. However, this results in problems with respect to
(a) uniformity of the process conditions on the large-surface target, with particular severity in reactive sputter coating
(b) erosion profile
(c) cooling
(d) strain on the large targets, in particular through atmospheric pressure and coolant pressure.
In order to solve the mechanical strain problem (d) relatively thick target plates have to be used which in turn reduces the magnetic penetration and consequently the electron trap effect for a given electrical input power. If the power is increased this results in cooling problems (c), in particular because elaborate methods are needed for achieving good contact between the target and the cooling medium, and also because of the obstruction resulting from the installations on the back for accommodating the magnets. It is also known that in magnetron sputtering, be it reactive or non-reactive, the target arrangement normally consisting of a sputtering area defining target plate made of the material to be sputtered and a bonded mounting plate, the target is sputter eroded along so-called “race tracks”. On the sputter surface one or several circular erosion furrows are created due to the tunnel-shaped magnet fields applied to the target along specific courses, which produce circular zones with elevated plasma density. These occur due to the high electron density in the area of the tunnel-shaped circular magnetron fields (electron traps). Due to these “race tracks” an inhomogenous film thickness distribution occurs already on relatively small-surface coating substrates arranged in front of the magnetron sputtering source. In addition the target material is inefficiently utilized because the sputter erosion along the “race tracks” removes little material from target areas outside these tracks which results in a wave-shaped or furrow-shaped erosion profile. Because of these “race tracks” the actually sputtered surface even of a large target is small relative to the substrate surface. For eliminating the effect of said “race tracks” on the coating it would be possible to move the sputtering source and the substrate to be coated relative to each other, as mentioned above, however, this results in a lower deposition rate per unit of time. If locally higher sputtering power is used, cooling problems are incurred in systems using relative motion.
In trying to achieve the desired goal basically four complexes of problems (a), (b), and (c), (d) are encountered whose individual solutions aggravate the situation with respect to the others; the solutions are mutually contradictory.
The objective of the present invention is to create a magnetron sputtering source through which said problems can be remedied, that can be implemented in practically any size, and that is capable of economically achieving a homogenous coating thickness distribution on at least one large-surface substrate that is stationary relative to the source. In addition to maintaining highly uniform process conditions the source shall be suitable for sensitive reactive processes with high deposition or coating rates. In reactive processes, inhomogenous “race track” effects lead to known, severe problems due to the large plasma density gradients.
This is achieved by the magnetron sputtering source according to the present invention in which at least two, preferably more than two, electrically isolated long target arrangements are placed parallel to each other at a distance that is significantly smaller than the width of the target arrangement, where each target arrangement has its own electrical connections, and where in addition an anode arrangement is provided. The targets of the target arrangements have preferably rounded corners, following the “race track” paths.
On such a magnetron sputtering source according to the invention with independently controllable electrical power input to the individual target arrangements, the film thickness distribution deposited on the substrate located above can already be significantly improved. The source according to the invention can be modularly adapted to any substrate size to be coated.
With respect to the overall arrangement the anode arrangement can—unless it is temporarily formed by the target arrangements themselves—be located outside the overall arrangement but preferably comprises anodes that are installed longitudinally between the target arrangements and/or on the face of the target arrangement, but particularly preferred longitudinally.
Also preferred is a stationary magnetron arrangement on the source; the latter is preferably formed by a magnet frame that encircles all the target arrangements, or is preferably implemented with one frame each encircling each target arrangement. Although it may be feasible and reasonable to implement the magnets on the frame(s), or on the stationary magnet arrangement at least partially by means of controllable electric magnets, the magnets of the arrangement or the frame are preferably implemented with permanent magnets.
Through a corresponding design of said stationary magnet arrangement, preferably the permanent-magnet frames with respect to the magnet field they generate on the immediately adjacent target arrangement, the aforementioned film thickness distribution on the substrate and the utilization efficiency of the long targets can be further enhanced through specific shaping of “race tracks”.
Magnet arrangements are provided preferably below each of the at least two target arrangements. These may be locally stationary and be fixed over time in order to create the tunnel shaped magnet field on each of the target arrangements. Preferably they are designed in such a way that they cause a time-dependent variation of the magnet field pattern on the target arrangements. With respect to the design and the generation of the magnet field pattern on each of the target arrangements according to the invention, we refer to EP-A-0 603 587 or U.S. Pat. No. 5,399,253 of the same application, whose respective disclosure content is declared to be an integral part of the present description.
According to FIG. 2 of EPO-A-0 603 587 the location of the magnet pattern and consequently the zones of high plasma density can be changed as a whole, but preferably it is not changed, or changed only insignificantly, whereas according to FIGS. 2 and 3 of said application the location of the apex—the point of maximum plasma density—is changed.
For changing the location of the zones or the apex on the magnet arrangements, selectively controlled electric magnets—stationary or movable—can be provided below each of the target arrangements, but far preferably this magnet arrangement is implemented with driven movable permanent magnets.
A preferred, moving magnet arrangement is implemented with at least two magnet drums arranged longitudinally below the driven and pivot bearing mounted target arrangements, again preferably with permanent magnets as illustrated, for an individual target, in FIGS. 3 and 4 of EP-A-0 603 587.
The magnet drums are driven with pendulum motion with a pendulum amplitude of preferably≦τ/4. With respect to this technique and its effect we again refer fully to said EP 0 603 587 or U.S. Pat. No. 5,399,253 respectively which also in this respect are declared to be an integral part of the present patent application description.
In summary, at least two driven and pivot bearing mounted permanent magnet drums extending along the longitudinal axis of the target arrangement are preferably provided.
In the preferred manner
with the electrical target arrangement supply
the field of said stationary magnet arrangement, in particular said frames
with the field/time-variable magnet arrangement below each target arrangement, preferably the magnet drums
a set of influencing variables is available which in combination allow extensive optimization of the deposited film thickness distribution, in particular with respect to its homogeneity. In addition a high degree of target material utilization is achieved. Highly advantageous is that preferably—with shift of the magnet field apex on the target arrangement—the plasma zones are not shifted in a scanning manner but that within the zones the plasma density is changed through wobbling.
To allow maximum sputter power input the target arrangements are optimally cooled by mounting them on a base where the target arrangement surfaces facing the base are largely covered by cooling media channels which are sealed against the base by means of foils. Large-surface heat removal is achieved because the pressure of the cooling medium presses the entire foil surface firmly against the target arrangements to be cooled.
On the magnetron sputtering source according to the invention a base, preferably made at least partially from an electrically insulating material, preferably plastic, is provided on which in addition to said target arrangements the anodes and, if existing, the stationary magnet arrangement, preferably permanent magnet frames, the magnet arrangement below the target arrangements, preferably the moving permanent magnet arrangements, in particular said drums, as well as the cooling medium channels, are accommodated. The base is designed and installed in such a way that it separates the vacuum atmosphere and the external atmosphere. In this way the target arrangement can be more flexibly designed with respect to pressure-induced mechanical strain.
Another optimization or manipulated variable for said large-surface film thickness distribution is obtained by providing gas outlet openings, distributed on the longitudinal side of the target arrangement, which openings communicate with a gas distribution system. This makes it possible to admit reactive gas and/or working gas with specifically adjusted distribution into the process chamber above the source according to the invention of a vacuum treatment chamber or system according to the invention.
The rectangular target arrangements are preferably spaced apart by max. 15%, preferably max. 10% or even more preferably max. 7% of their width,
In a preferred design the lateral distance between the individual target arrangements d is
1 mm≦d≦230 mm, where preferably
7 mm≦d≦20 mm.
Width B of the individual target arrangements is preferably
60 mm≦B≦350 mm, more preferably
80 mm≦B≦200 mm
and their length L preferably
400 mm≦L≦2000 mm.
The length of the individual target arrangements relative to their width is at least the same, preferably considerably longer. Although the sputtering surfaces of the individual target arrangements are flat or pre-shaped and preferably arranged along one plane, it is feasible to arrange the lateral sputtering surfaces closer to the substrate to be coated than the ones in the middle, possible also inclined, in order to compensate any edge effects on the film thickness distribution, if necessary.
The electrons of the magnetron plasma circulate along the “race tracks” in a direction defined by the magnet field and the electrical field in the target surface area. It has been observed that the routing of the electron path or its influence upon it and consequently the influence on the resulting erosion furrows on the target surfaces can be specifically optimized by creating the magnet field along the longitudinal axes of the target arrangements and by varying the shape or said field not only with respect to time but also location. With a magnet frame—preferably one each, and also preferably one permanent magnet frame each—this is preferably achieved by positioning and/or by the selected strength of the magnets on the frame, and/or by providing magnet arrangements each below the target arrangements, preferably said permanent magnet drums, by correspondingly varying the strength and/or relative position of the magnets on the magnet arrangement. As the electrons move in a circular path in accordance with the magnet field polarity, it has been observed that apparently due to drift forces the electrons, in particular in the narrow side areas of the target arrangements and in accordance with the direction of their movement, the electrons in corner areas that are diagonally opposite are forced outward. For this reason it is proposed that with the provided magnet frame the field strength created by the frame magnets which are specular symmetrical to the target “rectangle” diagonal be preferably designed with a locally different shape.
In a preferred design version of the source according to the invention the target arrangements are fixed by means of linear bayonet catches, in particular in combination with their cooling via pressure loaded foils of the aforementioned type. In this way the arrangements can be very easily replaced after the pressure in the cooling medium channels has been relieved; the greater part of the target arrangement back side remains accessible for cooling and no target arrangement fixing devices are exposed toward the process chamber.
A preferred source according to the invention features more than two target arrangements, preferably five or more.
By using a magnetron sputtering source according to the invention on a sputter coating chamber on which, with a clearance from the latter, a substrate holder for at least one, preferably planar substrate to be sputter coated is provided, it is possible to achieve an optimally small ratio V QS between the sputtered source surfaces F Q and the substrate surface P S to be sputtered, where:
V QS ≦3, preferably
V QS ≦2, where particularly preferred
1.5≦V QS ≦2.
This significantly increases the utilization efficiency of the source. In a sputter coating chamber according to the invention with said source this is achieved to an even higher degree by choosing the distance D between the virgin surface of the magnetron sputtering source and the substrate in such a way that it is essentially equal to the width of a longitudinal target arrangement, preferably
60 mm≦D≦250 mm,
preferably
60 mm≦D≦160 mm
On a vacuum coating system according to the invention with a sputter coating chamber according to the invention and consequently the magnetron sputtering source according to the invention, the target arrangements are each connected to an electrical generator or current sources, where said generators can be controlled independently of each other.
The sputter coating system according to the invention with at least three long target arrangements is preferably operated in such a way that the two outer target arrangements are operated with 5 to 35% more sputtering power, preferably with 10 to 20% more sputtering power than the inner target arrangements. The aforementioned “scanning” of the target arrangements with respect to the position of the plasma zones and in particular the preferred “wobbling” of the apex of the tunnel magnet fields and consequently the plasma density distribution, preferably realized by means of said magnet drums in pendulum operation, is preferably performed with a frequency of 1 to 4 Hz, preferably approx. 2 Hz. The pendulum amplitude of the drum is preferably {circumflex over ( )}φ≦π/4 ({circumflex over ( )}φmeaning the peak value for φ). The coating thickness distribution on the substrate is further optimized through an appropriate design of the path/time profiles of said shift in position.
It should be emphasized that for this purpose also the generators connected to the target arrangements can be controlled for outputting mutually dependent, time modulated signals.
In addition the electrical supply of the target arrangements and/or the distributed gas inlets and/or the magnet field distribution are controlled in such a way or modulated in time in such a way that the desired, preferably homogenous, film thickness distribution on the substrate is achieved.
The magnetron sputtering source is preferably operated with a power density p of
1 W/cm 2 ≦p≦30 W/cm 2 ,
in particular for reactive film deposition, preferably from metallic targets, and in particular ITO films with
1 W/cm 2 ≦p≦30 W/cm 2 ,
and for sputter coating metal films preferably with
15 W/cm 2 ≦p≦30 W/cm 2 .
As has been recognized in conjunction with the development of said magnetron sputtering source according to the invention, it is basically advantageous, in particular with target plate arrangements that are significantly longer than wide, to design the magnet field strength of the magnetron field, viewed in the longitudinal direction of the target arrangements and in particular their lateral areas, with a locally different shape.
However, this insight is generally applicable to long magnetrons.
For this reason it is proposed for a long magnetron source according to the invention which comprises a time-variable, preferably moving magnet system, to assign a magnet frame to the target arrangement, preferably a permanent magnet frame where the field strength of the frame magnets measured in one given chamber direction, is designed locally different along the longitudinal side of the target arrangements. For compensating said drift forces acting on the circulating electrons it is proposed to design this field strength locally different essentially specular symmetrical to the target diagonal.
The present invention under all its aspects is in particular suited to sputter coating substrates, in particular large-surface and preferably plane substrates by means of a reactive process, preferably with an ITO film (Indium Tin Oxide). The invention is also suited to coating substrates, in particular glass substrates, used in the production of flat panel displays, in particular TFT or PDP panels, where basically the possibility is opened to highly efficiently sputter coat also large substrates, for example, also semiconductor substrates, with minimal reject rates either by means of a reactive or non-reactive process, but in particular also reactive.
Especially in sputter coating processes, in particular in ITO coating, low discharge voltages for achieving high film quality, in particular low film resistances, also without tempering steps, are essential. This is achieved by means of the source according to the invention.
It also achieves effective suppression of are discharges.
The invention is subsequently explained based on illustrated examples:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 Magnetron sputtering source according to the invention, electrically operated in a first version;
FIG. 2 Schematic representation of the sputtering source according to FIG. 1 in another electrical circuit configuration;
FIG. 3 Another circuit configuration of the sputtering source according to the invention, shown analogously to FIG. 1;
FIG. 4 Cross-sectional detail of a magnetron sputtering source according to the invention;
FIG. 5 Top view of a linear bayonet catch is used preferably on the source according to FIG. 4;
FIG. 6 Simplified top view of a detail of a magnetron source according to the invention;
FIG. 7 Top view of a preferred design version of a permanent magnet drum preferably provided according to FIG. 6 on the magnetron sputtering source according to the invention;
FIG. 8 Schematic representation of a sputter coating system according to the invention;
FIG. 9 Erosion profile on a target arrangement of the source according to the invention;
FIG. 10 Distribution of the sputtered material, determined on a source according to the invention with five target arrangements;
FIG. 11 Film thickness relief pattern on a 530×630 mm 2 glass substrate coated by a source according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 schematically shows a magnetron sputtering source 1 according to the invention in its basic configuration. It comprises at least two, or as illustrated, for example, three long target arrangements 3 a to 3 c . The additional devices to be provided on a magnetron sputtering source, such as the magnet field sources, cooling facilities, etc. are not shown in FIG. 1 . Source 1 has separate electrical connections 5 on each target arrangement. For example, strip shaped anodes 7 a , 7 b are provided preferably between the longitudinally spaced target arrangements 3 .
Because the target arrangements 3 are electrically insulated from each other and have separate electrical terminals 5 , independent electrical wiring as subsequently also described in conjunction with FIGS. 2 and 3 is possible.
As shown in FIG. 1 each target arrangement 3 is connected to a generator 9 , each of which generators can be controlled independently of each other and which do not necessarily have to be of the same type. As shown schematically the generators can be all of the same type or implemented in any mixed combination of DC generators, AC generators, AC and DC generators, generators for outputting pulsed DC signals, or DC generators with intermediate generator output, and with the chopper unit for the corresponding target arrangement. With respect to their design and operating principle full reference is made to said EP-A-0 564 789 or U.S. application No. 08/887 091.
Also with respect to the electrical operation of the anodes 7 there is complete freedom in that they are operated either with DC, AC, DC with superposed AC or pulsed DC voltage, or possibly via one of the said chopper units, or, as shown at 12 a , connected to reference potential. By varying the electrical cathode or target arrangement mode and possibly also the electrical anode mode, distributed across the source surface formed by the target arrangements, the distribution of sputtered material and consequently the distribution on a substrate (not shown) arranged above the source can be adjusted.
Generators 9 can be time modulated with mutual dependence, as shown by the modulation inputs MOD, in order to specifically modulate in the form of a travelling wave, the electrical operating conditions above the target arrangements.
FIGS. 2 and 3 show, with the same position symbols, additional electrical wiring arrangements of source 1 according to the invention at which (not shown) an anode arrangement is not necessary.
As shown in FIGS. 2 and 3 the target arrangements 3 are connected in pairs to the inputs of AC generators 15 a , 15 b or 17 a 17 b respectively, where also here generators 15 or 17 can optionally output AC superposed DC signals or pulsed DC signals. Again, generators 15 , 17 are modulated, if desired, for example an AC output signal practically as carrier signal, with an amplitude modulation.
Whereas according to FIG. 2 one target arrangement 3 b each is connected to an input of one of the generators 15 a and 15 b , target arrangements 3 as shown in FIG. 3 are connected in pairs via generators 17 . As shown with dashed lines at 19 it is possible, in the sense of “common mode” signals, as well as in the design according to FIG. 2 as well as the one in FIG. 3, to jointly connect individual target arrangement groups to different potentials. If a wiring technique according to FIG. 2 or 3 is chosen, the generators in a preferred design version are operated with a frequency of 12 to 45 kHz. With respect to a “common mode” potential, as for example, the mass potential shown in FIG. 2, target arrangements connected in pairs to a generator are alternately connected to positive and negative potentials.
As can be seen from the diagrams in FIGS. 1 to 3 the magnetron source according to the invention allows very high flexibility for electrically operating the individual target arrangements 3 and consequently to specifically design the distribution of the sputtered material in process chamber 10 and the deposition on a substrate.
FIG. 4 is a cross-sectional detail of a magnetron sputtering source according to the invention in a preferred version. As shown in FIG. 4 the target arrangements comprise one target plate 3 a1 or 3 b1 each made of the material to be sputtered and which are bonded to one backing plate each 3 a2 or 3 k2 respectively. With the aid of the linear bayonet catches 20 the target arrangements 3 are fixed on their lateral periphery and/or in their center area to a metallic cooling plate 23 .
The design of the linear bayonet catches is illustrated in FIG. 5 according to which a hollow rail is provided either on target arrangement 3 or on cooling plate 23 , which rail has a U-shaped cross-section, with inwardly bent U-legs 27 on which recesses 29 are created at a certain distance. On the other of the two parts, preferably on target arrangement 3 , a linear rail with a T-shaped cross-section is provided on which the ends of the cross-member 33 feature protrusions 34 . By inserting the protrusions 34 into the recesses 29 and by linear shifting in direction S the two parts are interlocked. It is possible, of course, in the sense of reversal, to create protrusions on the hollow rails that engage into corresponding recesses on rail 31 .
The target arrangements 3 are clamped to the cooling plate 23 only when pressure is applied by the cooling medium in cooling channels 35 of cooling pate 23 . These channels 35 extend along the predominantly flat area of the target arrangement surface facing cooling plate 23 . Cooling channels 35 , pressurized by a liquid cooling medium under pressure as described above, are sealed against the target arrangement by a foil type membrane 37 , as is described in detail, for example, in CH-A-687 427 of the same applicant. Under pressure of the cooling medium foils 37 press tightly against the bottom of plate 3 a2 or 3 b2 respectively. Only when the cooling medium is put under pressure does the target arrangement become rigidly clamped in the bayonet catch. For removing the target arrangement 3 the complete cooling system or the corresponding cooling system section is pressure relieved, as a result of which the target arrangements can be easily pushed out and removed or replaced.
Anode strips 39 are positioned on the longitudinal side of the target arrangements 3 . The anode strips as well as cooling plate 23 are mounted on a supporting base 41 which preferably is made at least partially of insulating material, preferably plastic. Base 41 separates the vacuum atmosphere in process chamber 10 from the ambient or normal atmosphere in space 11 .
On the atmosphere side of base 41 , for example, two permanent magnet drums 43 , extending along the longitudinal dimension of the target arrangement, are supported in a rotating fashion and are driven with pendulum motion by motors (not shown). In pendulum motion they preferably perform a 180° angle pendulum movement—ω 43 . In the permanent magnet drums 43 , permanent magnets 45 are mounted along the longitudinal drum dimension, preferably diametrically.
Also on the atmosphere side of base 41 one permanent magnet frame 47 for each target arrangement 3 is mounted which essentially runs below and along the periphery of the corresponding target arrangement 3 , as shown in FIG. 6 .
In particular along the longitudinal sides of the target arrangements gas inlet lines 49 terminate as shown in FIG. 6, which can be controlled completely independently of each other, preferably in rows, with respect to the gas flow, as shown with dashed lines in FIG. 4 . This is schematically shown in FIG. 4 with servo valves 51 that are provided in a connection between lines 49 and a gas tank arrangement 53 with working gas such as argon and/or with a reactive gas.
With respect to the operation and design of the permanent magnet drum 43 we again refer fully to the disclosure content of EP-0 603 587 or U.S. Pat. No. 5 399 253 respectively.
FIG. 6 shows a simplified top view detail of a magnetron source in FIG. 4 according to the invention. As already described based on FIG. 4 a permanent magnet frame 47 is installed below each target arrangement 3 . Preferably the magnet frame 47 is designed in such a way that when viewed in a chamber direction, for example according to H z in FIG. 4, the magnet field generated by the permanent magnet frame changes locally along the longitudinal sides of the target arrangements 3 , as shown in FIG. 6 with x. In a preferred design the magnets arranged on the longitudinal legs 471 1 and 471 2 of frame 47 are subdivided in to zones, for example, four zones as shown in FIG. 6 . In the diagram of FIG. 6 the field strength of the permanent magnets in the individual zones Z 1 to Z 4 is qualitatively shown through coordinate x and thereby the field strength distribution in the x direction. In addition the permanent magnet dipole directions are shown in the corresponding zones Z.
On legs 47 1, 2 the same permanent magnet zones are preferably provided, however, specular symmetrical with respect to the diagonal D 1 of the long target arrangement 3 .
Through a specific design of the local magnet field distribution that is achieved through the permanent magnet frames 47 on the target arrangements 3 it is possible to optimize the path of the circulating electrons and consequently the location and shape of the erosion profiles on the individual target arrangements. This in particular by taking into consideration the path deformations caused by drift forces. On the broad sides of the target frames 47 permanent magnet zones Z S are provided which preferably correspond to zone Z 2 . As mentioned before also a single-target source according to FIGS. 4, 6 and 7 is inventive.
Magnet fields H which vary locally in the x direction above the corresponding target arrangements 3 which varies also as a function of the magnet drum pendulum motion and varies also in time, is specifically designed by choosing the field strength of the provided permanent magnets such as in zones Z 1 , Z 2 , Z 4 and/or through the spatial dipole orientation such as in zone Z 3 , and/or in the position (distance from the target arrangement).
As mentioned, at least two permanent magnet drums 43 are preferably provided on each of the target arrangements 3 provided on the sputtering source according to the invention. One such drum is shown in FIG. 7 .
Preferably different permanent magnet zones, for example, Z′ 1 , to Z′ 4 are provided also on drums 43 . FIG. 7 qualitatively shows the progression of the locally varying permanent magnet field H r (x) along the provided drums, in accordance with the preferred design.
On the source according to the invention the location and time distribution of the sputter rate is optimized through specific location and/or time distribution of the electrical supply of the individual target arrangements and/or specific location and/or time variation of the magnetron magnet field on the individual target arrangements and/or through specific location and/or time variation or design of the gas inflow conditions on the inlet openings 49 . In the preferred design version that has been explained based on FIGS. 4 to 7 , these variables are preferably exploited in combination in order to specifically design, preferably homogeneously, the film thickness distribution on a substrate to be sputter coated, in particular a flat substrate. FIG. 8 schematically shows a sputter coating system 50 according to the invention with a sputter coating chamber 60 according to the invention in which is also schematically shown a magnetron sputtering source 10 according to the invention. The schematically shown source 10 as implemented in a preferred version features six target arrangements 3 and is also preferably designed as has been explained based on FIGS. 4 to 7 . The source according to the invention with its target arrangements is operated with independent electrical supplies that can possibly be modulated, as shown in block 62 . Further, the gas inflow conditions—which can possibly be modulated, in particular along the longitudinal dimensions of the target arrangements as shown with servo valve 64 , are selectively set in order to admit a working and/or reactive gas from gas tank 53 into the process chamber.
With drive block 65 the drive—which can possibly be path/time modulated—for the permanent magnet drums on the source according to the invention is shown on which, preferably selectively, the desired drum pendulum motions can be set.
In chamber 60 according to the invention a substrate holder 66 is provided, in particular for holding a flat substrate to be coated. Based on the capabilities offered by the source according to the invention of optimally setting the time and location distribution of the material sputtered off by source 10 , in particular a uniform distribution that has been averaged over time, in particular also in the edge zones of the source, it is possible to make the ratio V QS of the sputtering surface F Q of the source to the substrate surface F S to be coated astonishingly small, preferably
V QS ≦3,
preferably
V QS ≦2,
and even more preferably
1.5≦V QS 2.
This ratio shows that the material sputtered off the source is used very efficiently because only correspondingly little of the sputtered material is not deposited on the substrate surface. This efficiency is further enhanced because distance D—due to the large-surface distributed plasma coating of the source—between the substrate surfaces to be sputtered and the virgin surface of the magnetron source 10 , can be selected very small, essentially equal to width B (see FIG. 4) of the sputter surfaces on target arrangements 3 and preferably
60 mm≦D≦250 mm
preferably
80 mm≦D≦160 mm.
Through said small distances D a high deposition rate is achieved with high sputtering efficiency which results in a highly economical coating process.
On the system shown in FIG. 8 the outermost target arrangements are preferably operated by generators 62 with higher sputtering power, preferably 5 to 35% higher, and even more preferably with 10 to 20% higher sputtering power than the inner target arrangements. The permanent magnet drums provided on source 10 according to FIG. 4 are preferably operated in pendulum mode with a pendulum frequency of 1 to 4 Hz, preferably with approx. 2 Hz. The magnetron sputtering source, sputtering chamber or system, in particular in preferred operation, are particularly suitable for magnetron sputter coating large-surface, in particular flat substrates, with a high-quality film, with desired distribution of the film thickness, in particular a homogenous film thickness distribution in combination with high process economy. A significant contribution to this is made by the large-surface, homogeneously distributed process conditions on the source according to the invention. As a consequence the invention can be used for coating large-surface semiconductor substrates, but in particular for coating substrates of flat display panels, in particular TFT or PDP panels. This invention is in particular used for reactive coating of said substrates, in particular with ITO films or for metal coating said substrates through non-reactive sputter coating. In the subsequent examples preferred sizes of the source according to the invention or the chamber or the system are summarized.
1. Geometry
1.1 On the Source
Lateral distance d according to FIG. 4 : maximum 15%, preferably maximum 10%, even more preferably maximum 7% of the width dimension B of the target arrangements and/or
1 mm≦d≦230 mm, preferably
7 mm≦d≦20 mm.
Virgin surfaces of the target arrangements along one plane;
Width B of the target arrangements:
60 mm≦B≦350 mm, preferably
80 mm≦B≦200 mm.
Length of the target arrangements L: at least B, preferably considerably longer, preferably
400 mm≦L≦2000 mm.
End area of the targets: e.g. semicircular.
1.2 Source/Substrate:
Ration V QS of the dimension of sputtering surface F Q to the dimension of the substrate surface F S to be coated:
V QS ≦3, preferably
V QS ≦2, or preferably even
1.5≦V QS ≦2.
Smallest distance of the virgin source surfaces/coating surfaces D:
60 mm≦D≦250 mm, preferably
80 mm≦D≦160 mm.
Substrate sizes: for example 750×630 mm, coated with a source having a sputtering surface of: 920×900 mm, or
Substrate size: 1100×900 mm, with a source having a sputtering surface of: 1300×1200 mm.
1.3 Cooling:
Ratio sputtering surface to cooling surface V SK .
1.2≦V SK ≦1.5.
2. Operating Variables
Target temperature T:
40° C.≦T≦150° C.,
preferably
60° C.≦T≦130° C.
Sputter power per unit of sputtering surface: 10 to 30 W/cm 2 , preferably 15 to 20 W/cm 2 .
Outermost target arrangements on each side, preferably with 5 to 35% more sputter power, preferably 10 to 20% more sputter power per unit of surface.
Pendulum frequency of the magnet drums: 1 to 4 Hz, preferably approx. 2 Hz.
Results: The following deposition rates were achieved:
ITO: 20 Å/sec.
Al: 130 to 160 Å/sec.
Cr: 140 Å/sec.
Ti: 100 Å/sec.
Ta: 106 Å/sec.
FIG. 9 shows the erosion profile on a 15 cm wide sputtering surface in a target arrangement on the source according to the invention. Due to the extremely uniform erosion the “race tracks” or erosion profiles are barely recognizable.
FIG. 10 shows the resulting coating rate distribution of ITO sputtering, based on a source according to the invention with five target arrangements, each with a sputtering surface width B of 150 mm. In this distribution, film thickness deviations of only ±3.8% are achieved on a substrate arranged at a distance D of 120 mm from the source surface.
In FIG. 11 the resulting film thickness distribution on a large-surface glass substrate is shown which has been coated as follows:
Total sputtering power P tot :
2 kW
Sputtering time:
100 sec.
Deposition rate R: 26 Å/sec., relative:
13 Å/sec. kW
Source with six target arrangements of which the
outermost arrangements have been operated with an
elevated sputter power 10 ot 15% respectively (p 1 ,
p 6 ):
Substrate size:
650 × 550 mm
In FIG. 11 the edge zones of the substrate that were above the target arrangements operated with elevated sputter power are marked. In the ITO coating process the film thickness deviation relative to the mean film thickness of 267 nm was ±6.3%.
The present invention avoids the following disadvantages of known sputtering sources, in particular with respect to the coating of large-surface workpieces:
Because according to the invention a uniform distribution of the process conditions over a large magnetron sputtering surface is possible with high deposition rate and high sputter rate utilization, high economy is achieved when coating large-surface substrates, or possibly in the simultaneous coating of many individual substrates.
Because on the source according to the invention simultaneous sputtering over a large surface takes place, better film thickness distribution on the substrate is achieved and arcing is prevented.
As the problem of reactive gas distribution and/or target erosion distribution is solved in a homogenizing sense, the substrates to be coated can be positioned much closer to the source and have much larger coating surfaces relative to the source surface, which improves the economy of a sputter coating system that is equipped with a source according to the invention.
The problem of plasma density differences between the target center and target periphery occurring on large-surface targets due to missing anodes in the target center is remedied.
The source can be adapted flexibly to the corresponding size requirements by means of modular target arrangements.
The problem occurring with large-surface targets where there is reactive process gas starvation in the middle of the target, is solved because the gas inlets 49 are distributed across the actual source surface.
Because (see FIG. 4) the base ( 41 ) is between process vacuum and atmospheric pressure it is no longer necessary to provide a heavy cooling plate ( 23 ) that can absorb this load. As a result the source becomes less elaborate and better penetration of the fields of the magnet arrangements ( 47 , 43 ) located below the target arrangement ( 3 ) is achieved.
Through the selective control of the following distributions:
by time and/or location, electrical operation of the target arrangements
by time and/or location, magnetic operation of the target arrangements
by time and/or location, gas inlet
it is possible to optimally adjust the film thickness distribution, especially homogeneously, of large-surface substrates.
Due to the provided bayonet catches in conjunction with the clamping of the target arrangements via the cooling media pressure extremely simple and fast exchange of the target arrangements is possible and large-surface, efficient cooling is achieved.
Due to the bayonet catches provided below the sputtering surfaces no fixing elements, and in particular no fixing elements made of non-sputtering material, are accessible from the process chamber, | A method for producing flat panels for TFT or plasma display applications includes forming a sputter source within a sputter coating chamber, the source having at least two electrically mutually isolated stationery bar-shaped target arrangements. A controlled magnet arrangement provided under each target with a time-varying magnetron field. | 7 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a semiconductor device incorporating a lead frame. More particularly, the invention relates to techniques adapted advantageously to a semiconductor device with a lead frame comprising numerous leads as well as heat radiation plates.
[0002] LSIs and other semiconductor devices have undergone ever-higher levels of circuit integration while incorporating higher functions and more complicated circuits than ever before. The enhanced functionality requires furnishing each semiconductor device with a large number of external terminals. This in turns involves increasing the number of pad electrodes provided on a semiconductor chip as well as the number of leads, i.e., external terminals of the semiconductor device. A typical logic semiconductor device may have hundreds of external terminals. Semiconductor devices of the so-called QFP (quad flat package) type, well known as a family of semiconductor devices each having numerous external terminals, are generally mounted on one side of a substrate and are called surface-mounted semiconductor devices. The QFP type semiconductor device is suitable for accommodating a large number of leads because each of the four sides of the package enclosing the semiconductor chip can carry a plurality of leads. When mounted on a substrate, this type of semiconductor device permits an effective use of the space around it.
[0003] A lead frame used in the assembling of such QFP type semiconductors is discussed illustratively in “VLSI Packaging Techniques (Vol. 1)” published by Nikkei BP (in Japan) on May 31, 1993, pp. 155-164. In particular, specific patterns of the frame are shown on pp. 157 and 159 of this publication.
[0004] Fine structures of the semiconductor chip comprise an increasing number of elements each operating at a higher speed than ever. This causes an increase of heat generation from the semiconductor chip. The problem is avoided illustratively by, a semiconductor device having a heat spreader, as described in the “VLSI Packaging Techniques” (Vol. 1), pp. 200-203. The semiconductor device has its semiconductor chip furnished with a heat spreader arrangement to promote heat dissipation of the device.
SUMMARY OF THE INVENTION
[0005] In accommodating a large number of leads, the lead frame needs to have its lead-to-lead spacing (i.e., lead pitch) narrowed and the width of its leads lessened.
[0006] The semiconductor chip also comprises numerous pad electrodes whose presence is necessitated by the enhanced functionality of the semiconductor device. Meanwhile, the spacing between pad electrodes (i.e., pad pitch) has been reduced over the years. Whereas there are different pad pitches for different semiconductor chips in general, the need to obtain as many chips as possible per wafer involves establishing the smallest possible chip size. The trend in turn requires having the smallest possible pitch between pad electrodes.
[0007] Given such reduced pad pitches and under restrictions associated therewith, the process of bonding the many leads to the corresponding pad electrodes using wires made of gold or like material tends to trigger an increasing number of short-circuits between adjacent wires.
[0008] During resin molding after the wire bonding, a decline in the mechanical strengths of leads or a narrowed wire spacing may allow wires to become deformed by molding resin fluidity. The deformation called wire flow can result in short-circuited wires.
[0009] Furthermore, in a QFP, the area in which it is desired to lay out leads becomes narrower the closer it gets to a centrally located semiconductor chip. The thickness and the pitch of the leads are subject to limitations stemming from the limitation of the manufacturing precision of the lead. More specifically, the lead pitch cannot be made sufficiently fine compared with the pad patch on the semiconductor chip. As the semiconductor chip shrinks in external dimensions, it becomes increasingly difficult to bring the tips of the leads close to the chip. When the lead tips to be bonded are distanced from the pad electrodes of the semiconductor chip under such circumstances, wires for bonding the pads to the leads must be extended. Extended wires are likely to cause more short-circuits or result in more wire flow than before.
[0010] While today's practical pad pitches are down to about 80 μm, the required pitch is expected to reach 60 to 45 μm in the future. As chips shrink further, bonding wires are extended correspondingly. At present, it is necessary to keep the wire length to a maximum of 5 or 6 mm in order to ensure stable bonding. This requires a further reduction in the pitch of the lead tips so as to avert wire extensions.
[0011] [0011]FIG. 1 shows results of simulations performed by the inventors relating to wire bonding. On 256-pin semiconductor chips with different pad pitches, correlations were simulated between inner lead tip pitches on the one hand and wire lengths for stable bonding on the other hand. The simulations revealed the need to restrict the lead tip pitch to a maximum of 180 μm with respect to the 60 μm pad pitch in order to ensure stable bonding.
[0012] Such micro-fabrication of the leads is bound to lower their mechanical strength. Even an extremely limited amount of force can thus deform the tenuous lead formation. The deformed leads trigger short-circuits.
[0013] A conventional solution to the above problem is the fastening of inner leads using an insulating tape to prevent lead deformation. FIG. 2 is a plan view of a conventionally structured tape-fastened lead frame. FIG. 3 is a cross-sectional view of a resin-sealed semiconductor device fabricated by use of the lead frame in FIG. 2.
[0014] The lead frame is illustratively made of a copper alloy. A semiconductor chip 1 (indicated by broken lines) is fixed to a tab 2 . A plurality of leads 3 are located around the entire periphery of the mounted semiconductor chip 1 . The leads 3 come in two types: inner leads 4 and outer leads 5 . The tips of the inner leads 4 surround the semiconductor chip 1 .
[0015] The leads 3 are integrated with a dam bar 6 or with a tie bar 8 constituting a framework of the lead frame. The inner and outer leads 4 and 5 are formed inside and outside of the dam bar 6 , respectively. The tab 2 is supported by tab suspending leads 7 furnished across the inner leads 4 . The inner leads 4 and the tab suspending leads 7 are fastened to a rectangular insulating tape 9 .
[0016] In the case of a semiconductor device using the above-described lead frame, the semiconductor chip 1 is fixed to the tab 2 by resin or by silver paste while the inner leads 4 are connected to pad electrodes 10 of the chip 1 by bonding wires 11 . After bonding, the semiconductor chip 1 , tab 3 , inner leads 4 and bonding wires 11 are molded by a molding member 12 illustratively made of epoxy resin. The dam bar 6 and tie bar 8 are cut so that the leads 3 are electrically isolated from one another. Thereafter, the outer leads 5 extending from the molding member 12 are illustratively formed in gull wing fashion as shown in FIG. 3. This completes fabrication of the semiconductor device.
[0017] With the tape-fastened lead frame, as shown in FIGS. 2 and 3, a middle part of the inner leads 4 is secured by the tape 9 to allow for flexible uses of the frame. In other words, the tape 9 is positioned away from the tips of the inner leads 4 . This is an inefficient and unstable structure for fastening the inner lead tips to which wires are to be bonded.
[0018] Furthermore, some recently developed semiconductor devices have been subject to significant heat generation from semiconductor chips because of their enhanced functionality and high performance. These devices have their semiconductor chips equipped with a heat radiation plate such as a heat spreader to facilitate heat dissipation.
[0019] [0019]FIG. 4 is a plan view of a lead frame for use with a heat spreader-incorporating QFP (called HQFP hereunder), wherein a copper foil devised by the inventors is attached by adhesive to a semiconductor chip as a heat radiation plate. This setup has not been disclosed until now. FIG. 5 is a cross-sectional view of a semiconductor device fabricated by use of the lead frame in FIG. 4.
[0020] As opposed to the lead frame and semiconductor device discussed earlier, this semiconductor chip 1 (indicated by broken lines) is fastened to a heat radiation plate 13 . The inner leads 4 are also fixed to the heat radiation plate 13 .
[0021] Such HQFP type semiconductor devices comprise numerous contacts between the molding member 12 and the heat radiation plate 13 . Because of a feeble adhesive strength between resin (i.e., molding member 12 ) and metal (heat radiation plate 13 ), moisture absorbed in the interface between the molding member 12 and the heat radiation plate 13 can evaporate and expand during reflow heating, causing a crack in the package. The reflow heating occurs during the process of mounting a surface-mounted semiconductor device onto a substrate. The semiconductor device of FIG. 4 addresses the reflow problem by having a round hole provided in the middle of the heat radiation plate 13 , the hole allowing the molding member 12 to contact the semiconductor chip 1 . However, this structure is still not sufficient to overcome the problem.
[0022] It is therefore an object of the present invention to provide techniques for stabilizing the bonding of a semiconductor device having numerous leads.
[0023] It is another object of the present invention to provide techniques for preventing a generation of a crack in the package of a semiconductor device furnished with a heat radiation plate.
[0024] A summary of typical aspects of the invention disclosed in the present application will be described in brief in the following manner.
[0025] In a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the semiconductor chip is connected to tips of inner leads having a lead width of w and a lead thickness of t, wherein the lead width w is less than the lead thickness t (w<t), and wherein at least the tips of the inner leads are fastened to the radiation plate.
[0026] In a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the semiconductor chip is connected to tips of inner leads having a lead width of w and a lead thickness of t, wherein the lead width w is less than the lead thickness t and wherein at least the tips of the inner leads are fastened to the radiation plate so as to support the radiation plate. This structure eliminates the need for installing conventional suspending leads supporting the radiation plate.
[0027] In a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the semiconductor chip is connected to tips of inner leads having a lead pitch of p, a lead width of w and a lead thickness of t, wherein the lead width w is less than the lead thickness (w<t), wherein the lead pitch p is equal to or less than 1.2 times the lead thickness t(p≦1.2 t), and wherein at least the tips of the inner leads are fastened to the radiation plate.
[0028] In a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the radiation plate has slits formed therein in a radial fashion to establish heat propagation paths radiating from a semiconductor chip mounting area on the plate toward inner leads.
[0029] In a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the tips of inner leads (tip thickness t′) are made thinner than the other portions of the inner leads (lead thickness t), and at least the tips of the inner leads are fastened to the radiation plate.
[0030] In a method of fabricating a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the method comprises the steps of: connecting the semiconductor chip to tips of inner leads having a lead pitch of p, a lead width of w and a lead thickness of t, wherein the lead width w is less than the lead thickness t (w<t) and wherein the lead pitch p is equal to or less than 1.2 times the lead thickness t(p≦1.2 t); fastening at least the tips of the inner leads to the radiation plate; and connecting the inner leads to pad electrodes of the semiconductor chip.
[0031] In a method of fabricating a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the method comprises the steps of: making slits in the radiation plate in a radial fashion to form heat propagation paths radiating from a semiconductor chip mounting area on the plate toward inner leads; and applying a sealant by letting it penetrate through the slits in the radiation plate during resin sealing.
[0032] In a method of fabricating a semiconductor device having a semiconductor chip fixed to a radiation plate and sealed by a sealant, the method comprises the steps of: fastening the semiconductor chip to the radiation plate on a lead frame
[0033] wherein tips of inner leads (tip thickness t′) are made thinner than the other portions of the inner leads (lead thickness t); and connecting the inner leads to pad electrodes of the semiconductor chip wherein at least the tips of the inner leads are fastened to the radiation plate.
[0034] In a lead frame comprising a plurality of leads and a radiation plate having a semiconductor chip mounting area onto which to fix a semiconductor chip, the semiconductor chip is connected to tips of inner leads among the leads, the inner lead tips having a lead pitch of p, a lead width of w and a lead thickness of t, wherein the lead width w is less than the lead thickness t (w<t), wherein the lead pitch p is equal to or less than 1.2 times the lead thickness t(p≦1.2 t), and wherein at least the tips of the inner leads are fastened to the radiation plate.
[0035] In a lead frame comprising a plurality of leads and a radiation plate having a semiconductor chip mounting area onto which to fix a semiconductor chip, the radiation plate having slits formed therein in a radial fashion to establish heat propagation paths radiating from the semiconductor chip mounting area on the plate toward inner leads.
[0036] In a lead frame comprising a plurality of leads and a radiation plate having a semiconductor chip mounting area onto which to fix a semiconductor chip, the tips of inner leads among the leads (tip thickness t′) are made thinner than the other portions of the inner leads (lead thickness t), and at least the tips of the inner leads are fastened to the radiation plate.
[0037] According to the present invention, there is provided a semiconductor device comprising: a heat radiation plate including a main surface and a back surface opposite to the main surface, the heat radiation plate having through type slits penetrating from the main surface to the back surface, a semiconductor chip having a semiconductor element and a plurality of electrodes furnished on a principal plane, the semiconductor chip being fastened to the main surface of the
[0038] heat radiation plate; a plurality of leads made of an inner lead and an outer lead each, tips of the inner leads being fixed to the heat radiation plate, the inner leads being connected electrically to electrodes of the semiconductor chip, and a molding member sealing the heat radiation plate, the semiconductor chip, and the inner leads; wherein the through type slits are laid out in a radial fashion radiating from outside a semiconductor chip mounting area of the heat radiation plate toward a region surrounded by the tips of the inner leads.
[0039] In the above semiconductor device, the heat radiation plate may be rectangular in shape and the through type slits may be fabricated to extend toward four corners of the heat radiation plate.
[0040] Further, according to the present invention, there is provided a semiconductor device comprising: a heat radiation plate including a main surface and a back surface opposite to the main surface, the heat radiation plate having through type slits penetrating from the main surface to the back surface; a semiconductor chip having a semiconductor element and a plurality of electrodes furnished on a principal plane, the semiconductor chip being fastened to the main surface of the heat radiation plate; a plurality of leads made of an inner lead and an outer lead each, tips of the inner leads being fixed to the heat radiation plate, the inner leads being connected electrically to electrodes of the semiconductor chip; and a molding member sealing the heat radiation plate, the semiconductor chip, and the inner leads; wherein the through type slits are laid out in a radial fashion radiating toward a region surrounded by the inner leads on the heat radiation plate.
[0041] In the above semiconductor device, the through type slits may be fabricated so that the back surface of the semiconductor chip is partially exposed.
[0042] In the above semiconductor device, the heat radiation plate may be rectangular in shape and the through type slits may be fabricated to extend toward four corners of the heat radiation plate.
[0043] As outlined above and according to the invention, the tips of the inner leads are fastened to the heat radiation plate. The structure eliminates the need for installing tab suspending leads supporting tabs that carry the semiconductor chip. The area that was conventionally allocated to the tab suspending leads is utilized for accommodating the inner leads. Given the same lead pitch, the structure allows the inner lead tips to be located closer to the semiconductor chip than before.
[0044] The inventive structure in which the inner lead tips are fastened to the heat radiation plate stabilizes bonding and prevents deformation of the inner leads.
[0045] According to the invention, the heat radiation plate has slits formed therein in a radial direction to establish heat propagation paths. The structure enhances protection against the reflow problem while minimizing a decline in the heat radiation characteristic.
[0046] Also according to the invention, the inner lead tips are made thinner than before so as to improve the accuracy in fabricating the tips. Fixing the inner lead tips to the heat radiation plate reinforces resistance to the deformation of the tips.
[0047] These and other objects, features and advantages of the invention will become more apparent upon a reading of the following description and appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] [0048]FIG. 1 is a graphic representation showing results of simulations about wire bonding;
[0049] [0049]FIG. 2 is a plan view of a conventionally structured tape-fastened lead frame;
[0050] [0050]FIG. 3 is a cross-sectional view of a resin-sealed semiconductor device fabricated by use of the lead frame in FIG. 2;
[0051] [0051]FIG. 4 is a plan view of a lead frame for HQFP use devised by the inventors;
[0052] [0052]FIG. 5 is a cross-sectional view of a resin-sealed semiconductor device fabricated by use of the lead frame in FIG. 4;
[0053] [0053]FIG. 6 is a plan view of a lead frame representing as an embodiment of the invention;
[0054] [0054]FIG. 7 is a cross-sectional view of a resin-sealed semiconductor device fabricated by use of the lead frame in FIG. 6, the view being taken on line A-A′ in FIG. 6;
[0055] FIGS. 8 ( a ) and 8 ( b ) are cross-sectional views of tips of inner leads on the lead frame in FIG. 6;
[0056] FIGS. 9 ( a ) and 9 ( b ) are cross-sectional views of tips of inner leads on the lead frame in FIG. 2;
[0057] [0057]FIG. 10 is a graphic representation comparing different types of slits in terms of thermal resistance;
[0058] [0058]FIG. 11( a ) is a plan view and FIG. 11( b ) is a cross-sectional view showing how inner lead tips or pad electrodes of a semiconductor chip are laid out;
[0059] [0059]FIG. 12( a ) is a plan view and FIG. 12( b ) is a cross-sectional view depicting how inner lead tips or pad electrodes of a semiconductor chip are laid out;
[0060] [0060]FIG. 13( a ) is a plan view and FIG. 13( b ) is a cross-sectional view illustrating how inner lead tips or pad electrodes of a semiconductor chip are laid out;
[0061] [0061]FIG. 14( a ) is a plan view and FIG. 14( b ) is a cross-sectional view indicating how inner lead tips or pad electrodes of a semiconductor chip are laid out;
[0062] [0062]FIG. 15A is a plan view of a lead frame with differently shaped slits in the heat radiation plate;
[0063] [0063]FIG. 15B is a cross-sectional view of a resin-sealed semiconductor device fabricated by use of the lead frame in FIG. 15A, the view being taken on line B-B′ in FIG. 15A;
[0064] [0064]FIG. 16 is a plan view of another lead frame with differently shaped slits in the heat radiation plate;
[0065] [0065]FIG. 17 is a plan view of another lead frame with differently shaped slits in the heat radiation plate;
[0066] [0066]FIG. 18 is a plan view of another lead frame with differently shaped slits in the heat radiation plate;
[0067] [0067]FIG. 19 is a plan view of another lead frame with differently shaped slits in the heat radiation plate; and
[0068] [0068]FIG. 20 is a cross-sectional view of a variation of the embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0069] Preferred embodiments of this invention will now be described with reference to the accompanying drawings. Throughout the drawings, like reference characters designate like or corresponding parts, and their descriptions are omitted where they are repetitive.
First Embodiment
[0070] [0070]FIG. 6 is a plan view of a lead frame for an HQFP type semiconductor device practiced as a first embodiment of the invention. FIG. 7 is a cross-sectional view of a semiconductor device fabricated by use of the lead frame in FIG. 6, the view being taken on line A-A′ in FIG. 6. FIGS. 8 ( a ) and 8 ( b ) are cross-sectional views of tips of inner leads on the lead frame in FIG. 6. FIG. 8( a ) shows lead tips formed by etching, while FIG. 8( b ) shows lead tips formed by presswork.
[0071] The lead frame is made illustratively of an Fe—Ni alloy or a copper alloy. The entire periphery of a semiconductor chip 1 (indicated by broken lines) is surrounded by tips of inner leads 4 among a plurality of leads 3 . The leads 3 are integrated with a dam bar 6 or with a tie bar 8 constituting a framework of the lead frame. An inside and an outside portion of the dam bar 6 make up the inner leads 4 and outer leads 5 , respectively. The semiconductor chip 1 is bonded fixedly to a heat radiation plate 13 using a polyimide type adhesive 14 and a die bonding agent 17 . The inner leads 4 are fastened to the heat radiation plate 13 by use of the adhesive 14 .
[0072] In the case of a semiconductor device using the above-described lead frame, the semiconductor chip 1 is fixed to the heat radiation plate 13 by resin or by silver paste 17 while the inner leads 4 are connected to pad electrodes 10 of the chip 1 by bonding wires 11 . After the bonding, the semiconductor chip 1 , heat radiation plate 13 , inner leads 4 and bonding wires 11 are sealed by a molding member 12 illustratively made of epoxy resin. The dam bar 6 and tie bar 8 are cut so that the leads 3 are electrically isolated from one another. Thereafter, the outer leads 5 extending from the molding member 12 are illustratively formed in a gull wing shape or in another appropriate manner. This completes fabrication of the semiconductor device 21 .
[0073] On an etched lead frame, the lead top width is made greater than the lead bottom width so that the lead tops will be wide enough to accommodate bonding while the lead width w is minimized. To produce such a cross-sectional structure-illustratively requires altering the etching conditions on the tops and bottoms of the leads.
[0074] At the lead tips where the lead pitch p is narrow, the lead thickness t is less than the lead width w. This lead structure tends to suffer from poorly fastened wires at the time of bonding and is vulnerable to crosswise deformation. It follows that on a lead frame where the pitch of the inner lead tips is 180 μm, i.e., 1.2 times the lead thickness or less, the inner leads 4 are preferably fixed to the heat radiation plate 13 .
[0075] With the inner leads 4 fixed to the heat radiation plate 13 , the lead tips are kept anchored during wire bonding. This ensures reliability of wire bonding. The benefit is corroborated by comparison with cross-sectional views of FIGS. 9 ( a ) and 9 ( b ) showing inner leads 4 of the lead frame in FIG. 2.
[0076] Today, lead frames are approximately 150 μm in thickness, about as thin as they can get in the face of possible deformation of the outer leads 5 . The lead pitch is typically 185 μm, the lead width is 100 μm, and the lead spacing is 85 μm. In the future, on lead frames with a narrow lead pitch, the lead pitch at the tips of the inner leads 4 will be 180 μm or less. Likewise the lead width w is expected to be less than the lead thickness (w c t) and the inner lead tip pitch p is expected to be equal to or less than 1.2 times the lead thickness t(p<1.2 t). In such cases, according to the invention, the inner leads 4 are to be fixed to the heat radiation plate 13 on the lead frame to keep the lead tips anchored during wire bonding. The structure should enhance the reliability of wire bonding.
[0077] On the lead frame of the invention, the semiconductor chip 1 is fastened to a semiconductor chip mounting area on the heat radiation plate 13 fixed by the inner leads 4 . In this setup, there are no tab suspending leads furnished conventionally to support tabs on which to mount a semiconductor chip. Regions where the tab suspending leads used to be provided are utilized for the layout of inner leads 4 .
[0078] In the setup above, the corners where tab suspending leads were conventionally furnished also accommodate inner leads 4 . Given the same lead pitch, it is thus possible to locate the tips of the inner leads 4 closer to the semiconductor chip 1 than before. This in turn shortens the lengths of wires to be bonded after the semiconductor chip 1 is mounted. As a result, wire deformation is minimized and short-circuits between wires are reduced during sealing by use of resin.
[0079] It is also possible to widen the lead pitch or increase the number of leads without getting the tips of inner leads 4 coming closer to one another.
[0080] Slits 15 are made in the heat radiation plate 13 between the area on which to mount the semiconductor chip 1 on the one hand and the inner leads 4 on the other hand. The slits 15 allow the molding member 12 to penetrate through the heat radiation plate 13 and make it difficult for the plate 13 and the molding member 12 to separate. With the molding member 12 penetrating the heat radiation plate 13 , an enhanced level of resistance to the reflow problem is attributable to two causes: an increased force of the molding member holding down the semiconductor chip 1 , and a separated interface between the heat radiation plate 13 and the molding member 12 also disconnecting forces caused by evaporation and expansion of the moisture content. The semiconductor chip 1 to be mounted varies in size depending on what function is specifically required of it. In this embodiment, the semiconductor chips land the slits 15 are unchanged in their sizes. When a larger semiconductor chip is to be mounted, the edges of the chip are partially overlaid with the slits 15 , and the chip is secured by the resin 12 .
[0081] The slits 15 are shaped so that heat propagation paths X of the heat radiation plates 13 are formed in a radial direction, as indicated by arrows X. Illustratively, putative conventional slits 16 , indicated by broken lines, arranged perpendicular to the heat propagation paths X, shown here for reference, will interrupt propagation of heat along the paths X. FIG. 10 is a graphic representation comparing different types of slits in terms of thermal resistance. In FIG. 10, the inventive slit setup represented by slit 15 and the conventional slit setup denoted by slit 16 are compared with a setup with no slit. It can be seen that the inventive slit setup 15 maintains the rise in thermal at a level lower than the other setups and minimizes the possibility of deterioration caused by heat dissipation.
[0082] With the HQFP type semiconductor device described above, the tips of the inner leads 4 or the pad electrodes 10 of the semiconductor chip 1 may be laid out in an alternate arrangement (staggered fashion). The staggered layout provides further reliability in bonding wires.
[0083] Conventionally, as shown in FIG. 11( a ) and FIG. 11( b ), the tips of the inner leads 4 or the pad electrodes 10 of the semiconductor chip 1 are arranged in a single row along each side of the chip 1 . According to the invention, as shown in FIG. 12( a ) and FIG. 12( b ), the adjacent pad electrodes 10 of the semiconductor chip 1 may be alternately arranged (staggered) along each side of the semiconductor chip 1 , with wires bonded at different elevations to the electrodes. The layout makes the bonding of wires to the pad electrodes 10 easier than before.
[0084] Likewise, as illustrated in FIG. 13( a ) and FIG. 13( b ), the tips of the adjacent inner leads 4 may be staggered, with wires bonded at different elevations to the lead tips. Furthermore, as depicted in FIG. 14( a ) and FIG. 14( b ), the tips of the adjacent inner leads 4 as well as the adjacent pad electrodes 10 of the semiconductor chip 1 may be staggered, with wires bonded at different elevations to the lead tips and the electrodes. The layout makes it easier than before to bond wires to the inner leads 4 and pad electrodes 10 .
[0085] The slits 15 to be furnished in the heat radiation plate 13 may take diverse patterns as shown in FIGS. 15A through 19.
[0086] The patterns shown by way of example in FIGS. 15A and 17 give priority to the resistance to the reflow problem by enlarging the area for the slits 15 , while the example shown in FIG. 16 favors an enhanced capability of heat dissipation because the slits 15 are made narrower than those in FIG. 15A and FIG. 17 so as to enlarge the paths for heat dissipation correspondingly. The pattern shown by way of example in FIG. 18 seeks a trade-off between resistance to the reflow problem and better heat dissipation. The slits 15 in FIG. 16 are shaped in such a manner that sufficient heat dissipation is guaranteed while the resistance to the reflow problem is improved. The slit pattern in FIG. 15A and that in FIG. 17 are similar in shape and different in orientation. In the pattern of FIG. 15A, the molding member 12 provides higher resistance to the reflow problem by securing the corners of the semiconductor chip 1 , i.e., by anchoring the chip corners with resin. In the pattern of FIG. 17, a widened area of contact between the semiconductor chip 1 and the heat radiation plate 13 ensures a better heat dissipation characteristic. A suitable slit pattern may thus be selected depending on what is particularly required of the semiconductor device. FIG. 15B is a cross-sectional view of a semiconductor device fabricated by use of the lead frame in FIG. 15A, the view being taken on line B-B′ in FIG. 15A: In FIG. 15B, the parts already shown in FIG. 7 are given the same reference numerals, and details thereof are omitted. Some portions of the back of the semiconductor chip 1 are not overlaid with the heat radiation plate 13 ; these portions are sealed directly by the sealing resin 12 .
[0087] The slits 15 in the pattern of FIG. 19 are identical in shape to those in FIG. 15A. The difference is that the tips of the inner leads 4 in FIG. 19 are laid out in an alternating arrangement to make the bonding of wires easier. That layout of the inner leads 4 may also apply to the other examples having different slit shapes in FIGS. 16 through 18. The same also applies to the pad electrodes 10 of the semiconductor chip 1 . Illustratively, a semiconductor chip 1 with its pad electrodes 10 staggered as shown in FIG. 12 may be applied to the lead frames in FIGS. 15A through 19.
[0088] [0088]FIG. 20 shows a variation of this embodiment wherein the tip thickness t′ of the inner leads is made greater than the thickness t of the other portions of the leads 3 . Such partially different lead thicknesses may be acquired illustratively by localized etching. When the leads are to be fabricated, their thickness constitutes an important factor in achieving the desired precision. That is, the accuracy of lead fabrication is ensured by making the tips of the inner leads 4 thinner than before (i.e., where precision counts); and, the remaining lead portions are made sufficiently thick to guarantee sturdiness. When the tips of the inner leads 4 are thinned for accuracy, it is important to fasten the leads to the heat radiation plate 13 to prevent their deformation.
[0089] Although the description above contains many specificities, these should not be construed as limiting the scope of the invention but as merely providing illustrations of the presently preferred embodiment of this invention. It is to be understood that changes and variations may be made without departing from the spirit or scope of the claims that follow.
[0090] For example, although the embodiment above was shown as having rectangular heat radiation plates on which to secure the leads, this is not a limitation of the invention. Alternatively, the heat radiation plates may be circular. Such round heat radiation plates have the advantage of smoother resin flow during resin molding, which reduces the incidence of voids inside.
[0091] The heat radiation plate of the embodiment described above may be equipped with a bonding area for bonding to ground. This arrangement makes up a lead frame ready for bonding to ground, which further enlarges the scope of applications for the inventive semiconductor device.
[0092] There need not be a single semiconductor chip to be mounted on the heat radiation plate. Alternatively, a plurality of semiconductor chips may be mounted on the heat radiation plate. That is, the invention also applies advantageously to multi-chip semiconductor devices.
[0093] Although the description above has dealt primarily with the field of semiconductor devices constituting the technical background of this invention, that field is not a limitation of the invention. The present invention also applies extensively to devices wherein electronic components are installed using lead frames.
[0094] The major effects of this invention as disclosed herein are summarized below.
[0095] (1) According to the invention, the tips of the inner leads are secured to the heat radiation plates.
[0096] (2) The feature (1) above offers the benefit of stabilizing the bonded wires.
[0097] (3) The feature (1) above also prevents deformation of the inner leads.
[0098] (4) According to the invention, the tips of the inner leads are laid out at equal intervals on all sides of the semiconductor chip mounting area. The layout offers the benefit of locating the inner lead tips closer to the semiconductor chip mounting area than before.
[0099] (5) The feature (4) above shortens the wires to be bonded.
[0100] (6) According to the invention, the heat radiation plate has slits formed therein in a radial fashion to establish heat propagation paths. The structure enhances protection against the reflow problem.
[0101] (7) According to the invention, the slits formed in the heat radiation plate in a radial fashion to establish heat propagation paths will minimize a decline in the heat radiation characteristic.
[0102] (8) Also, according to the invention, the inner lead tips are made thinner than before so as to improve the accuracy in fabricating the tips.
[0103] (9) Further, according to the invention, the inner lead tips are made thinner than before and are secured to the heat radiation plate. This structure prevents deformation of the inner lead tips. | A method of manufacturing a semiconductor device is provided including preparing a lead frame having a plurality of leads, wherein the lead widths of the lead tips are smaller than the lead thickness of the tips. A plate is also prepared having a first portion and second portion on a main surface thereof, the second portion being located at the outer periphery of said first portion. A semiconductor chip having a semiconductor element and a plurality of electrodes is fastened to the first portion of the plate and the lead tips are fastened on the second portion of the plate. Bonding wires are then formed to electrically connect the lead tips and the electrodes of the semiconductor chip, and then the lead tips, the plate, the semiconductor chip and the bonding wires are sealed with a molding member. | 7 |
This is a continuation of application Ser. No. 08/122,664, filed Sep. 17, 1993 now abandoned, which is a divisional of Ser. No. 07/964,464, filed Oct. 21, 1992 (U.S. Pat. No. 5,260,097), which is a continuation of Ser. No. 07/700,888, filed May 10, 1991, now abandoned which is a continuation of Ser. No. 07/411,377, filed Sep. 22, 1989 now abandoned.
The invention relates to a method for masking at least a part of a surface to be treated wherein an element that is resistant to surface treatment operations is removably applied to said part of said surface and is removed after finishing said treatment. The invention also relates to a masking means, wherein said masking means is formed by a removable element which is resistant to surface treatments.
BACKGROUND OF THE INVENTION
Such a masking method and masking means is known from the use of a masking tape, or from the use of a grooved panel of plastic foam as described in the European patent application No. 0207720. These known methods are for example applied in priming and painting of vehicle coachwork, in particular automobile coachwork, or in refinishing work, sandblasting or other surface treatments. In order to prevent paint or other substances to be applied on a surface to be treated from penetrating or covering at least a part of the surface to be treated, that part is masked by using an element that is resistant to surface treatment operations. The element is resistant to surface treatments operations and masks the surface during the treatment and is removed following the treatment.
A drawback of the grooved plastic foam panel is that, due to its panel shape, it is primarily appropriate for masking a planar surface. In particular for surface treatment operation on the body of a vehicle it is not enough to mask only the planar surfaces, since the vehicle body shows a lot of irregularities. Those irregularities usually masked with protection paper and/or masking tape which is a time-consuming operation, because it has to be performed very carefully. Also these known masking methods do not always result in a satisfactory surface treatment. The dust left in the openings can cause contamination of the treated surface. Turbulences can occur around those openings or edges causing an uneven application of the substance to be applied on the surface to be treated.
An object of the invention is to mitigate the above mentioned drawbacks.
According to the present invention a compressible cushion is applied as said element on at least a portion of an irregularity in said surface wherein said cushion is adaptable to said portion of said irregularity on which it is applied.
Due to the fact that the masking element is formed by a compressible cushion, it is no longer necessary to use protection paper nor to apply several masking tape layers in order to mask an irregularity, thus providing a substantial time saving. The compressible cushion adapts itself for filling or covering surface irregularities such as openings or edges. Thus the cushion prevents the formation of turbulences and so the contamination by dust originating from the openings, and enables an adequate masking of the irregularities.
The gist of the present invention is to use an adaptable compressible cushion as masking element in order to mask irregularities. Due to the fact that the cushion is adaptable to the irregularity it takes the exact shape of the irregularity thus providing an excellent masking.
A masking means according to the invention is characterized in that said element is a compressible cushion which is adaptable to the irregularity to which it is applied.
Masking means having the shape of a particular irregularity are known and are for example described in the European patent application No. 0263637. However the difference between a masking means according to the present invention and the masking means according to the latter patent application is that the masking means according to EPA 0269 637 have a particular preformed shape which is on beforehand completely adapted to the irregularity and can thus only be used for masking an irregularity of that particular shape. The masking means according to the present invention is not on beforehand adapted to a particular irregularity but adapts itself to the irregularity to which it is applied. The masking means according to the present invention is thus universally applicable to many kinds of irregularities while the masking means according to EPA 2263637 is not universally applicable.
One should not confuse a masking gasket with a conventional sealing gasket. Indeed, in automobiles it is well known to apply a sealing gasket on the innerlip of a door, hood or a trunk, in the frame of the door or in the other openings which prevents inter alia water and noise from penetrating inside the vehicle. Those sealing gaskets are applied by the manufacturer of the car at a well-defined place and are generally manufactured for each particular automobile model. Those sealing gaskets are quasi-permanently fixed in place. On the other hand, a masking gasket according to the invention only serves for masking, as its name indicates, and not for permanent sealing purposes.
The use of a thermoplastic foam for masking purposes is described in the U.S. Pat. No. 4,714,633. That patent describes the use of an expending and shrinking thermoplastic foam member that contains a cavity. During the surface treatment operation or when the member is heated afterwards, the member according to the U.S. patent will change its form in order to be separated in a natural way of the article on which it has been fixed. On the other hand, the masking means of the invention resists surface treatment operation, i.e. its original configuration will not modify under influence of the surface treatment, unlike the member described in the patent. Contrary to the masking means according to that patent, the masking means according to the invention need not include a cavity which enables a separation operation. The member according to the cited U.S. patent is clearly used in surface treatment operations where its extending and shrinking properties are essential, while the masking means according to the invention is applied in surface treatment operations where its resistance to the treatment plays an important role.
The invention thus provides a non-evident application of a masking means. Indeed, the idea of using a cushion is not evident with respect to the well known use of masking tapes. Several solutions such as pre-treatment of surfaces (see for example the Japanese patent applications 85021787 or 81211929 have already been tested out in order to reduce secondary effects due to the masking during surface treatment operations. The use of a masking means according to the present invention not only enables a substantial time saving but also a quality improvement without use of pre-treatment operations or the like.
SUMMARY OF THE INVENTION
A first preferred embodiment of a masking means according to the invention is characterized in that said cushion is an elongated cushion. The elongated cushion offers the advantage that it can be applied in one piece over the whole length of the irregularity to be masked, thus avoiding connection parts which coul cause turbulences having a negative influence on the achievement quality.
Preferably that said cushion has substantially the same cross section over its whole length. This enables a uniform masking.
A first preferred embodiment of a masking method according to the invention is characterized in that said cushion is applied to an elongated irregularity. Elongated irregularities are usual in vehicles. The cushion according to the invention enables an excellent masking of such irregularities in vehicles.
In a second preferred embodiment of a method according to the invention said cushion is positionably adhered on said part of said irregularity. This enables accurate positioning of the cushion when it has incorrectly been applied.
The invention also relates to a device for applying the masking means according to the invention. The device according to the invention is characterized in that it comprises a drum for unwinding said cushion.
In another preferred embodiment a method according to the invention is characterized in that said cushion is formed by applying to said part of said irregularity a polymerizing foam comprising at least a reactive substance. That method is for example applied for masking parts which are difficult to access and thus provides an easy application of the foam on the irregularity to be masked.
A second preferred embodiment of a masking means according to the invention is characterized in that said masking means comprise an elastic foam cushion which is provided with a pressure sensitive adhesive layer, which covers at least a part of said cushion. The cushion can thus easily be applied on the irregularity by simply adhering the cushion thereon.
Preferably said cushion is hollow. this enables saving of material and also gives more flexibility to the cushion.
Preferably said cushion is wound in a coil. This offers an adequate packing for the masking means.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described more in details by means of examples illustrated in the drawing in which:
FIG. 1 illustrates a first preferred embodiment of a masking means according to the invention;
FIG. 2 illustrates a second preferred embodiment of a masking means according to the invention;
FIG. 3 illustrates the result of a method according to the invention when applied on the open door of an automobile;
FIG. 4 illustrates a cross-section of a masking means according to the invention applied on an automobile;
FIG. 5 illustrates an example of a device for applying a masking means according to the invention;
FIG. 6 illustrates a masking means according to the invention which masking means is wound on a coil and packed in a box.
DETAILED DESCRIPTION
On the different figures corresponding elements are referred to with the same reference numerals. It will be veident that the invention is not limited to the described embodiments and that within the scope of the invention different embodiments are possible.
In the example shown in FIG. 1, the masking means according to the invention is formed by a cushion 1 which is cylindrically shaped and elongated. The cushion is a compressible cushion preferably made out of an absorbing material. The cushion 1 is at least partially provided with a pressure sensitive adhesive layer formed by an self adhesive film. that adhesive layer enables the fixing of the cushion and also the easy removing thereof after the surface treatment has been accomplished.
Preferably the cushion 1 is an elastic foam cushion which is made of a material resistant to surface treatment operations. The foam thus for example resists high temperatures of a spraying cabin for automobiles, to solvents and humidity. The material used for manufacturing the cushion is preferably a synthetic material such as for example polypropylene, neoprene, polyester, polyurethane or acrylic. It will be evident that other materials, elastic or not, synthetic or natural, which resist surface treatment operations can also be used. The adhesive layer 2 is for example formed by an adhesive based on rubber, resin, acrylic, or other suitable material, having an immediate tack. If necessary, the cushion could be provided with a repositionable adhesive layer, which should be resistant to solvents and changes in temperature.
The cushion can have different cross-sections, for example it can have a diameter within a range of 5 to 50 mm, and is preferably presented rolled up. The cushion can also have a rectangular cross-section, such as shown in FIG. 2 or a cross-section of any other geomatrical form, such as for example triangular or trapezoidal. Preferably the cushion has substantially the same cross-section over it whole length.
This cushion can be either solid or hollow, such as for example illustrated in dotted line in FIG. 1. A hollow cushion improves the elasticity of the masking means while saving material.
The adhesive layer 2 can be covered by a liner 3 , which is removed before the masking means is applied. The adhesive layer can also be applied to the whole or to a substantial portion of the exposed portion of the cushion, for example when a rectangular cushion is used such as illustrated in FIG. 2, the adhesive layer can be applied to two or more sides of the cushion thus enabling a better and/or easier application of the cushion.
The adhesive substance is preferably self-sticking, thus forming with the foam a self-sticking assemblage realized either by a pressure sensitive adhesive film which at least partially covers the cushion, such as illustrated in FIGS. 1 and 2, or by manufacturing a cushion from a foam which itself is tacky. In the latter case, the foam can be completely covered by a protection liner. A foam which is provided with a pressure sensitive adhesive is particularly advantageous for appliations on vehicle body reparing. Indeed, the surface to be masked can sometimes impose multiple contorsions upon the cushion. When the foam is provided with an adhesive layer, one can reliably obtain a satisfying adhesion, notwithstanding the geometric form of the irregularity to be masked.
However the cushion 1 can also be fixed on the irregularity which has to be masked by other means, which are not necessarily self-sticking. For example it is possible to use a cushion which is not self-sticking and to first spray an adhesive on the surface on which the cushion has to be applied, and thereafter stick the cushion on the applied adhesive.
In another embodiment of the masking method, the elastic foam cushion is formed by applying on the surface, which has to be masked, a polymerising foam made from a suitable reactive substance or substances. That reactive substance is for example stored in an aerosol container and is prayed on the surface to be masked. This enables a masking of places which are otherwise difficult to access for applying thereon a masking cushion.
The FIGS. 3 and 4 illustrate the masking according to the invention as applied to the door of an automobile. Suppose that the external surface 11 of a door 4 has to be painted by spraying. In order to prevent paint from penetrating into a crevice or opening between the door and the surrounding parts of the coachwork and adhering to the sealing gasket, or weatherstrip 12 , it is necessary to mask the opening. therefore the cushion 1 according to the invention is applied for example by means of its adhesive layer, on the border of the lip of the door 4 , of the side 5 of the door, and on all the other portions which represent an irregularity with respect to the surface of the door such as the border lines of the windows, bottom of the car body, the latches of the doors and other surrounding surfaces, that do not need to be treated. By closing the door, a pressure will be applied to the cushion. due to the fact that the cushion is compressible, it will be lightly compressed thereby adapting itself to the portion or the whole irregularity on which it is applied and sealing the opening or at least partially filling or bridging the surface irregularity. When the paint is applied to the door, the cushion will, on the one hand, prevent the paint from penetrating in the opening by absorbing that paint and, on the other hand, due to the fact that the cushion obstructs the opening or fills at least partially the irregularity, the effects due to turbulences in and around the openings are practically eliminated and will not affect the achievement of a satisfactory surface treatment. Also due to the fact that the openings are obstructed, residues of dust, humidity and others, which remain in the openings will remain enclosed therein and will no longer be affected by the pressure of compressed air and will thus no longer affect the achievement of a satisfactory surface treatment.
When the surface treatment operation is finished, the cushion is removed from the parts on which it has been applied. the substances used for the surface treatment can not reach and thus will not affect the protected surface irregularities. This is particularly the case when using an absorbing material for the cushion and which also absorbs any liquid substances used for the surface treatment. Due to the absorption capacity of the cushion, traces along the border forming the transition between the cushion which has hust been removed and the treated surface can no longer be seen. Indeed, the substance used for the surface treatment and which is applied either on the cushion or on the border between the cushion and the treated surface is now been absorbed by the cushion.
The cushion can also be applied on portions of the surface which are not damaged, or which are made from a different material as the one used for the door to be treated, such as for example the brightwork surrounding the windows.
The method according to the invention is very appropriate for application on modern vehicles having a low Cx value (in the order of 0.30; Cx=air penetration coefficient). Indeed for aerodynamical reasons some sealing gaskets are applied very close to the openings. Due to its compressibility and elasticity the cushion according to the invention allows simultaneously masking of the sealing gaskets and the opening which remains between the sealing gaskets and the coachwork.
As shown in the FIGS. 1 and 2 the cushion is an elongated cushion. Such an elongated cushion is particularly suitable to be applied on an elongated irregularity such as for example a crevise between a door, a hood or a hatch and the vehicle body. Since the cushion is elongated it can be applied practically in one piece over the whole length of the elongated irregularity, thus avoiding openings between cushion parts which could cause turbulances during the surface treatment or penetration of paint and the like between those cushionparts. Further due to the fact that the cushion is compressible and elastic it can easily be bent in all kind of corners shown by the irregularity to be masked, which offers a continuous masking. Also due to the fact that the cushion is made of elastic foam its thickness can easily be zdapted to the depth of the irregularity by simply stretching or compressing in length the elongated cushion.
Another advantage of the cushion according to the invention is that it is repositionable which offers the possibility to reposition the cushion when it has incorrectly be applied on the irregularity to be masked.
The cushion can be directly fixed to the metal body of the car or be superposed on the sealing gasket. Indeed, the adhesive characteristics of the masking gasket according to the invention allows the cushion to be applied as well on metal, rubber, as to any other materials, such as for example plastics. It is also possible to remove first the sealing gasket of the vehicle and then to masks the opening thus formed using a cushion according to the invention.
Due to the easy application and the technical characteristics of the cushion a substantial time saving of nearly two thirds of the time required for the conventional masking of a vehicle door opening using the masking tape method can be gained and thus a substantial economy realized.
The masking means according to the invention can be applied either by hand or by means of a device such as shown in FIG. 5 . The device comprises a drum or core on which the cushion is wrapped. The device is provided with an handle 7 and with three rollers 8 , 9 and 10 . The cushion 1 passes between the rollers 8 and 9 . By pressing the, roller 8 against the surface to be masked, the rolling of the latter will engage the roller 9 which on its turn will cause the cushion to unwind from the drum 6 . When the cushion comprises a protective liner covering the adhesive substance, that protective liner 3 passes between the rollers 9 and 10 . The engagement of the rollers 9 and 10 will cause the detachement and the removal of the protection liner when the cushion is applied on the surface to be masked.
The device can also be provided with a further roller on which the protective liner is rolled after it has been remoed from the cushuin. The device enables an easy and quick application of the cushion on the surface to be masked.
FIG. 6 illustrates a packing box 14 comprising a masking means according to the invention. The packing box 14 is provided with a central opening 16 through which the cushion is pulled out. The cushion is wound on a coil 15 in the same fashion as electrical wire often is marketed. This way of packing offers the advantage that the cushion is suitably protected when it is inside the box, that it remains coiled and that it can easily be pulled out of the box which during the application of the masking means can simply rest on the floor.
It is also possible to fix the device on a robot arm in which the trajectory along which the cushion has to ba applied on the irregularity to be masked is loaded into the arm's memory.
It will be clear that the invention is not only applicable on automobiles but can also be applied on all kind of surface treatment operations such as for example the painting of the frame of a window of a home or cleaning at high pressure. | A method and means for masking at least a part of a surface to be treated wherein an element that is resistant to surface treatment operations is removably applied to said part of said surface and is removed after finishing said treatment. As element a compressible cushion is applied on at least a portion of an irregularity in said surface wherein said cushion is adaptable to the irregularity on which it is applied. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
The present Application is based on International Application No. PCT/IL2008/001701 filed on Dec. 31, 2008, which is based on US Provisional Application No. 61/018,592 filed on Jan. 2, 2008.
FIELD OF THE INVENTION
The present invention relates primarily to oxygen separation membranes and, in particular, to ceramic tubes utilized in such applications.
BACKGROUND OF THE INVENTION
Ceramic membrane devices are used to efficiently separate oxygen gas using heat and electricity without any moving parts, and can even be used to produce pure oxygen under pressure by electrical current flow only. Ceramic membranes are less than one millimeter thick. At room temperature they are completely impervious to all gases, but allow oxygen to pass through when heated to high temperatures. One type of ceramic tube membrane has a porous electrode on each side of the membrane, enabling an electrical voltage difference to be applied across the membrane. At high temperature, oxygen on one side of the membrane will collect extra electrons to form negatively charged oxygen ions. These ions conduct through the membrane, being driven by the voltage difference across the membrane. In a second type, the ceramic membranes conduct both oxygen ions and electrons. When a gas pressure difference is applied across these membranes, oxygen ions form on one side by catalytic action, but their conduction through the membrane is pressure-driven, and electrons flow in the opposite direction.
Oxygen separation by ceramic membranes is based either on a solid electrolyte that conducts oxygen ions only or on a mixed ionic electronic conductor. In the first type of device with a solid electrolyte, two electrodes and leads or current collectors have to be used; and, the oxygen ionic current is driven by an applied voltage. In the second case with a mixed ionic electronic conductor, there is no need for extra layers (electrodes) and a pressure difference drives the oxygen ionic current through the permeation membrane.
Ceramic tubes are well known in industry and have many different uses. In most situations, the ceramic tubes are made of a single material, which is usually a single phase. Due to their inherent properties, ceramic tubes have been found to be of particular usefulness in oxygen separation membranes. The use of a tube comes from the need to have good sealing when separating oxygen for example. It is difficult to achieve sealing at elevated temperatures and the tube having a cold part at room temperature allows this to be achieved at room temperature.
A group of ceramic oxide materials with the perovskite structure are, in particular, used to make ceramic membranes for oxygen separation. Preferably the perovskite is Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (sometimes known as BSCFO or BSCF). This material exhibits a very high permeability of oxygen, thereby making it very well suited for oxygen separation membranes.
In order to optimize the oxygen separation process, certain electrical properties of the material are useful. This includes high electron and oxygen ion conductivities. Only certain perovskites exhibit this. Among the various suitable perovskites, BSCFO is the best, as it has a high electron (hole) conductivity, the highest ionic conductivity and thus the highest overall high oxygen permeation flux. Not only perovskites exhibit oxygen permeation, but they are among the best i.e. exhibit the highest (normalized) permeation rate.
Despite its advantages, BSCFO ceramic tubes have a key disadvantage. At temperatures below 850° C., such tubes react with CO 2 and H 2 O and can thus deteriorate. This instability is primarily caused by the components Barium (Ba) and Strontium (Sr). Further, generally any perovskite ceramic, which has either Barium or Strontium, will suffer from this same problem. The exact limiting temperature need not be 850° C., as it varies between Ba and Sr and between CO 2 and H 2 O and it depends also on the concentration of CO 2 and H 2 O. For instance 820° C. is a limiting temperature for BaO (a component in BSCFO) in the presence of ambient CO 2 concentration. In this case one could safely use 850° C. as the working temperature
Therefore, there is a need in the industry to provide a perovskite ceramic tube that will not react with CO 2 or H 2 O and deteriorate at temperatures below 850° C.
SUMMARY OF THE INVENTION
These and other objects of the present invention may be obtained from a ceramic tube made of two parts.
A first part of the tube is made of a sensitive material, such as BSCFO, for facilitating oxygen separation in the membrane. The second part is made of a different material that does not react with CO 2 or H 2 O.
The BSCFO part is kept at a high temperature (above 850° C.) at which adverse chemical reactions with CO 2 and/or H 2 O do not take place. The other material of the second part is exposed to lower temperatures down to room temperature. It need not allow permeation of oxygen. It serves to connect the active hot BSCFO part to the housing which is at room temperature
No one in the industry knew to combine two materials into one tube and thereby allowing the use of BSCFO. In point of fact, the prevailing opinion was that, while BSCFO is a very good oxygen permeation material, it cannot be used since it deteriorates with time due to interaction with CO 2 and H 2 O which are present in the atmosphere. Thus by combining BSCFO with another material, the instant invention achieves a productive, new and novel application that the industry thought could not be achieved.
Accordingly, by means of the present invention, there is provided a ceramic tube that is stabilized and does not deteriorate upon exposure to CO 2 or H 2 O when exposed to a range of temperatures below the operating temperatures.
Other features and advantages of the invention will become apparent from the following drawings and description.
BRIEF DESCRIPTION OF THE INVENTION
For a better understanding of the invention with regard to the embodiments thereof, reference is made to the accompanying drawings, in which like numerals designate corresponding elements or sections throughout, and in which:
FIG. 1 is a view showing a two part ceramic tube, according to the teaching of the present invention;
FIG. 2 is a view similar to FIG. 1 , but additionally showing a transition region between the active part and the handle part., according to the teaching of the present invention;
FIG. 3 is a cross sectional view, along line III-III of FIG. 1 , showing the composition of the material for the active part (Hot zone—Phase A); and
FIG. 4 is a cross sectional view similar to FIG. 3 , along line IV-IV of FIG. 1 , but showing the composition of the material of the handle part (Colder zone—Phase B).
DETAILED DESCRIPTION OF THE INVENTION
In a broad sense, the present invention is about using two materials to form a single tube. One material is functional for one purpose and the other for another purpose. The first material can do one task, but under certain restricting conditions; and, the second material can operate under these restricting conditions, but do something else. In this way the materials complement each other, and thereby form a single tube that can do a desired complex task.
To be specific, the task the first material does is to allow permeation of oxygen through it. This has to be done under certain conditions, i.e. high temperatures. The second material operates at lower temperatures and its task is to hold or support the first material and allow connection to a device housing at a cold end of the tube, which is at room temperature. The second material need not and in many cases cannot do the task of the first material, i.e. allow oxygen to permeate through it. Even if the second material does allow oxygen permeation, then the performance is worse as compared to that of the first material. The first material is, therefore, preferred to do the task of oxygen permeation.
The restricting condition for the first material is that it cannot be used at intermediate temperatures due to harmful interactions with CO 2 and H 2 O in the atmosphere. Carbonates and hydroxides are the products of these reactions. The first material cannot be used along the whole tube, i.e. make the tube of a single material, as there is a temperature gradient along the tube. At the high temperature end, the first material can be used. At room temperatures, it could also be used as the harmful reactions are sluggish. The problem is that part of the tube, between the part kept hottest and the part kept cold at room temperature, denoted as the “colder zone” in FIGS. 1 and 2 , would be at an intermediate temperatures range of a few hundred Celsius, where harmful reactions can occur quickly. By combining the two materials, the first part (Phase A) is kept at elevated temperatures for which the harmful reactions does not take place (in the instant case above 850° C.), while the second material (Phase B) forms the rest of the tube and is exposed to the intermediate temperatures down to room temperature.
In order to match possible differences in thermal expansion coefficients, it is preferable to also use an intermediate composition (Intermediate Composition I) of the two materials in between the above mentioned parts where each is made of one of the materials.
It turns out that heating above a certain limiting temperature is an effective method for resolving the expected adverse reaction with CO 2 as well as with H 2 O.
A standard ceramic tube used in an oxygen separation membrane is subjected to a very broad range of temperatures. At one extreme it is exposed to temperatures above 850° C., but the other extreme is room temperature (about 20° C.). The so called “cold zone” is about room temperature and is needed so that the ceramic tube can be connected to the housing of the cell. This cannot be accomplished at very high temperatures. At elevated temperatures (above 850° C.), there is no problem with using a sensitive material. The temperature is high enough that it will not react with the CO 2 or H 2 O and deteriorate. It is only when the ambient temperature is lower and the ceramic tubes are exposed to it that the problem arises.
The colder zone has a broad range of temperatures of several hundreds of degrees, extending from just below the elevated temperatures all the way down to room temperature. If it is made of only the sensitive material, the part in the lower temperature range will react with CO 2 and/or H 2 O and deteriorate.
When the cell is turned on (or off), the ceramic tube necessarily is heated (or cooled) and passes temporarily through temperatures where it will also react with CO 2 and/or H 2 O and deteriorate. To solve this additional problem is it intended to heat and cool the tube rapidly.
A ceramic tube is, therefore, proposed in the present invention that has a sensitive material (Phase A) for use at elevated temperatures and also a colder zone (Phase B) for use when connecting to the housing of the cell.
According to the present invention, the ceramic tube 10 has two parts 12 and 14 . The first part 12 is for use in the hot temperature zone and is made of an oxygen permeable material. Preferably it is perovskite and the best results seem to result from use of Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCFO). This part of the ceramic tube is kept at a sufficiently high temperature so that it does not react with CO 2 or H 2 O and deteriorate.
Among the possible other materials for the sensitive first part 12 are: La 1-x Sr x Co 1-y Fe y O 3-δ . with 0<x,y<1, in particular: x=0.2, 0.4, 0.5, y=0.2, 0.5, 0.8, 1.0 and also SrCo 0.8 Fe 0.2 O 3-δ . The best materials (highest permeation flux) contain Ba and Sr and then Ba or Sr. Others for example without Sr and Ba are LaCo 1-x Ni x O 3 , LaCo 1-x-y Fe x Ni y O 3 , x=0.1-0.2, y=0.1-0.3 and also LaGa 1-x Ni x O 3-δ . There are many other suitable substances for the sensitive part, but the permeation flux is lower than for BSFCO.
The second part 14 of the ceramic tube is generally elongate, like a type of handle. It is made of a different ceramic material and is not sensitive to CO 2 or H 2 O and does not react to them; therefore, it does not deteriorate when exposed to it. Preferably it should also not be sensitive to other harmful gases.
The harmful gases that prevail in a normal atmosphere are CO 2 and water vapor H 2 O, but they are harmful at intermediate temperatures only. At low temperatures, the reaction rate is practically zero and at elevated temperatures, such as 900° C., the products of such reaction are not stable. In particular for CO 2 , Ba forms BaCO 3 and Sr, SrCO 3 . However, this occurs below about 850° C. for room atmosphere at standard pressure of one atmosphere. The exact limiting temperature depends on whether one considers Ba or Sr and it increases when the CO 2 partial pressure or H 2 O partial pressure increases.
Necessarily the second part may not be made of Barium or Strontium or Calcium, as they react to CO 2 . Preferably it should be made of LaCoO 3-δ (Lanthanum cobaltite) or LaCo 0.8 Fe 0.2 O 3-δ (sometimes known as LCF or as doped Lanthanum cobaltite).
The preferred material of the second end is one that has a similar expansion coefficient and similar sintering temperature to the sensitive material of the first part. In most cases, the sintering temperature is about 1100-1300° C. In some applications, it may be hard to match the expansion coefficient and it may, therefore, be desirable to include an intermediate region where there is an intermediate composition which is a mixture of phases A and B. Materials that have a rather close expansion coefficient to that of BSCFO (˜18×10 −6 under reduced oxygen partial pressure of 10 −5 bar (J. F. Vente et al., J. membr. Sci., 276 (2006)178-184) and 19.7×10 −6 K −1 in air (B. Wei et al. Electrochem. Solid-State Lett. 8 (2005) A428-A431)) and can be used for the second part include: LaCo y Fe 0.2 Ni 0.2 O 3δ , y=0.5 and 0.6 with expansion coefficients (α): 18×10 −6 and 19.2×10 −6 (K −1 ) respectively (B. Wei et al. Electrochem. Solid-State Lett. 8 (2005) A428-A431).
As is known, the expansion coefficient can be tuned by slightly changing the composition of Co. This material does not contain Sr neither Ba. (It also exhibits oxygen permeation but lower and is used here for a different purpose). Other example: LaGa 0.3 Co 0.6 Mg 0.1 O 3δ , LaGa 0.4 Co 0.4 Mg 0.2 O 3δ , LaGa 0.4 Co 0.35 Mg 0.25 O 3δ , exhibit α=19.8×10 −6 , 15.4×10 −6 and 12.4×10 −6 (K −1 ) (B. Wei et al. Electrochem. Solid-State Lett. 8 (2005) A428-A431). Again small changes in composition allow tuning the expansion coefficient to match that of BSCFO. These materials do not contain Sr or Ba.
When selecting the material for the second part of the ceramic tube, it must be such that it will create a sufficiently dense and strong tube. Preferably it should have the same (or at least a similar) coefficient of expansion as the sensitive material. If there are significantly different coefficients, the integrity of the tube is obviously compromised.
As is known in the industry, the ceramic tube may be made by extrusion. First the sensitive material of the active part is extruded, followed by the inactive material for the colder zone. It may also be prepared in two parts by slip casting and gluing by sintering the parts together.
The composition of the thus ceramic extruded tube of the present invention is varied by varying the composition of the material being extruded. When material is continuously supplied from two containers, then the supply should be regulated as required. If only one container is used, then the different compositions should be placed in the correct order and supplied accordingly.
Effectively the ceramic tube has either two or three parts or phases. There is the sensitive or active portion or hot zone (part 12 ), the inactive portion or colder zone (part 14 ) and a possible transition portion (part 16 ) containing a mixture of the two materials.
One way to effect the mixing is to put into the extruder a mixture of the two materials in between the active and inactive phases (or portions). Alternatively, no mixture is used, and the extruding process itself creates mixing and inter growths of the two materials, shown in FIG. 2 .
An advantage of the transition portion is that it compensates for any small difference between the coefficients of expansion of the two materials.
Due to rapid heating, there is no longer a problem with the sensitive material being exposed to CO 2 or H 2 O and deteriorating. With new techniques, the heating can be accomplished in about 10-100 seconds. The heating rate is limited mainly by the stability of the ceramic tube. Since the sensitive material is exposed to low temperature for only a very short time, the problem of exposure to CO 2 or H 2 O and deterioration is substantially eliminated.
This new and unique two part ceramic tube is stable at elevated, continuous working temperatures and can still be used at lower temperature to connect to the housing of a cell.
The present invention is described in detail with reference to a particular embodiment, but it should be understood that various other modifications can be effected and still be within the spirit and scope of the invention, as defined by the appended claims. | The invention is a ceramic tube made of two parts. A first part of the tube is made of a sensitive material for facilitating oxygen separation in the membrane. The second part is made of a different material that does not react with CO2 and/or H2O. Accordingly, by means of this Invention, there is provided a ceramic tube that is stabilized and does not deteriorate upon exposure to CO2 and/or H2O at temperatures below the operating temperatures. | 2 |
FIELD OF THE INVENTION
The present invention generally relates to a tool for use in clampingly securing the ends of boiler tubes in aligned relation to enable the ends of the boiler tubes to be joined together by welding. More specifically, this invention relates to a boiler wall tube tool in which boiler tubes in the form of a wall can be clampingly secured to retain adjacent ends of the boiler tubes forming the wall in aligned relation when connecting the ends of the boiler tubes forming the wall when being joined by welding.
BACKGROUND OF THE INVENTION
Tools for clamping and aligning boiler tubes when connecting the ends of the boiler tubes by welding are known as disclosed in prior U.S. Pat. Nos. 4,493,139, 4,579,272 and 4,722,468. The devices disclosed in the above-mentioned patents include structures for securing boiler tube ends in aligned and adjacent relation and function effectively when the boiler tubes are in spaced relation. However, in boiler wall tubes, the boiler tubes are positioned in closely spaced relation and are interconnected by webs to form a continuous boiler tube sheet or wall. The tools disclosed in the above-mentioned patents are not especially adapted for use with boiler tubes forming a boiler wall.
Other patents disclosing tools for use with boiler walls include U.S. Pat. Nos. 4,846,931 and 4,936,500.
SUMMARY OF THE INVENTION
The water wall fit up tool of the present invention will fit a wide range of tube panel sizes such as ⅞ inch through 3¼ inch tube sizes. It uses the adjacent tubes to force the tube panel into alignment. One unit can fit up two tubes yet can be used in conjunction with two or more tools. The water wall membrane keeps the tubes rigid and the portion of the tube panel where the membrane has been removed allows for movement.
An object of the present invention is to provide a boiler wall tube tool for clampingly securing adjacent ends of boiler tubes in aligned and adjacent relation when the ends of the tubes are being connected by welding and the boiler tubes form a tube wall in the boiler.
Another object of the invention is to provide a tool in accordance with the preceding object which includes a pair of opposed bar members made of 410 stainless steel, for example, to clampingly engage a pair of adjacent ends of boiler tubes of possibly differing diameters and tube spacing to retain them in aligned and adjacent relation with each of the opposed bar members including an area providing access to the ends of the boiler tubes for welding.
A further object of the invention is to provide a boiler wall tube tool which includes a pair of clamp members having a bolt passing therethrough for moving the clamp members into clamping engagement with the adjacent ends of boiler tubes.
Still another object of the invention is to provide a tool in accordance with the preceding objects in which each of the clamp members includes different radii on opposite sides of the clamping bars.
Yet another object of the invention is to provide a tool for boiler wall tubes as set forth in the preceding objects which is simple to use, effective for its purposes and relatively inexpensive to manufacture and maintain.
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 illustrates the opposed clamping bars of the present invention as interconnected by a through bolt passing through each of the clamping bars and including a tethered magnetic plate for securely anchoring the clamping bars to a water wall so as to prevent the clamping bars from falling.
FIG. 2 is a transverse sectional view taken substantially upon a plane passing along section line 2 — 2 on FIG. 1 illustrating the structural details of one of the clamping bars.
FIG. 3 is a perspective view of a boiler wall tube assembly with the tool of the present invention installed in operative position thereon.
FIG. 4 is a transverse, sectional view taken substantially upon a plane passing along section line 4 — 4 on FIG. 3 illustrating further structural details of the tool.
FIG. 5 is a transverse sectional view taken substantially upon a plane passing along section line 4 — 4 on FIG. 3 illustrating the 180 degree rotation of the two clamping bars as compared to the clamping bars shown in FIG. 4 to illustrate a set of water wall tubes of different separation from that shown in FIG. 4 and the use of a smaller radius side of each of the clamping bars to accommodate a different separation distance of the tubes and to accommodate different tube sizes.
FIG. 6 is a side view of an alternate embodiment of opposed clamping bars.
FIG. 7 is a transverse, sectional view taken substantially upon a plane passing along section line 7 — 7 on FIG. 6 illustrating the structural details of one of the clamping bars of the alternate embodiment.
FIG. 8 is a transverse, sectional view similar to the views shown in FIGS. 4 and 5 to illustrate an alternate arrangement of clamping bars for positioning of tube ends.
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.
With reference to the drawings, in general, and to FIGS. 1 through 3 , in particular, a water wall fit up tool embodying the teachings of the subject invention is generally designated as 10 . With reference to its orientation in FIG. 1 , the tool includes two clamping bars 12 . The bars are of identical construction and are approximately 5 inches long and approximately one inch to 1 ½ inches in width. Extending through a central bore 13 of each bar 12 is a threaded bolt 15 including a tightening head 17 and a removably secured nut 19 . Bore 13 is ⅜ to 7/16 of an inch in diameter.
As shown in FIG. 2 , the clamping bar 12 includes three portions 14 , 16 and 18 . Portion 14 is of a semicircular configuration having a radius of 0.5 inches. Portion 18 is of a semicircular configuration having a radius of 0.63 inches. Interconnecting portion 16 , includes straight side walls 16 a , 16 b to interconnect the semicircular exterior configuration of portions 14 and 16 .
Each of the bars 12 includes a cable tether 20 secured at one end to the bar 12 by set screw locking the cable in a groove in the bar at an opposite end to a magnet 22 or 24 , for example. It is only necessary that one of the bars 12 include a magnet for securing the tool 10 to a water wall since bars 12 are interconnected by bolt 15 . Alternatively, each bar may include a magnet on opposite sides of the water wall. Magnets 22 and 24 are alternative exampels of a magnet configuration which may be used with the present invention. It is understood as being within the scope of the invention that alternate arrangements of a magnet may be used.
In FIG. 3 , a water wall panel 30 is shown comprised of a plurality of tubes 32 a , 32 b , 32 c , 3 d , 32 e . . . in opposed relationship with tubes 34 a , 34 b , 34 c , . . . At a location spaced from the opposed ends of the tubes 32 , 34 , adjacent tubes are welded together by weld webs 36 .
The opposed ends of the tubes 32 , 34 are therefore free to move with respect to each other. To correct the misalignment of the ends of the opposed tubes, the tool of the present invention is used to exert side pressure on the ends of the opposed tubes until the ends are in alignment.
This is accomplished by placement of a clamping bar 12 on each side of the water wall panel with a curved portion of at least one of the bars tangentially contacting the tubes of the water panel and curving in a direction opposite to a curvature of the tubes for contacting two tubes therebetween. The bolt 15 is then passed through the opposed clamping bars and tightened to draw the clamping bars towards each other. The two clamping bars can be used as a single set or in conjunction with multiple sets of clamping bars to move the ends of the opposed tubes into alignment for subsequent welding. The passage 13 through each of the bars may be cylindrical, with the diameter of the hole being slightly greater than the diameter of the bolt 15 , and due to the absence of threads, allows the clamping bars to shift slightly to accommodate different diameter boiler tubes.
In addition, as shown in FIGS. 4 and 5 , depending upon the placement of the clamping bars between the tubes 32 c and 32 d , for example, whether larger diameter portion 18 or smaller diameter 14 is used to contact the ends of the tubes, different diameter water wall tubes may be accommodated and moved into aligned position for subsequent welding. When portion 14 of the clamping bars engages the tubes, a ⅞ inch through two inch diameter water wall tube may be aligned into position. However when portion 18 of the clamping bars 12 engages the water wall tubes, a 1.75 to 3.25 inch diameter water wall tube end may be moved into alignment.
In an alternate embodiment, clamping bars 40 are configured dependent upon a specific diameter of water panel tubes to be aligned. Larger bars 40 may be used for larger diameter of water wall tubes. In addition, a flat surface 42 is used to seat a bolt head 44 of a bolt 46 as well as provide a seat for a nut 48 as shown in FIG. 8 .
In the embodiment of FIGS. 6 through 8 , the bore hole through the bars 40 is threaded to ensure a secure connection between the clamping bars 40 . This may be necessary where severe misalignment of the tube ends is present so as to ensure both vertical alignment and axial alignment of the water wall tube ends. The contact of the clamping bars with the tube ends can pull the tube ends together even if the tube ends are divergent at an angle of up to approximately 45 degrees. Alternatively, the bore hole is cylindrical having a smooth side wall as in FIGS. 4 and 5 .
The foregoing description should be considered as illustrative only of the principles of the invention. Since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and, accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | The water wall fit up tool will fit a wide range of tube panel sizes such as ⅞ inch through 3¼ inch tube sizes. It uses the adjacent tubes to force the tube panel into alignment. One unit can fit up two tubes yet can be used in conjunction with two or more tools. The water wall membrane keeps the tubes rigid and the portion of the tube panel where the membrane has been removed allows for movement. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to fastening means, in particular to positive connecting means, as for example clips for fastening of clothing strips to flat rods.
Modern textile processing machines, in particular, cards are furnished with different carding segments, depending on the process stage. Stationary carding segments and/or carding rods to the carding segments of the card belong, in particular, in the pre-carding and re-carding zone and the carding segments. Most cards nowadays are furnished with revolving flat aggregates, i.e., they possess revolving flat rods. Cards with stationary flats and, respective, stationary flat rods are less common. With cards, it is common to furnish the flat or revolving flat rods with so-called clothing strips. The clothing strips are furnished with flexible or semi-rigid clothing, which differ from all steel clothing and/or saw tooth type clothing in such a way, that they are inserted and/or punched individually, or as U-shaped double hooks, into more or less flexible fabric and plastic layers.
The clothing strips are attached with fastening means, so-called clips or clothing strip clips, to the carding rods of the carding segments. Various clips of the state of the art are shown, for example, in the disclosures U.S. Pat. No. 5,755,012, U.S. Pat. No. 5,898,978 and DE 513728. Such an arrangement is, for example, also shown in FIG. 1 . The clips 1 are made of sheet metal and/or steel and they advantageously simplify the fastening and replacing of the clothing strips 2 onto the flat rods 3 . The clips 1 have the function of fixedly clamping the clothing strips 2 onto the flat rods. They do this by establishing a positive connection between the clothing strip and the flat rod. Normally, the clips are employed in pairs, so that a clip is to ensure for respective clamping on both sides of the flat rod (see FIG. 1 ). On one side, the clips have teeth 4 . These teeth 4 are inserted and/or punched into the clothing strips 2 (illustrated in FIG. 1 with a broken line). Thereby, these teeth 4 are positively connected with the clothing strip. The other side 5 of the clips is pressed around the rib 6 of the flat rod 3 by applying a suitable tool. Thus, the clips 1 firmly clamp the clothing strips 2 to the flat rod 3 over its entire length. This type of fastening has proved successful in the past. The clips can be attached very easily to the flat rods with a suitable tool and can also be easily removed again.
The carding rods, and in particular the flat rods for the card, were formerly manufactured in the form of a—usually T-shaped—cast iron. Recently they have also been manufactured in the form of hollow profiles (extruded profiles) of light metal and/or light metal alloys (e.g., flat rod 3 in FIG. 1 ). Aluminum is often used as a material for the production. The carding segments co-operate with rotary rollers, as do the flat rods, which co-operate with the cylinder of the card. Thereby, the carding rods or flat rods must be somewhat longer than the working width of the card, so that they can rest on the adjustable flex bends on the left and on the right side of the cylinder and can be transported (or, in the case of stationary flat rods, be fastened thereon). The flat rods are exposed to a relatively high mechanical load (shearing load) applied through their carding work. Therefore, they must have a high stability or rigidity, in order not to deflect or deform during operation.
The carding quality, and thus the quality of the produced card web, depends substantially on the set carding gap (space between the clothing of the flat rods and the clothing of the cylinders). This carding gap is nowadays adjusted within the range of tenth of millimeters. Usually, it measures between 0.2 and 0.3 mm, depending on the processed fibre material and the desired carding quality. It can be observed that the tendency in the spinning mills points in the direction of setting or adjusting the carding gap within ever more narrow ranges. Carding gap settings of 0.15 mm represent at the present the rather extreme case, however, such narrow settings might be wished in the future more frequently by spinning mills. Therefore, the accurate setting of the carding gap is very important. It is, therefore, understood that fluctuations and inaccuracies in the adjusted space have considerable negative effects on the quality of the carding process. For the carding process it is very important that the carding gap over the entire work area within which carding work is done can be adjusted evenly. For example, the carding gap must be accurately adjusted over the total length of the flat rods and over the whole area of the flat (i.e., within the work area of all flat rods being arranged one behind the other). The narrower, however, the carding gap is chosen, the more difficult it is to adjust it and to keep it constant. The narrower the range gets within which the carding gap is to be kept, the more sensitive the flat area reacts, with the set carding gap, to each effect and to each change, like for example temperature fluctuations. The carding gap is adjusted and/or checked during standstill with a feeler gauge. Usually this setting takes place once in each case after each adjustment of the flats of the card, for example, after maintenance (the replacement of the flats) or in the case of a change of the processed material (fiber material to be treated newly often requires another carding gap adjustment). Adjusting of the flats actually always takes place on the “cold machine”, i.e. at normal ambient temperature, which can differ, depending on the location of the machine within the spinning mill, between 20 and 30 degrees Celsius. During operation of the card, the operating temperatures at the flat rods, depending on the air conditioning, can amount to between 20 degrees Celsius (during starting period of the machine) and 40 degrees Celsius (with a warm machine and bad air conditioning within the spinning mill). It is understood that the carding gap, even with such temperature fluctuations, is always to be held at the desired value. However, the narrower the carding gap needs to be adjusted, the more sensitive is the reactions of the carding process to changes of the gap.
Recently, the flat rods have been made of light metal, in particular of aluminum, and/or of light metal alloys as extruded hollow profiles, produced by extrusion method (see FIG. 1 ). Such flat rods are provided with solid headpieces at their two ends. Examples of such flat rods can be seen in the disclosures DE 43 04 148 A1, EP 627,507 B1 or U.S. Pat. No. 4,827,573. The headpieces are usually positively connected with the aluminum profile and have a machined bearing surface, which slides accurately and with low friction on the sliding guides of the card (flex bends). In the case of revolving flat rods, the headpieces are furthermore connected with the drive components of the flat aggregate, e.g., with a driving chain or a driving belt. This design has a number of advantages in comparison to the older type flat rods made as casting. In particular, they can be manufactured more simply and cheaper.
The use of light metal or light metal alloys as material for the flat rods can, however,—under certain operating conditions—also have disadvantages. With such types of flat rods up to now, common type clips made of sheet metal or steel were used. Measurements now revealed that these flat rods can deform when the temperature rises to the operating temperature in the card. The reason for this is that the clips are mounted onto the flat rods at room temperature. In the case of a temperature rise of the card to the operating temperature, the mounted flat rods resume a concave type of shape seen in their longitudinal direction, so that the carding gap is larger in the center of the flat rod than at its end. Thus, the carding process can be impaired. The impairment of the carding process is the more serious the narrower the carding gap is set and the longer the flat rods are. With the carding gap settings applied nowadays, it should therefore be avoided that the flat rods become bent.
OBJECTS AND SUMMARY OF THE INVENTION
Therefore, a principal object of the present invention is thus to avoid the deformation of the flat rods. Additional objects and advantages of the invention will be set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the invention.
The light metal or the light metal alloy of the flat rods has a higher coefficient of elongation and/or coefficient of thermal expansion than the sheet metal and/or the steel from which the clip is made. The commercially available clips thus consist of a material (sheet metal or steel) that has a too high E-modulus for flat rods made of light metal, i.e., they have a low flexibility. They are, in particular, far less flexible than the flat rods. In addition, the clips, apart from the material properties, also have (primarily due to the selected wall thickness) a high rigidity due to the design. In the mounted condition, the clips have a high clamping force and are, practically seen, inelastic. The wall thickness of commercially available clips amounts to at least 0.5 mm. The clothing strips are positively connected (“clipped-on”) onto the flat rod at room temperature with the help of the clips and a suitable tool. Afterwards the flat rods are examined for their accuracy with regard to the clothing. If necessary, the clothing points are reground (by a few hundredths of a millimeter), so that the gap between the sliding surfaces of the head pieces of the flat and the area defined by the clothing points resume an accurate predetermined value. This examination is accomplished in the spinning mills at ambient temperature and is made in order to precisely adjust the carding gap. The flat rods with the attached clips and clothing strips are subsequently mounted into the card, at which point they have the ambient temperature. If the card becomes warm through its operation, then also the flat rods warm-up. Consequently, the flat rods expand (or try to expand). The problem, thereby, is that the flat rod has, due to the material type (light metal or a respective alloy), a higher coefficient of thermal expansion than the clip (commercially made of sheet metal or steel). Besides, the clip has, due to the applied material, a high E-modulus (low elasticity), which is additionally reinforced due to its design (wall thickness). The result is a high strength connected with a very low elasticity (at least a lower elasticity than the flat rod). The positive connection of the clips (at least two clips per flat rod are required for the fastening) with the flat rod within the area of the ribs 6 (see FIG. 1 ) has a high clamping force. It is so high that no relative motion can take place at these points between the flat rod and the strip. In particular, the material with the higher coefficient of elongation cannot expand. Consequently, the lower thermal expansion of the clips prevents the flat rod from expanding within the clamped section 7 in the same way in longitudinal direction as within the upper non-clamped section 8 of the flat rod, where no obstacle prevents the thermal expansion. The arc-shaped bend of the flat rod resulting from this causes an undesired, non-uniform carding gap over the length of the carding flat. Particularly, with narrow settings, where the carding gap is to amount to between 0.2 to 0.15 mm, then this effect is particularly negative.
According to the general idea of the invention, it is to be avoided that the flat rod, due to the fastening device, i.e., the clip, is prevented from expanding evenly. This idea can be realized by different embodiments according to the invention.
According to a first embodiment of the invention, the fastening devices are made of a material that possesses the same coefficient of elongation as the flat rod. In a particularly preferred embodiment, the fastening devices are made of, thereby, also at the same time, of the same material as the flat rod. According to this embodiment of the invention, it is essential that light metal flat rods are being used in combination with the fastening devices (clothing clips), which, according to the invention, comprise the same (or nearly the same) material characteristics.
This first embodiment according to the invention refers to flat rods that are not manufactured of steel or cast iron. It refers, in particular, to flat rods that are manufactured of a light metal or a light metal alloy, in particular, aluminum or an aluminum alloy.
In a second embodiment according to the invention, fastening devices for the fastening of clothing strips on flat rods are used, which are made of aluminum, or aluminum alloy, or another light metal or light metal alloy. This second embodiment according to the invention is concerned with the selection of the material from which the fastening devices are made. In a secondary embodiment the flat rods can be made of a light metal or a light metal alloy, in particular, they can be made of aluminum or an aluminum alloy.
According to a third embodiment of the invention, fastening device for fastening the clothing strips on flat rods are applied that are characterized in that the fastening means are more flexible in their longitudinal direction than in their cross direction.
Such fastening means, or devices, can have such characteristics due to their specific way of design.
These can be realized in particular in that they are designed with predetermined weak points. Such predetermined weak points can be realized in such a manner that the fastening means, with regard to their extension, have different values of elasticity.
In a fourth embodiment according to the invention, fastening devices for fastening the clothing strips on flat rods are applied that have a wall thickness which is smaller than 0.4 preferably smaller than 0.3 mm. By this design measure, it is in particular suitable to apply well known materials for the fastening means, for example, sheet metal or steel. Due to the small cross-section and/or wall thickness, the fastening means, despite an unchanged high E-modulus, is structurally weakened and therefore less rigid. Thereby, the flat rod is given the possibility to expand the fastening means, i.e., the clips, in a longitudinal direction. In fact, the structural weakening reduces the clamping force of the fastening means. The wall thickness however can be selected in such a manner that the weakening does not critically affect the clamping force.
A fifth embodiment according to the invention is characterized in that, between the contact surfaces of the fastening means, or device, and the flat rod, a sliding means is attached.
The sliding means is arranged in such a manner, that it permits the fastening means, as well as the flat rod, to move and/or expand in a longitudinal direction (i.e., along the flat rod) relative to the other element. This relative motion in the longitudinal direction takes place in particular when the temperature of the flat rod rises, so that the component with the higher coefficient of elongation (e.g., the flat rod) can expand in the longitudinal direction unhindered from the other component (e.g., fastening means). This basically means that the fastening means does not have to take part in this movement or expansion of the flat rod: The flat rod can expand unhindered, and, thus, no tensions can develop, which could cause a bending of the components. The clamping effect of the fastening means (transverse to the longitudinal direction of the flat rod) does not become affected.
In a variation of this fifth embodiment, the sliding means between the contact surfaces of fastening means and flat rod is realized as a glide layer with a low coefficient of friction.
With this embodiment of the invention, the flat rod is preferably made of a light metal or a light metal alloy. In particular, it is made of aluminum or an aluminum alloy.
The object of the invention, which in all foregoing embodiments of the invention is called “fastening means, or device” can also be a so-called clip, in particular, for fastening of clothing strips onto flat rods (revolving flat or stationary flat rods) of the card. In addition, the clothing strips can be furnished with an allsteel clothing (saw tooth type clothing). The object of the invention is not limited to the application in flat rods of the card. It can also serve, in particular, as fastening means for other carding segments with other clothing types (carding segments of the card, such as those of other blow room machine, in particular, cleaners). The object of the invention is also preferentially suitable as a fastening means for carding segments with all steel clothing. The fastening means according to the invention can therefore also be applied in other carding segments in the card or in a cleaner of the blow room. Together, with the card go the carding segments in the pre-carding zone or re-carding zone of the cylinder, or the carding segments at the licker-in. With cleaners, the fastening means can be applied with stationary carding segments. If the fastening means is a clip, then it can be made of sheet metal, preferably of steel.
If the sliding means between the contact surfaces of fastening means and flat rod is being realized as a gliding layer with a low coefficient of friction, then the gliding layer can be applied in the form of a coating, in particular, a plastic coating, on the fastening means and/or on the flat rod. The application of the coating can also take place later. In a preferred embodiment, the coating is applied only on the contact surfaces between the fastening means and the flat rod.
In a further preferred embodiment of the invention, the fastening device has teeth, which are stable enough to be entered or punched into the fabric and/or plastic layers of the clothing strips. This feature applies in particular to fastening means which are not made of steel or sheet metal, but, for example, are made of aluminum or some other material. Such fastening means according to the invention are, in particular, suitable for the fastening of clothing strips on machine components of the card.
For the fastening of the clothing strips on the flat ends preferably at least two fastening means are applied according to the invention.
The present invention is further described in the following figures by ways of examples.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a flat rod with clips according to the state of the known art;
FIG. 2 shows a fastening means according to an embodiment of the invention;
FIG. 3 shows a variation according to another embodiment of the invention;
FIG. 4 shows a fastening means according to a further embodiment of the invention with sliding means; and
FIG. 5 shows a further fastening means according to the invention.
DETAILED DESCRIPTION
Reference will now be made in detail to the presently preferred embodiments of the invention, one or more examples of which are shown in the figures. Each example is provided to explain the invention and not as a limitation of the invention. In fact, features illustrated or described as part of one embodiment can be used with another embodiment to yield still a further embodiment. It is intended that the present invention cover such modifications and variations.
The flat rod in FIG. 1 was already described further above. Therefore, there is no need for further explanation. The clips 1 are manufactured of sheet metal or steel according to the state of the art and have a wall thickness of 0.5 mm. The flat rod 3 is made of a light metal or a light metal alloy. This combination has the above-described disadvantages.
In FIG. 2 , a fastening means, or device, according to an embodiment of the invention is shown (in two views). The fastening means 9 according to the invention is more flexible in its longitudinal direction 10 than in its transverse direction 11 . This characteristic was achieved at the fastening means 9 by way of its structural design. It has groove shaped predetermined weak points 12 at regular spaces in its longitudinal direction 10 . The wall thickness is reduced at these points, so that the fastening means 9 has an overall reduced rigidity in longitudinal direction 10 and thus a higher elasticity. By this structural design, the clamping force in cross direction 11 is hardly reduced and the elasticity of the fastening means 9 is only insignificantly increased.
The FIG. 3 shows a further variation of the embodiment in FIG. 2 according to the invention, likewise in two views. Here also, predetermined weak points 12 in the form of punched material are worked into the fastening means, or device, 13 . Thus, the fastening means receive a direction-controlled elasticity and/or rigidity, and thus the fastening means 13 becomes lengthwise flexible. In cross direction 11 , however, it keeps the required rigidity.
The FIG. 4 shows a flat rod 3 . 1 with a clothing strip 2 , which is attached by two fastening means, or devices, 15 according to the further embodiment of the invention.
Between the contact surfaces of fastening means 15 and the flat rod 3 . 1 sliding means 14 are attached. In this embodiment, the two fastening means 15 also have teeth 4 , which engage in the clothing strip 2 of the fabric layer. The sliding means 14 are here only to be understood as schematic illustrations. They permit the flat rod 3 . 1 and the fastening means 15 to move relatively to each other (in viewing direction, i.e., in a longitudinal direction of the flat rod 3 . 1 ), in particular to expand relatively to each other at a temperature rise. As sliding means 14 , gliding layers could, for example, be applied, which have a low coefficient of friction. The sliding means 14 can be applied both on the fastening means 15 and/or on the flat rod 3 . 1 . The sliding means 14 can only be attached on the contact surfaces (as shown), or extend beyond one and/or the other component (fastening means 15 or flat rod 3 . 1 ) covering it entirely or partly (not shown). For example, the fastening means 15 could be completely surrounded and/or coated by the sliding means 14 . The illustrated sliding means 14 can also be a plastic coating (or a silicone layer).
The FIG. 5 shows a detail of a fastening means, or device, 16 according to the invention. Thereby the fastening means 16 is shown in two conditions. The illustration on the left shows the fastening means 16 in the unbent condition on which one sees in particular the teeth 4 .
According to one design of an embodiment of the invention, the fastening means 16 can comprise a wall thickness d, which is thinner than 0.4 mm, preferably thinner than 0.3 mm.
The illustration on the right shows the fastening means 16 in the form as it is applied in mounted condition (without flat rod or clothing strip). One sees the way the teeth 4 are pointing upward. During a normal assembly, these are punched and/or pressed into the fabric layers of the clothing strip (see teeth of FIG. 4 ). The teeth 4 according to the invention are designed in such a manner (e.g., by their form and dimensions) that they are stable enough in order to be engaged in the fabrics and/or plastic layers of the clothing strips.
The fastening means according to the invention consists preferably of a material which possesses the same coefficient of elongation as light metal or light metal alloys, under which particularly is to be understood aluminium or aluminium alloys. The fastening means consists in particular of a material which possesses the same coefficient of elongation as the material of which the flat rods are manufactured, whereby these are preferably produced of light metal or light metal alloys.
The invention also concerns the use of fastening means on the flat rods, made of light metal, for the fastening of clothing strips.
With the expression “fastening means” clips for the fastening of clothing are to be understood in particular. These clothing could be flexible clothing, in particular so-called clothing strips, but also allsteel clothing, e.g. saw tooth clothing. Preferably the fastening means according to the invention are applied for the flat rods of the card. They are, however, not limited to this application. The fastening means according to the invention can in particular also serve for the fastening of other carding segments, in particular for stationary carding segments in the pre-carding zone and in the re-carding zone of the card, as well as at its licker-in and at cleaners in the blow room. The fastening means according to the invention can be used for example for applications according to the disclosures CH 659,832, CH 654,341, CH 655,521 in place of the conventional clips or clips described there, in particular for holding allsteel clothing and so-called card clothing.
The invention is not limited to the possibilities and embodiments explicitly being specified. These variations are rather meant as suggestions for the specialist for the realisation of the idea of the invention in a most favourable manner. From the described forms of embodiments, therefore, further favorable applications and combinations are easily derivable, which likewise reflect the idea of the invention and which are to be protected by this application. It will be appreciated by those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the invention. It is intended that the present invention include such modifications and variations as come within the scope of the appended claims and their equivalents. | The invention relates to fastening means (in particular to so called clothing clips) for the fastening of clothing strips on flat rods, made of light metal or light metal alloys. Thereby the fastening means are laid-out in such a manner that, when the flat rods assume their operating temperature, these are not deformed. | 3 |
BACKGROUND OF THE INVENTION
The invention relates to a weft thread conveying apparatus for shuttleless weaving machines, more particularly for nozzle-type weaving machines having two insertion nozzles, with a pair of conveying rollers which are capable of being driven continuously.
In a known weft thread conveying apparatus of this kind, there are provided two pairs of conveying rollers which can be driven separately from one another, the first conveying roller of each pair being situated in a stationary fashion and each second roller being capable of being lifted away from the first roller associated with it to an extent which prevents the conveying of the weft thread. The two conveying rollers of each pair are in each case connected with toothed wheels which are kept constantly in engagement with one another.
When each second conveying roller is lifted away from the first conveying roller associated with it, the associated toothed wheels are also moved away from one another but only to such an extent that they remain in engagement in one another.
This movement of the toothed wheels associated with the conveying rollers relatively to one another has the effect that in the event of the larger inter-axes spacing of the toothed wheels corresponding to the lifted-away position of the second conveying roller, the teeth of the said wheels run with a relatively considerable amount of play. This results on the one hand in increasing the amount of noise produced to a considerable extent and on the other hand results in an increased amount of wear on the toothed wheels.
The closest prior art known to applicant in connection with this application is U.S. Pat. No. 3,885,599.
SUMMARY OF THE INVENTION
The present invention obviates the aforesaid disadvantages in that the pair of conveying rollers is formed by two rollers the periphery of which consists in each case of two conical peripheral portions situated at an inclination to one another and each intended to convey one weft thread, these peripheral portions extending upwards from the edge of the roller towards the middle of the roller, and one of the two conveying rollers is mounted to be capable of tilting movement for the selective pressure application of one of its peripheral portions against the corresponding peripheral portion of the other conveying roller.
Thus in contrast to the known apparatus, the weft thread conveying apparatus according to the present invention comprises only a single pair of conveying rollers, but owing to the conical peripheral portions of these rollers they can convey two weft threads. Since the conveying rollers do not have any driving toothed wheels which are moved away from one another and towards one another, the problems involved with this movement of the toothed wheels are also eliminated.
The invention also concerns a weft thread conveying apparatus for nozzle-type weaving machines which can be used for the conveying of more than two weft threads, for example four different weft threads.
This weft thread conveying apparatus is characterized in that a plurality of pairs of conveying rollers are provided, and there are associated with each pair of conveying rollers two insertion nozzles, and that each of the rollers comprises a third peripheral portion situated between the two conical peripheral portions and in the form of a straight circular cylinder; and when the two rollers of a pair of conveying rollers abut on one another at their third peripheral portions, the two associated weft threads are released and are not conveyed.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and advantages of the invention will become apparent from the detailed explanation with reference to constructional examples and the illustrations shown in the drawings, in which:
FIG. 1 is a diagrammatic plan view showing a nozzle-type weaving machine utilizing the invention;
FIG. 2 is a view in perspective showing a detail of the single pair of conveying rollers;
FIG. 3 is a view in the direction of the arrow III of FIG. 2;
FIG. 4 is a diagrammatic plan view showing a nozzle-type weaving machine for four-color operation;
FIG. 5 is a perspective view showing a pair of conveying rollers of the weft thread conveying apparatus of the weaving machine shown in FIG. 4; and
FIGS. 6 and 7 are diagrammatic views each showing two pairs of conveying rollers and their control mechanism.
DESCRIPTION OF PREFERRED EMBODIMENTS
The nozzle-type weaving machine shown in FIG. 1 is of the type as described in U.S. Pat. No. 3,885,599 and shows substantially a warp beam 1 from which warp threads 2 run over shafts 3 to a beaten-up edge 4 of fabric 8 formed during the weaving operation, a reed 5, a picking or insertion device 6, and a beam 7 on which the fabric is wound.
At one side of the weaving machine frame there is arranged a holder (not shown) for two weft thread bobbins 9, and weft threads S 1 , S 2 , respectively, which are drawn from each of these bobbins by a conveying apparatus 10. Between the weft thread bobbins 9 and the conveying apparatus 10 and also immediately upstream of the insertion device 6 there is provided for each weft thread S 1 , S 2 a controlled thread brake 11 and 12 respectively. Each of the thread brakes 11 and 12 respectively comprises a pair of clamping discs between which a weft thread S 1 and S 2 passes. In each pair of discs, one disc is capable of being lifted away from the other disc so that the weft thread in the lifted-away position can travel freely through between the discs and is clamped fast in the other position of the discs. The weft threads S 1 and S 2 are guided from the conveying apparatus 10 by way of guide rollers to a storage device 13 and run from this device over further guide rollers and through the thread brakes 12 to the insertion device 6.
The storage device 13 has a shape resembling a tuning fork with a U-shaped storage portion and a suction tube extending away from the bottom of the U-shaped portion. The tube is connected to a suction source 13a by means of which air can be drawn continuously through the two legs of the U-shaped storage portion. This air suction carries along a weft thread S 1 , S 2 conveyed by the conveying device 10, and draws it into the particular leg of the storage portion.
The insertion device 6 is formed of a stationary, multiple nozzle arrangement, for example a double nozzle. A nozzle arrangement of this kind, formed essentially of two nozzles in the form of small curved tubes, is described in Swiss Pat. No. 571,597 and in U.S. Pat. No. 4,081,000. In a nozzle arrangement of this kind, owing to the compact arrangement, the positioning operations which are usually required at each weft thread change for the individual nozzles are dispensed with.
Each nozzle of the insertion device 6, through each of which a weft thread S 1 or S 2 runs, is connected by way of a fluid conduit 14 to a change-over valve 15. The change-over valve 15 is connected by way of a conduit 16 to a pump means 14a. The pump means conveys intermittently a fluid which is fed by way of the change-over valve 15 of the nozzle of the insertion device 6 which is required at the instant in question, whereupon the particular weft thread S 1 or S 2 is introduced into the shed in the direction indicated by an arrow. A weft thread parting device 17 is arranged in the space between the insertion device 6 and the adjacent fabric edge.
At the side of the machine frame situated opposite from the insertion device 6 there is situated a program setter means 18 which, by means of a given program, controls the operations of the thread brakes 11 and 12, the conveying apparatus 10, and the change-over valve 15. The program setter means 18 is connected with all these elements, but for the sake of leaving the drawings easier to read, only the connection 19 between the program setter means 18 and the conveying apparatus 10 is shown. The control of the conveying of the fluid in the conduit 16 is effected by coupling the pump means 14a, connected to the conduit 16, with the drive of the weaving machine.
In FIGS. 2 and 3 the conveying apparatus 10 shown in FIG. 1 illustrates substantially a pair of conveying rollers comprising a measuring roller 20 and a pressure roller 21. The measuring roller 20 is mounted on a driving shaft 22 and during operation rotates constantly in the direction indicated by an arrow. The pressure roller 21 is mounted to be capable of free rotational movement by means of a shaft 23 in the fork-shaped end 24 of a two-arm lever 25. The fork 25 is mounted approximately at its central portion on a stationary pivot pin 26. The other end of the lever 25 is connected pivotably to an operating lever 27 capable of being controlled by program setter means 18 by way of a connection 19. At the central portion of the lever 25 mounted on the pivot pin 26 for movement about the said pin there are situated two guide eyelets 28 for the weft threads S 1 , S 2 .
The periphery of the measuring roller 20 and the periphery of the pressure roller 21 consists in each case of two conical peripheral portions 29, 30 and 31, 32 respectively which are inclined relatively to one another. These peripheral portions have an outline which extends upwards from the edge of the roller towards the middle of the roller. A weft thread S 1 and S 2 respectively abuts tangentially on each of the peripheral portions 29, 30 of the measuring roller 20.
The pressure roller 21 can be tilted by the operating lever 27 so that one of its conical peripheral portions 31 or 32 selectively can be pressed against the corresponding peripheral portion 29 or 30 as appropriate of the measuring roller 20, and accordingly the other of its conical peripheral portions is lifted away from its associated peripheral portion on the measuring roller 20. As a result, in dependence on the pivoted position of the lever 25, the weft thread situated between the pressed-together peripheral portions of the two rollers is the one which is conveyed in each case, and the weft thread situated between the peripheral portions lifted away from one another remains stationary.
The measuring roller 20 and the pressure roller 21 always abut on one another at their highest surface line, i.e., at the surface line with the largest circumference. Since the measuring roller 20 is constantly driven and the pressure roller 21 abuts constantly at its highest surface line against the measuring roller 20, the pressure roller 21 is also in continual rotation. The angle between the two pivoted positions of the lever 25 which is shown with full lines and broken lines in FIG. 3 amounts to about 6°.
In the position of lever 25 and pressure roller 21 which is shown in FIG. 2 and in FIG. 3 (full-line position of lever 25 and pressure roller 21) the peripheral portion 31 of the pressure roller 21 is pressed against the peripheral portion 28 of the measuring roller 20 and the peripheral portion 32 of the pressure roller 21 is lifted away from the peripheral portion 30 of the measuring roller 21. Accordingly the weft thread S 1 is conveyed and the weft thread S 2 remains at rest.
Another embodiment is shown in FIG. 4 in which the nozzle-type weaving machine is for four-color operation and differs from that shown in FIG. 1 in that there are provided four weft thread bobbins 9, from each of which a weft thread S 1 , S 2 , S 3 , S 4 is drawn off, that there are in each case four thread brakes 11 and 12, and two storage devices 13, and that the insertion device 6 is constituted by a quadruple nozzle. A quadruple nozzle of this kind is described in Swiss Pat. No. 571,797 and in copending U.S. patent application Ser. No. 758,763.
In FIGS. 5 through 7 the conveying apparatus 10 shown in FIG. 4 consists substantially of two pairs of conveying rollers comprising a measuring roller 20 or 20' and a pressure roller 21 or 21'. The measuring rollers 20 and 20' are mounted on a common driving shaft 22 and during operation rotate constantly in the direction indicated by an arrow. Each pressure roller 21, 21' is mounted by way of a shaft 23, 23' to be freely rotatable in the fork-shaped end 24, 24' of a two-arm lever 25, 25'. Each lever 25, 25' is mounted substantially at its central portion on a stationary pivot pin 26, 26'. The other end of each lever 25, 25' is connected pivotably to an operating lever 27, 27' which can be controlled by the program setter means 18 by way of a connection 19 and a control mechanism. Two pairs of guide eyelets 28 and 28' in each case for the weft threads S 1 , S 2 , S 3 and S 4 are arranged on the central portion of the levers 25, 25' mounted on the pivot pin 26, 26'.
The periphery of the measuring rollers 20, 20' and of the pressure rollers 21, 21' consists in each case of two first and second conical peripheral portions which are inclined relatively to one another, 29, 30 and 31, 32 on the one hand and 29', 30' and 31', 32' on the other hand, and of a third peripheral portion 33, 34 on the one hand and 33', 34' on the other hand which is arranged between the conical peripheral portions and is in the form of a straight circular cylinder. The first and second peripheral portions comprise an upwardly extending outline from the edge of the roller to the third peripheral portion. A weft thread S 1 , S 2 , S 3 , S 4 abuts tangentially on each of the first and second peripheral portions 29, 30 and 29', 30' of the measuring roller 20 and 20' respectively.
The pressure rollers 21, 21' can be swung or tilted by the operating lever 27 or 27' respectively in such a manner that selectively one of their peripheral portions 31, 31', 32, 32' or 34, 34' is pressed against the corresponding peripheral portion 29, 29', 30, 30' or 33, 33' respectively of the measuring rollers 20, 20', and the other of their peripheral portions are correspondingly lifted away from their associated peripheral portion on the measuring roller 20, 20'. In this way, in accordance with the tilted position of the lever 25, 25', in each case the weft thread situated between the pressed-together conical peripheral portions of two rollers is the one which is conveyed, and the weft threads which are situated between the conical peripheral portions which are lifted away from one another remain stationary, and at each pair of conveying rollers which does not have a weft thread to convey, in FIG. 6 this is the left-hand pair of conveying rollers 20, 21, measuring roller 20 and pressure roller 21 are pressed together at their third peripheral portion 33, 34 and as a result run idly and do not convey a weft thread.
The measuring rollers 20, 20' and the pressure rollers 21, 21' abut constantly on one another at one of their peripheral portions. Since the measuring rollers 20, 20' are continually driven, the pressure rollers 21, 21' are also constantly in rotation. The angle between the two extreme positions of the levers 25, 25' amounts to about 6°.
In the position of the levers 25, 25' and pressure rollers 21, 21' shown in FIG. 6, the peripheral portion 34' of the pressure roller 21' is pressed against the peripheral portion 33' of the measuring roller 20' and the peripheral portion 31 of the pressure roller 21 is pressed against the peripheral portion 29 of the measuring roller 20. Correspondingly the weft thread S 3 is conveyed and the weft threads S 1 , S 2 and S 4 remain stationary.
The operating levers 27, 27' are each pivotably connected on an arm of a common three-arm lever 36 which is pivotable about a bearing point 35 adjustable into two positions E and F. The third arm of the lever 36 is connected pivotably by way of an intermediate rod 37 to one end of a two-arm control lever 39, a first control lever pivotable about a first fixed bearing 38. The other end of the first control lever 39 is connected to the connection 19 leading to the program setter means 18, see FIG. 4.
The bearing point 35 of the three-arm lever 36 is situated at one end of a pivotable rod 40 whose other end is secured pivotably on a second stationary bearing 41. The pivotable rod 40 is connected pivotably by means of an intermediate rod 42 to one end of a right-angled second control lever 43. The second control lever 43 is pivotably mounted at its apex at the stationary bearing point 38 and is connected at its other end to the connection 19 leading to the program setter means 18.
The operation of the control mechanism just described for the operating levers 27, 27' will now be described in conjunction with FIGS. 6 and 7: The first and second control levers 39 and 43 are each pivotable between two pivoted positions A and B on the one hand and C and D on the other hand. When the second control lever 43, whereby the bearing point 35 of the three-arm lever 36 is secured, is in its pivoted position C, the bearing point 35 is pivoted towards the right, that is to say into the pivoted position F. The pivoted position E of the bearing point 35 corresponds to the pivoted position D of the second control lever 43.
In each pivoted position of one control lever, the other control lever can take up two different pivoted positions, and vice versa.
When for example the second control lever 43 is in the pivoted position C (FIG. 6), the first control lever 39 can take up the two pivoted positions A or B. In pivoted position A (FIG. 6, lever positions shown in full lines), the pressure roller 21' of the left-hand pair of conveying rollers 20', 21' is in its neutral conveying position N' in which none of the weft threads S 1 or S 2 is conveyed. In the case of the right-hand pair of conveying rollers 20, 21, the pressure roller 21 is tilted over towards the left so that the weft thread S 3 is conveyed and the weft thread S 4 is not conveyed.
If, with the pivoted position C of the second control lever 43 unaltered, the first control lever 39 takes up the pivoted position B (FIG. 6, lever positions shown in broken lines) at the left-hand pair of conveying rollers 20', 21', the pressure roller 21' is tilted over towards the left and the weft thread S 1 is conveyed and the weft thread S 2 is not conveyed. At the right-hand pair of conveying rollers 20, 21 the pressure roller 21 is tilted over into its neutral conveying position N so that none of the weft threads S 3 or S 4 is conveyed.
If the second control lever 43 is in the pivoted position D (FIG. 7), the first control lever 39 can also take up the two pivoted positions A or B: In the pivoted position A (FIG. 7, lever positions shown in full lines) at the left-hand pair of conveying rollers 20', 21' the pressure roller 21' is tilted over towards the right and the weft thread S 2 is conveyed, and the weft thread S 1 is not conveyed.
In the case of the right-hand pair of conveying rollers 20, 21 the pressure roller 21 is tilted over into its neutral conveying position N, so that neither of the weft threads S 3 or S 4 is conveyed.
If with the pivoted position D of the second control lever 43 unaltered, the first control lever 39 takes up the pivoted position B (FIG. 7, lever positions shown in broken lines) at the left-hand pair of conveying rollers 20', 21' the pressure roller 21' is tilted into its neutral conveying position N', so that neither of the weft threads S 1 or S 2 is conveyed. In the case of the right-hand pair of conveying rollers 20, 21 the pressure roller 21 is tilted over towards the right and the weft thread S 4 is conveyed and the weft thread S 3 is not conveyed.
It will be appreciated that each of the two operating levers 27, 27' could be connected to a separate control mechanism. These control mechanisms, however, have to ensure not only that in that particular pair of conveying rollers which does not have a weft thread to convey, the pressure roller 21 or 21' is in its neutral conveying position N or N' respectively, but also that when one pair of conveying rollers is conveying the other pair reliably must not convey. To meet this second condition, a coupling in the manner of a locking device must be provided between the two control mechanisms. It has been found that the control mechanism shown in FIGS. 6 and 7 meets both conditions in the best possible way and with simple means.
It will be appreciated further that the weft thread conveying apparatus according to the invention is of course not limited to being used on four-color nozzle weaving machines, but, by arranging a plurality of pairs of conveying rollers in a series can be expanded to deal with any number of colors without altering anything in the essential features of the subject of the invention.
It is submitted that the corresponding arrangement of the control mechanism for the operating levers of the pressure rollers is within the understanding and ability of the average person skilled in the art and does not have to be explained in detail here. | A weft thread conveying apparatus having at least one pair of weft thread conveying rollers with each roller having two conical shaped peripheral portions inclined to each other and extending upward from the roller edge towards the middle thereof and means for tilting one of the rollers to selectively engage a weft thread positioned between corresponding peripheral portions of the rollers. | 3 |
[0001] Method and apparatus for renting, customizing, manufacturing intermediating, and delivering risk and/or volatility products.
RELATED APPLICATIONS
[0002] U.S. Patent Documents
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Foreign Patent Documents
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(2004) “Volatility asymmetry in high-frequency data”, downloaded from Website http://www.missouri.edu/˜econwww/MEG_Papers/Julia %20Litvinova.pd f, in Mar. of 205. Stulz, René, 1996, “Rethinking Risk Management,” Journal of Applied Corporate Finance, Vol. 9, No. 3 (Fall), pp. 8-24. Cumming, Christine, and Beverly Hirtle, 2001, “The Challenges of Risk Management in Diversified Financial Companies,” FRBNY Economic Policy Review (March), pp. 1-17. Andersen, Torben, Tim Bollerslev, Francis X. Diebold, and Peter Christoffersen, 2004, “Practical volatility and correlation modeling for financial market risk management,” in Mark Carey and Rene M. Stulz, The risks of financial firms, forthcoming. Artzner, Philippe, Freddy Delbaen, Jean-Marc Eber, and David Heath, 1999, “Coherent measures of risk,” Mathematical Finance 9, 208-223. Danielsson, Jon, and Casper de Vries, 1997, “Value-at-Risk and Extreme Returns,” Discussion Paper No. 273, pp. 1-33 (London: School of Economics and Political Science). Ju, Xiongwei, and Neil Pearson, 1998, “Using value-at-risk to control risk taking: how wrong can you be?,” The Journal of Risk 1, 5-36. Duffie, Darrell, and Jun Pan, 1997, “An overview of value at risk,” The Journal of Derivatives, Vol. 4, No. 3 (Spring) pp. 7-49. Litterman, Robert, 1996, “Hot Spot and Hedges,” Journal of Portfolio Management, Special Issues, 52-75. Committee on the Global Financial System, Basel, 2001, “A Survey of Stress Tests and Current Practice at Major Financial Institutions,” (Switzerland: Bank for International Settlements). Hull, John, and Alan White, 1998, “Value at Risk When Daily Changes in Market Variables are Not Normally Distributed,” The Journal of Derivatives, Vol 5, No 3 (Spring) pp. 9-19. 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[0039] Geczy, Christopher, Bernadette Minton, and Catherine Schrand, “Why Firms Use Currency Derivatives,” Journal of Finance, September 1997, 1323-1348. http://fisher.osu.edu/˜fin/journal/archive_papers/isssept97/ms48 06.pdf
Artzner, Philippe, Freddy Delbaen, Jean-Marc Eber, and David Heath, 1999, “Coherent measures of risk,” Mathematical Finance 9, 208-223. www.math.ethz.ch/˜delbaen/ftp/preprints/CoherentMF.pdf Duffie, Darrell, and Jun Pan, 1997, “An overview of value at risk,” The Journal of Derivatives, Vol. 4, No. 3 (Spring) pp. 7-49. *Berkowitz, Jeremy and James O'Brien, “How Accurate are Value-at-Risk Models at Commercial Banks?”, Journal of Finance 57 , No 3, 1093-1111. Estimating Value at Risks for Short and Long Trading Positions http://www.eco.fundp.ac.be/cerefim/varpaper/200200. %20(Sriananth akumar %20 and %20Silvapulle)-Estimating %20VaR %20for %20Long %20 and %20Short %20Trading %20Position s.pdf Granger, C. and S.-H. Poon (2002), Forecasting Volatility in Financial Markets: A Review, September. Allayannis, George, and James P. Weston, “The Use of Foreign Currency Derivatives and Firm Market Value,” The Review of Financial Studies, Spring 2001, 243-276. http://faculty.darden.virginia.edu/allayannisy/ATT148761.pdf “subscribe to risk” exact phrase search using the following Google URL: http://www.google.com/search?q=+%22subscribe+to+risk %22&num=100& hl=en&lr=&as_qdr=all&start=100&sa=N Security Futures OCC Operational Overview http://www.optionsclearing.com/initiatives/security_futures/secu rity_futures_overview.jsp Lexis Nexis® Risk Management Solutions http://www.lexisnexis.com/risksolutions/management/Default. asp EGAR Technology, Inc. http://www.egartech.com/company_sum.asp About Us http://www.riskdataflow.com
BACKGROUND OF THE INVENTION
[0052] 1. Field of the Invention
[0053] The invention relates generally to processes for customizing, renting, purchasing, manufacturing, and intermediating risk and/or volatility products in particular but not limited (i.e. the invention also relates to gene sequencing and weather) to the following areas:
[0054] a. Customizable Electronic Works,
[0055] b. Remote Renting and/or Purchasing,
[0056] c. Automated Manufacturing and Ordering over the Internet,
[0057] d. Accessing Investment Information and Analysis,
[0058] e. Displaying Investment Information and Analysis,
[0059] f. Automated Analysis for Financial Assets,
[0060] g. Automated Volatility Analysis for Financial Assets,
[0061] h. Risk Management Systems,
[0062] i. Strategic and Financial Planning Systems,
[0063] j. Real Estate Systems,
[0064] j. Insurance/Retirement Systems, and
[0065] k. Credit Systems.
[0066] l. Misc.
[0067] m. Advantages of the present invention
[0068] 2. Description of Related Art
[0069] a. Customizable Electronic Works
[0070] Customizing electronic works, is well known to the art. For example, by Cook, et al., “Personal digital content system,” U.S. Pat. No. 6,842,604 (Jan. 11, 2005), Burson, et al., “System and method for automated access to personal information,” U.S. Pat. No. 6,405,245 (Jun. 11, 2002), Zirngibl, et al., Zirngibl, et al., “System and method for the creation and automatic deployment of personalized, dynamic and interactive voice services, including deployment through digital sound files,” U.S. Pat. No. 6,606,596 (Aug. 12, 2003), and Eberle, et al., “System and method for the creation and automatic deployment of personalized dynamic and interactive voice services,” U.S. Pat. No. 6,850,603 (Feb. 1, 2005), each of which is herein incorporated by reference in its entirety, related to customizable electronic works. None of these references, however, provides for provide for electronic work customization, automatic electronic work manufacturing, and the data administration of the present invention. This prior art does not provide for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0071] b. Remote Renting and/or Purchasing
[0072] Remote Renting and/or Purchasing, is well known to the art. For example, Bernard, et al., “System and method for automated remote previewing and purchasing of music, video, software, and other multimedia electronic works,” U.S. Pat. No. 5,918,213 (Jun. 29, 1999), Hastings, “Method and apparatus for renting items,” U.S. Pat. No. 6,584,450 (Jun. 24, 2003), Green, et al., “Remote ordering system,” U.S. Pat. No. 5,664,110 (Sep. 2, 1997), each of which is herein incorporated by reference in its entirety, related to automated remote and/or purchasing. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0073] c. Automated Manufacturing and Ordering over the Internet
[0074] Providing an automated process and a system for ordering and manufacturing personalized electronic works over the Internet, is well known to the art, such as the one described by Lemchen, “Automated customized remote ordering and manufacturing process,” U.S. Pat. No. 6,594,642 (Jul. 15, 2003) incorporated herein by reference. This prior work does not provide for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0075] d. Accessing Investment Information and Analysis
[0076] Several patents have been issued in accessing investment information and analysis. For example, by Galant, et al., “Method and system for providing financial information and evaluating securities of a financial debt instrument,” U.S. Pat. No. 6,839,686 (Aug. 19, 2003), and Hastings, “Automated system and method for customized and personalized presentation of products and services of a financial institution,” U.S. Pat. No. 6,349,290 (Feb. 19, 2002) each of which is herein incorporated by reference in its entirety, related to accessing investment information and analysis. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0077] e. Displaying Investment Information and Analysis
[0078] Several patents have been issued in displaying investment information and analysis. For example, by Gatto, et al., “Security analyst estimates performance viewing system and method,” U.S. Pat. No. 6,681,211 (Jan. 20, 2004), Impink, Jr., “Display apparatus,” U.S. Pat. No. 6,211,880 (Apr. 13, 1998), Stewart, “Volatility plot and volatility alert for display of time series data,” U.S. Pat. No. 6,195,103 (Nov. 18, 1997), Stewart, “User interface for a financial advisory system,” U.S. Pat. No. 5,918,217 (Nov. 18, 1997), and Escher, “Method for chart markup and annotation in technical analysis,” U.S. Pat. No. 6,801,201 (Dec. 17, 2002), each of which is herein incorporated by reference in its entirety, related to displaying investment information and analysis. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0079] f. Automated Analysis for Financial Assets
[0080] Several patents have been issued in automated analysis for financial assets. For example, by Burfield, et al., “Object-based numeric-analysis engine,” U.S. Pat. No. 6,298,334 (Oct. 2, 2001) and Li, “Automated analysis for financial assets,” U.S. Pat. No. 6,453,303 (Sep. 17, 2002), each of which is herein incorporated by reference in its entirety, related to automated analysis for financial assets. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0081] g. Automated Volatility Analysis for Financial Assets
[0082] Several patents have been issued in automated volatility analysis for financial assets. For example, Pang, et al., “Apparatus and method of pricing financial derivatives,” U.S. Pat. No. 6,546,375 (Apr. 8, 2003), Mathews, et al., “Systems, methods and computer program products for performing a generalized contingent claim valuation,” U.S. Pat. No. 6,862,579 (Aug. 19, 2003), Bekaert, et al., Kant, et al., “System and method for financial instrument modeling and using Monte Carlo simulation,” U.S. Pat. No. 6,772,136 (Aug. 3, 2004), and Makivic, “Simulation method and system for the valuation of derivative financial instruments,” U.S. Pat. No. 6,061,662 (May 9, 2000), each of which is herein incorporated by reference in its entirety, related to automated volatility analysis for financial assets. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0083] h. Risk Management Systems
[0084] Several patents have been issued in risk management systems. For example, Greener, et al., “Enhanced online sales risk management system,” U.S. Pat. No. 6,829,590 (Dec. 7, 2004), Irving, et al., “System and method for proactively monitoring risk exposure,” U.S. Pat. No. 5,991,743 (Nov. 23, 1999), Tom, “System and method for performing risk and credit analysis of financial service applications,” U.S. Pat. No. 5,696,907 (Dec. 9, 1997), Basch, et al., “Financial risk prediction systems and methods therefor,” U.S. Pat. No. 6,119,103 (Sep. 12, 2000), Smith, II, et al., “Methods and apparatus for collateral risk monitoring,” U.S. Pat. No. 6,850,643 (Feb. 1, 2005), each of which is herein incorporated by reference in its entirety, related to risk management systems. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0085] h. Strategic Planning, Financial Planning, and/or Portfolio Systems
[0086] Several patents have been issued in strategic planning, financial planning, and/or portfolio systems. For example, DeTore, et al., “Automated decision-making arrangement,” U.S. Pat. No. 5,732,397 (Mar. 24, 1998), Honarvar, et al., “Decision management system with automated strategy optimization,” U.S. Pat. No. 6,708,155 (Mar. 16, 2004), Bernheim, et al., “Economic security planning method and system,” U.S. Pat. No. 6,611,807 (Aug. 26, 2003), DiCresce, “Method and apparatus that processes financial data relating to wealth accumulation plans,” U.S. Pat. No. 5,991,744 (Nov. 23, 1999), Scott, et al., “Enhancing utility and diversifying model risk in a portfolio optimization framework,” U.S. Pat. No. 6,292,787 (Sep. 18, 2001), Robinson, “Automated portfolio selection system,” U.S. Pat. No. 6,484,152 (Aug. 28, 2001), each of which is herein incorporated by reference in its entirety related to planning, financial planning, and/or portfolio systems. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0087] i. Real Estate Systems
[0088] Several patents have been issued in real estate systems, and/or portfolio systems. For example, Jost, et al., “Real estate appraisal using predictive modeling,” U.S. Pat. No. 5,361,201 (Nov. 1, 1994) and Rothstein, “Real estate appraisal using predictive modeling,” U.S. Pat. No. 6,058,369 (May 2, 2000), each of which is herein incorporated by reference in its entirety, related to real estate systems. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0089] i. Insurance/Retirement Systems
[0090] Several patents have been issued in insurance and/or retirement systems. For example, Schoen, et al., “Computer apparatus and method for defined contribution and profit sharing pension and disability plan,” U.S. Pat. No. 6,235,176 (May 22, 2001) Schirripa, “Computer system and methods for management, and control of annuities and distribution of annuity payments,” U.S. Pat. No. 6,275,807 (Aug. 14, 2001) Lewis, et al., “Method and system for providing account values in an annuity with life contingencies,” U.S. Pat. No. 6,611,815 (Aug. 26, 2003), each of which is herein incorporated by reference in its entirety, related to insurance and/or retirement systems. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0091] j. Credit Systems
[0092] Several patents have been issued in credit systems. For example, Saladin, et al., “Expert credit recommendation method and system,” U.S. Pat. No. 5,262,941 (Nov. 16, 1993), Lebda, et al., “Method and computer network for co-ordinating a loan over the internet,” U.S. Pat. No. 6,385,594 (May 7, 2002), and Aziz, et al., “Method and system for improved collateral monitoring and control,” U.S. Pat. No. 6,018,721 (Jan. 25, 2000), each of which is herein incorporated by reference in its entirety, related to credit systems. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0093] j. Financial Information Intermediary System
[0094] Financial information intermediary system, is well known to the art. For example, by Motoyama, “Financial information intermediary system,” U.S. Pat. No. 5,913,202 (Jun. 15, 1999), which is herein incorporated by reference in its entirety, related to credit systems, related to financial information intermediary system. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0095] Institutional Banking and Existing Online Risk Applications
[0096] Several commercial applications have been disclosed. For example, Lexis Nexis Risk Management Solutions has disclosed a one-click access to a comprehensive range of investigation, due diligence, and fraud prevention solutions—all from a single Web page. EGAR's free and/or non-customized products FOCUS, EGAR ONE, EGAR ETS, EGAR Dispersion ASP and IVolatility data services, each of which is herein incorporated by reference in its entirety, related to existing commercial applications. None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention. Several institutional applications have been disclosed. For example, Security Futures OCC Operation the Options Clearing Corporation (“OCC”) has disclosed a system modifications for the trading of Single Stock and Narrow Based Index Futures (security futures). Martyn, et al. “On-line transaction processing system for security trading,” U.S. Pat. No. 6,195,647 (Feb. 27, 2001) and Musmanno, et al. “Securities brokerage-cash management system,” U.S. Pat. No. 4,376,978 (Mar. 15, 1983). None of these references, however, provides for risk and/or volatility product customization, automatic risk and/or volatility product manufacturing, risk and/or volatility product purchasing and/or rental, risk and/or volatility product intermediating, risk and/or volatility product display and data administration/integration of the present invention.
[0097] m. Advantages of the Present Invention
[0098] This invention discloses a method and apparatus for renting, customizing, producing, intermediating, and delivering one or more element selected from a group comprising of as means for measuring, monitoring, and/or displaying “liquidity risk,” means for measuring, monitoring, and/or displaying “settlement risk,” means for measuring, monitoring, and/or displaying “operational risk,” means for measuring, monitoring, and/or displaying “credit risk,” and means for measuring, monitoring, and/or displaying “systematic risk,” means for measuring, monitoring, and/or displaying “historical volatility,” and/or means for measuring, monitoring, and/or displaying “implied volatility,” and/or means for measuring, monitoring, and/or displaying “FX” and means for measuring, monitoring, and/or displaying “FX options,” and means for measuring, monitoring, and/or displaying “Margin trading,” and means for measuring, monitoring, and/or displaying “Fixed Income,” and means for measuring, monitoring, and/or displaying “Interest rate derivatives,” and means for measuring, monitoring, and/or displaying “Energy derivatives,” and means for measuring, monitoring, and/or displaying “Commodity and Metals trading and derivatives and Equity trading,”
SUMMARY OF THE INVENTION
[0099] According to one aspect of the invention, a method is provided for renting, customizing, and delivering risk and/or volatility products to customers on a subscription basis. Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0100] According to one aspect of the invention, a method is provided for renting, customizing, and delivering risk and/or volatility products to customers. Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0101] According to another of the invention, a computer-implemented method is provided for renting, customizing, and delivering risk and/or volatility products to customers. According to the method, one or more risk and/or volatility product selection criteria are received that indicate one or more risk and/or volatility products that a customer desires to rent. Up to a specified number of the one or more risk and/or volatility products indicated by the one or more risk and/or volatility product selection criteria are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0102] According to another aspect of the invention, a computer-implemented method is provided for renting, customizing, and delivering risk and/or volatility products to customers. According to the method, one or more risk and/or volatility product selection criteria are received that indicate one or more risk and/or volatility products that a customer desires to rent. Up to a specified number of the one or more risk and/or volatility products indicated by the one or more risk and/or volatility product selection criteria are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0103] According to another aspect of the invention, a method is provided for renting, customizing, and delivering risk and/or volatility products to customers. Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0104] According to another aspect of the invention, a method is provided for renting, customizing, and delivering one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “historical volatility,” and/or means for measuring, monitoring, and/or displaying “implied volatility” to customers. Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more said group product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0105] According to another aspect of the invention, a method is provided for renting, customizing, and delivering one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “liquidity risk,” means for measuring, monitoring, and/or displaying “settlement risk,” means for measuring, monitoring, and/or displaying “operational risk,” means for measuring, monitoring, and/or displaying “credit risk,” and means for measuring, monitoring, and/or displaying “systematic risk” to customers. Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more said group product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0106] According to another aspect of the invention, a method is provided for renting, customizing, and delivering one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “liquidity risk,” means for measuring, monitoring, and/or displaying “settlement risk,” means for measuring, monitoring, and/or displaying “operational risk,” means for measuring, monitoring, and/or displaying “credit risk,” and means for measuring, monitoring, and/or displaying “systematic risk” to customers.
[0107] According to another aspect of the invention, a method is provided for renting, customizing, and delivering one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “FX” and means for measuring, monitoring, and/or displaying “FX options,” and means for measuring, monitoring, and/or displaying “Margin trading,” and means for measuring, monitoring, and/or displaying “Fixed Income,” and means for measuring, monitoring, and/or displaying “Interest rate derivatives,” and means for measuring, monitoring, and/or displaying “Energy derivatives,” and means for measuring, monitoring, and/or displaying “Commodity and Metals trading and derivatives and Equity trading.”
[0108] Up to a specified number of risk and/or volatility products are provided to the customer. In response to one or more said group product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0109] According to another aspect of the invention, a computer-implemented method is provided for renting one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “historical volatility,” and/or means for measuring, monitoring, and/or displaying “implied volatility” to customers. According to the method, one or more said group selection criteria are received from a customer that indicates one or more risk and or volatility products that the customer desires to rent. Up to a specified number of the one or more said indicated by the one or more risk and/or volatility selection criteria are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0110] According to another aspect of the invention, a computer-implemented method is provided for renting one or more element selected from a group comprising of means for measuring, monitoring, and/or displaying “liquidity risk,” means for measuring, monitoring, and/or displaying “settlement risk,” means for measuring, monitoring, and/or displaying “operational risk,” means for measuring, monitoring, and/or displaying “credit risk,” and means for measuring, monitoring, and/or displaying “systematic risk” to customers. According to the method, one or more said group selection criteria are received from a customer that indicates one or more risk and or volatility products that the customer desires to rent. Up to a specified number of the one or more said indicated by the one or more risk and/or volatility product selection criteria are provided to the customer. In response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0111] According to another aspect of the invention, an apparatus for renting, customizing, and delivering risk and/or volatility products risk and/or volatility products to customers is provided. The apparatus comprises one or more processors and a memory communicatively coupled to the one or more processors. The memory includes one or more sequences of one or more instructions which, when executed by the one or more processors, cause the one or more processors to perform several steps. First, one or more risk and/or volatility product selection criteria are received that indicate one or more risk and/or volatility products that a customer desires to rent. Up to a specified number of the one or more risk and/or volatility products indicated by the one or more risk and/or volatility product selection criteria are provided to the customer. Finally, in response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0112] According to another aspect of the invention, an apparatus is provided for renting, customizing, and delivering risk and/or volatility products to customers. The apparatus comprises a risk and/or volatility product rental mechanism configured to receive one or more risk and/or volatility product selection criteria that indicate one or more risk and/or volatility products that a customer desires to rent. The risk and/or volatility product rental mechanism is also configured to provide to the customer up to a specified number of the one or more risk and/or volatility products indicated by the one or more risk and/or volatility product selection criteria. Finally, the risk and/or volatility product rental mechanism is configured to in response to one or more risk and/or volatility product delivery criteria being satisfied (such as the payment of a specified fee), one or more other risk and/or volatility products are provided to the customer, wherein a total current one or more risk and/or volatility products provided to the customer can only be used during a specified time.
[0113] In the foregoing specification, the invention has been described with reference to specific embodiments thereof. However, various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative sense rather than a restrictive sense.
[0114] Many modifications and alterations may be made by those having ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, it must be understood that the embodiment illustrations has been set forth only for the purposes of example and that it should not be taken as limiting the invention as defined by the following claims. For example, notwithstanding the fact that the elements of a claim are set forth below in an obvious combination, it must be expressly understood that the invention includes other combinations of fewer, more or different elements, which are disclosed in above even when not initially claimed in such combinations.
[0115] The claims are thus to be taught to include what is specifically illustrated and described above, what is an equivalent concept, what can be obviously substituted and also what essentially incorporates the essential idea of the invention.
BRIEF DESCRIPTION OF THE DRAWING
[0116] Embodiments of the invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
[0117] FIG. 1 is a diagram depicting an approach for renting risk and/or volatility products to customers according to an embodiment.
[0118] FIG. 2 is a flow diagram depicting an approach for renting risk and/or volatility products to customers according to an embodiment.
[0119] FIG. 3 is a flow diagram depicting a “Specific Time Limit” approach for renting risk and/or volatility products to customers according to an embodiment.
[0120] FIG. 4 is a flow diagram depicting a “Negotiated Time Limit with Intermediate” approach for renting risk and/or volatility products to customers according to an embodiment.
[0121] FIG. 5 is a diagram depicting an approach for renting risk and/or volatility products to customers over the Internet according to an embodiment.
[0122] FIG. 6 is a flow diagram illustrating an approach for renting risk and/or volatility products to customers over the Internet using both “Specific Time Limit” and “Negotiated Time Limit with Intermediate” according to an embodiment; and
[0123] FIG. 7 is a block diagram of a data processing system upon which embodiments of the invention may be implemented.
[0124] FIG. 8 is a block diagram of a risk and/or volatility product producer system upon which embodiments of the invention may be implemented.
DETAILED DESCRIPTION OF THE INVENTION
[0125] In the following description, reference will now be made in detail to the presently preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Well-known structures and devices are depicted in block diagram form in order to avoid unnecessarily obscuring the invention. Yet, it will be apparent that the invention may be practiced without these specific details.
[0126] Various aspects and features of example embodiments of the invention are described in more detail hereinafter in the following sections: (1) utilitarian overview; (2) risk and/or volatility products selection criteria; (3) risk and/or volatility products delivery; (4) “Specific Time Limit”; (5) “Negotiated Time Limit with Intermediate”; (6) register management; (7) implementation equipment, and (8) provider services.
[0127] 1. Utilitarian Overview
[0128] FIG. 1 is a block diagram 100 that illustrates an approach for renting risk and/or volatility products to customers according to various embodiments described herein. As used herein, the term “risk and/or volatility product” refers to any commercial risk and/or volatility measurement and/or monitoring electronic work that can be rented to customers. Examples of risk and/or volatility products include means for measuring and/or monitoring credit risk, liquidity risk, settlement risk, operational risk, and systematic risk, and/or means for measuring and/or monitoring historical volatility and implied volatility stored on a non-volatile memory such as a tape, other magnetic medium, optical medium, read-only memory or the like, and the invention is not limited to any particular type of risk and/or volatility product. In general, the decision of what risk and/or volatility products to rent is separated from the decision of when to rent the risk and/or volatility products. Customers may specify what risk and/or volatility products to rent using one or more risk and/or volatility product selection criteria separate from deciding when to receive the specified risk and/or volatility products. Furthermore, customers are not constrained by conventional rental “shopping carts” and instead can have continuous, serialized rental of risk and/or volatility products.
[0129] According to one embodiment, a customer 140 provides one or more risk and/or volatility product selection criteria to a provider 120 over a link 110 . Link 110 may be any medium for transferring data between customer 140 and provider 120 .
[0130] The risk and/or volatility product selection criteria indicate risk and/or volatility products that customer 140 desires to rent from provider 120 . In response to receiving the risk and/or volatility product selection criteria from customer 140 , provider 120 provides the risk and/or volatility products indicated by the risk and/or volatility product selection criteria to customer 140 over a delivery channel 120 . Delivery channel 120 may be implemented by any mechanism or medium that provides for the transfer of risk and/or volatility products from provider 120 to customer 140 and the invention is not limited to any particular type of delivery channel. Examples of delivery channel 120 include delivery using the Internet. Provider 120 may be centralized or distributed depending upon the requirements of a particular application.
[0131] According to an embodiment, a “Specific Time Limit” approach allows up to a specified number of risk and/or volatility products to be rented simultaneously to customer 140 by provider 120 . According to another embodiment, a “Negotiated Time Limit with Intermediate” approach allows up to a specified number of risk and/or volatility product exchanges to occur during a specified period of time. The “Specific Time Limit” and “Negotiated Time Limit with Intermediate” approaches may be used together or separately with a variety of subscription methodologies.
[0132] The approach just described for renting risk and/or volatility products to customers is now described with reference to a flow diagram 200 of FIG. 2 . After starting in step 202 , in step 204 , customer 140 creates risk and/or volatility product selection criteria. In step 206 , customer 140 provides the risk and/or volatility product selection criteria to provider 120 . In step 208 , in response to provider 120 receiving the risk and/or volatility product selection criteria from customer 140 , provider 120 provides one or more risk and/or volatility products indicated by the risk and/or volatility product selection criteria to customer 140 . The process is complete in step 210 .
[0133] 2. Risk and/or Volatility Product Selection Criteria
[0134] The one or more risk and/or volatility product selection criteria provided by customer 140 to provider 120 indicate the particular risk and/or volatility products that customer 140 desires to rent from provider 120 . Thus, the risk and/or volatility product selection criteria define a customer-specific order queue that is fulfilled by provider 120 . According to one embodiment, the risk and/or volatility product selection criteria specify attributes of risk and/or volatility products to be provided by provider 120 to customer 140 . Risk and/or volatility product selection criteria may specify any type of risk and/or volatility product attributes and the invention is not limited to particular risk and/or volatility product attributes. Examples of risk and/or volatility product attributes include, without limitation, identifier attributes, type attributes and cost attributes. Risk and/or volatility product selection criteria may be changed at any time to reflect changes in risk and/or volatility products that customers desire to rent from a provider.
[0135] 3. Risk and/or Volatility Product Delivery
[0136] According to one embodiment, risk and/or volatility products are delivered by provider 120 to customer 140 over delivery channel 120 based upon risk and/or volatility product delivery criteria. More specifically, the delivery of risk and/or volatility products from provider 120 to customer 140 is triggered by risk and/or volatility product delivery criteria being satisfied. The risk and/or volatility product delivery criteria may include a wide range of Internet delivery criteria and the invention is not limited to any particular risk and/or volatility product delivery criteria. Examples of risk and/or volatility product delivery criteria include, without limitation, customer messaging, customer web services, customer remote method invocation, customer p2p, and customer email.
[0137] The risk and/or volatility product delivery criteria may be specified by customer 140 to provider 120 or negotiated by customer 140 and provider 120 as part of a subscription service. For example, a particular subscription service may include risk and/or volatility product delivery criteria that specifies that a particular number of risk and/or volatility products are to be delivered monthly. As another example, risk and/or volatility product delivery criteria may specify that an initial set of risk and/or volatility products is to be delivered by provider 120 to customer 140 upon initiation of a subscription service and that additional risk and/or volatility products are to be delivered to customer 140 upon return of risk and/or volatility products to provider 120 . Risk and/or volatility product delivery criteria may be applied uniformly to all risk and/or volatility products to be delivered to a customer, or may be risk and/or volatility product specific. For example, risk and/or volatility product delivery criteria may specify a particular date, i.e., the third Wednesday of every month, for all risk and/or volatility product deliveries. Alternatively, separate risk and/or volatility product delivery dates may be assigned to each risk and/or volatility product.
[0138] 4. “Specific Time Limit”
[0139] According to one embodiment, a “Specific Time Limit” approach is used to manage the number of risk and/or volatility products that may be simultaneously rented to customers. According to the “Specific Time Limit” approach, up to a specified number of risk and/or volatility products may be rented simultaneously to a customer. Thus, the “Specific Time Limit” approach establishes the size of an register of risk and/or volatility products that may be maintained by customers. The specified number of risk and/or volatility products may be specific to each customer or may be common to one or more customers. In the present example, if the specified number of risk and/or volatility products is nine, then up to nine risk and/or volatility products may be rented simultaneously by provider 120 to customer 140 . If the specified number of risk and/or volatility products are currently rented to customer 140 and the specified risk and/or volatility product delivery criteria triggers the delivery of one or more additional risk and/or volatility products, then those risk and/or volatility products are not delivered until one or more risk and/or volatility products are returned by customer 140 to provider 120 .
[0140] According to one embodiment, in situations where the specified number of risk and/or volatility products are currently rented to customer 140 and the specified risk and/or volatility product delivery criteria triggers the delivery of one or more additional risk and/or volatility products, then the one or more additional risk and/or volatility products are delivered to customer 140 and customer 140 and a surcharge is applied customer 140 . The specified number of risk and/or volatility products may then be increased thereafter to reflect the additional risk and/or volatility products delivered to customer 140 and increase the size of the register maintained by customer 140 . Alternatively, the specified number of risk and/or volatility products may remain the same and number of risk and/or volatility products maintained by customer 140 returned to the prior level after risk and/or volatility products are returned to provider 120 by customer 140 . When used in conjunction with the “Negotiated Time Limit with Intermediate” approach described hereinafter, the specified number of risk and/or volatility products may be unlimited.
[0141] The “Specific Time Limit” approach for managing the number of risk and/or volatility products that may be simultaneously rented to customers is now described with reference to a flow diagram 300 of FIG. 3 . After starting in step 302 , in step 304 , one or more initial risk and/or volatility products are delivered to customer 140 to establish the register maintained by customer 140 . Note that an initial delivery of risk and/or volatility products is not required and according to one embodiment, the register of customer 140 is incrementally established over time.
[0142] In step 306 , a determination is made whether the risk and/or volatility product delivery criteria have been satisfied. If not, then the determination continues to be made until the risk and/or volatility product delivery criteria are satisfied. As described previously herein, the delivery criteria may include customer notification generally, customer notification that an risk and/or volatility product is being returned, the actual return of an risk and/or volatility product, the occurrence of a specific date, or that a specified amount of time has elapsed.
[0143] Once the risk and/or volatility product delivery criteria are satisfied, then in step 308 , a determination is made whether the specified number of risk and/or volatility products have been delivered. If not, then control returns to step 304 and one or more additional risk and/or volatility products are delivered by provider 120 to customer 140 . If however, in step 308 , the specified number of risk and/or volatility products have been delivered, then in step 310 , a determination is made whether the specified number of risk and/or volatility products, i.e., the “Specific Time Limit” limit, is to be overridden. As previously described, the specified number of risk and/or volatility products may be overridden by increasing the specified number of risk and/or volatility products, i.e., the “Specific Time Limit” limit, to allow additional risk and/or volatility products to be delivered to customer 140 and charging a fee to customer 140 . Alternatively, the specified number of risk and/or volatility products is not changed and a surcharge applied to customer 140 . This process continues for the duration of the subscription and is then complete in step 310 .
[0144] 5. “Negotiated Time Limit with Intermediate”
[0145] According to one embodiment, a “Negotiated Time Limit with Intermediate” approach is used to rent risk and/or volatility products to customers. According to the “Negotiated Time Limit with Intermediate” approach, up to a specified number of risk and/or volatility product exchanges may be performed during a specified period of time. For example, referring to FIG. 1 , suppose that provider 120 agrees to rent risk and/or volatility products to customer 140 with a “Negotiated Time Limit with Intermediate” limit of nine risk and/or volatility products per month. This means that customer 140 may make up to nine risk and/or volatility product exchanges per month. This approach may be implemented independent of the number of risk and/or volatility products that a customer may have rented at any given time under the “Specific Time Limit” approach. The approach is also independent of the particular risk and/or volatility product delivery criteria used.
[0146] According to one embodiment, the “Negotiated Time Limit with Intermediate” approach is implemented in combination with the “Specific Time Limit” approach to rent risk and/or volatility products to customers. In this situation, up to a specified number of total risk and/or volatility products are simultaneously rented to customer 140 and up to a specified number of risk and/or volatility product exchanges may be made during a specified period of time. Thus, using the “Specific Time Limit” and the “Negotiated Time Limit with Intermediate” approaches together essentially establishes a personal risk and/or volatility product register for customer 140 based upon the “Specific Time Limit” limit that may be periodically refreshed based upon the “Negotiated Time Limit with Intermediate” limit selected.
[0147] In some situations, customer 140 may wish to exchange more than the specified number of risk and/or volatility products during a specified period. According to one embodiment, in this situation, provider 120 agrees to rent additional risk and/or volatility products above the specified number to customer 140 and to charge customer 140 for the additional risk and/or volatility products. For example, suppose that provider 120 agrees to rent risk and/or volatility products to customer 140 with up to nine risk and/or volatility product turns (exchanges) per month. If, in a particular month, customer 140 requires two additional turns, then the two additional risk and/or volatility products are provided to customer 140 and a surcharge is applied to customer 140 for the additional two risk and/or volatility products.
[0148] In other situations, customer 140 may not use all of its allotted turns during a specified period. According to one embodiment, customers lose unused turns during a subscription period. For example, if customer 140 has a “Negotiated Time Limit with Intermediate” limit of four risk and/or volatility product exchanges per month and only makes two risk and/or volatility product exchanges in a particular month, then the two unused exchanges are lost and cannot be used. At the start of the next month, customer 140 would be entitled to four new risk and/or volatility product exchanges.
[0149] According to another embodiment, customers are allowed to carry over unused turns to subsequent subscription periods. For example, if customer 140 has a “Negotiated Time Limit with Intermediate” limit of four risk and/or volatility product exchanges per month and only makes two risk and/or volatility product exchanges in a particular month, then the two unused exchanges are lost and cannot be used. At the start of the next month, customer 140 would be entitled to six new risk and/or volatility product exchanges, two from the prior month and four for the current month.
[0150] The “Negotiated Time Limit with Intermediate” approach for renting risk and/or volatility products to customers is now described with reference to a flow diagram 400 of FIG. 4 . After starting in step 401 , in step 404 , customer 140 and provider 120 agree upon the terms of the “Negotiated Time Limit with Intermediate” agreement. Specifically, customer 140 and provider 120 negotiate a time limit.
[0151] In step 405 , in response to risk product being provided within terms of time limit, provider 120 provides one or more risk and/or volatility products to customer 140 over delivery channel 120 . Any type of risk and/or volatility product delivery criteria may be used with the “Negotiated Time Limit with Intermediate” approach and the invention is not limited to any particular delivery criteria. For example, the initial one or more risk and/or volatility products may be delivered to customer 140 in response to a subscription payment made by customer 140 to provider 120 , the initiation of a specified subscription period, or by request of customer 140 for the initial rental risk and/or volatility products. The availabilty of initial one or more risk and/or volatility products must not exceed the terms of the “Negotiated Time Limit with Intermediate” agreement.
[0152] In step 408 , in response to one or more delivery criteria being satisfied, a determination is made whether additional risk and/or volatility products can be provided to customer 140 within the terms of the “Negotiated Time Limit with Intermediate” agreement. For example, if the number of risk and/or volatility products rented to customer in the current subscription period is less than the agreed-upon “Negotiated Time Limit with Intermediate,” then additional risk and/or volatility products can be rented to customer 140 within the terms of the “Negotiated Time Limit with Intermediate” agreement. In this situation, this determination may be made in response to customer 140 returning one or more risk and/or volatility products to provider 120 , or by customer 140 requesting additional risk and/or volatility products.
[0153] If, in step 405 , a determination is made that additional risk and/or volatility products can be rented to customer 140 within the terms of the “Terms of a Time Limit” agreement, then control returns to step 406 where one or more additional risk and/or volatility products are delivered to customer 140 . If however, in step 404 , a determination is made that customer 140 AND provider 120 CANNOT NEGOTITATE A TIME LIMIT AGREEMENT, then in step 403 , a determination is made whether to override the current agreement terms. If so, then in step 403 , the agreement terms are changed to allow for a larger number of terms and customer 140 is charged accordingly, or the terms are left unchanged and a surcharge is applied for the additional risk and/or volatility products to be delivered. Control then returns to step 405 , where a determination is made whether the risk product can be provided to customer 140 within terms of a time limit.
[0154] If in step 410 , a determination is made that the risk product can be provided within the terms of a time limit, then in step 406 , risk and/or volatility products are delivered to customer 140 until the next subscription period. For example, the request for additional risk and/or volatility products may be received at the end of a subscription period and instead of renting the additional risk and/or volatility products immediately, they are instead delivered during the subsequent subscription period. Control then returns to step 404 where one or more additional risk and/or volatility products are rented to customer or the process is complete in step 410 .
[0155] The approach for renting risk and/or volatility products described herein is now described in the context of renting to customers risk and/or volatility products, such as a means for measuring and/or monitoring credit risk, liquidity risk, settlement risk, operational risk, and systematic risk, and/or means for measuring and/or monitoring historical volatility and f implied volatility. FIG. 5 is a diagram 500 that depicts a set of customers 511 that desire to rent risk and/or volatility products from a set of providers 521 . Customers 511 communicate with providers 521 over links 512 , the global packet-switched network referred to as the “Internet,” and a link 518 .
[0156] Links 512 and 518 may be any medium for transferring data between customers 511 and the Internet 523 and between the Internet 523 and providers 521 , respectively, and the invention is not limited to any particular medium. In the present example, links 512 and 518 may be connections provided by one or more Internet Service Providers (ISPs) and customers 511 are configured with generic Internet web browsers. Links 512 and 518 may be secure or unsecured depending upon the requirements of a particular application.
[0157] In accordance with an embodiment, customers 511 enter into a rental agreement with providers 521 to rent risk and/or volatility products 510 from providers 521 according to the “Specific Time Limit” and/or “Negotiated Time Limit with Intermediate” approaches described herein. No limiting to any particular approach for entering into the rental agreement is placed on the invention. For example, customers 511 and providers 521 may enter into a rental agreement by fax, mail, telephone or over the Internet, by customers 511 logging into a web site associated with providers 521 .
[0158] Customers 511 create and provide risk and/or volatility product selection criteria to providers 521 over links 512 and 518 and the Internet 523 . The invention is not limited to any particular approach for specifying and providing risk and/or volatility product selection criteria to providers 521 . For example, according to one embodiment, customers 511 provide risk and/or volatility product selection criteria to providers 521 in one or more data files. According to another embodiment, customers 511 log onto a web site of providers 521 and use a graphical user interfaced (GUI) to specify attributes of the risk and/or volatility product that customers desire to rent from providers 521 .
[0159] The risk and/or volatility product selection attributes may include any attributes that describe, at least in part, risk and/or volatility product that customers 511 desire to rent. Customers 511 may identify specific risk and/or volatility product by the risk and/or volatility product selection criteria, or may provide various attributes and allow providers 521 to automatically manufacture and deliver risk and/or volatility product that satisfy the attributes specified.
[0160] Once customers 511 and providers 521 have entered into a rental agreement and customers 511 have provided risk and/or volatility product selection criteria to providers 521 , then risk and/or volatility products 510 are rented to customers 511 over delivery channels 514 in accordance with the terms of the rental agreement. Specifically, according to the “Specific Time Limit” approach described herein, an initial set of risk and/or volatility products 510 , such as means for measuring, monitoring, and/or displaying “liquidity risk,” means for measuring, monitoring, and/or displaying “settlement risk,” means for measuring, monitoring, and/or displaying “operational risk,” means for measuring, monitoring, and/or displaying “credit risk,” and means for measuring, monitoring, and/or displaying “systematic risk,” means for measuring, monitoring, and/or displaying “historical volatility,” and/or means for measuring, monitoring, and/or displaying “implied volatility,” and/or means for measuring, monitoring, and/or displaying “FX” and means for measuring, monitoring, and/or displaying “FX options,” and means for measuring, monitoring, and/or displaying “Margin trading,” and means for measuring, monitoring, and/or displaying “Fixed Income,” and means for measuring, monitoring, and/or displaying “Interest rate derivatives,” and means for measuring, monitoring, and/or displaying “Energy derivatives,” and means for measuring, monitoring, and/or displaying “Commodity and Metals trading and derivatives and Equity trading,”
[0161] are delivered to customers 511 over delivery channels 514 according to the terms of the rental agreement. Subsequent risk and/or volatility products 510 are delivered whenever the specified risk and/or volatility product delivery criteria are satisfied. For example, additional risk and/or volatility products 510 may be delivered upon the return of one or more risk and/or volatility products 510 to provider, a request from customers 511 , the arrival of a particular date, e.g., a specific day of the month, or the expiration of a specified period of time, e.g., fifteen days.
[0162] In accordance with the “Specific Time Limit” approach described herein, once the maximum number of risk and/or volatility products 510 have been rented to a particular consumers 511 , then no additional risk and/or volatility products 510 are rented until one or more rented risk and/or volatility products 510 are returned to providers 521 , or unless a surcharge is applied to the particular consumers 511 . Alternatively, the rental agreement between the particular consumers 511 and providers 521 may be modified to increase the maximum number of risk and/or volatility products 510 that may be rented simultaneously to the particular consumers 511 .
[0163] The rental agreement between customers 511 and providers 521 may also specify a maximum number of turns in combination with the “Specific Time Limit” approach. In this situation, a specific time limit restricts how quickly customers 511 may refresh their risk and/or volatility product 512 out baskets. For example, suppose that a particular consumers 511 agrees with providers 521 to rent up to four risk products with a time limit of 3 month. Under this agreement, the particular consumers 511 may maintain a personal register of up to four risk products for 3 months. Thus, the particular consumers 511 can completely “replace” his personal register once per month. If the particular consumers 511 agreed to a specific time limit of 2 months, then the particular consumers 511 would be able to completely replace his personal register for two months.
[0164] Providers 521 may be centralized or distributed depending upon the requirements of a particular application. For example, providers 521 may be a centralized data processing center from which all risk and/or volatility products 510 are manufactured and delivered. Alternatively, providers 521 may be implemented by a network of distributed data processing center.
[0165] FIG. 6 is a flow diagram that illustrates an approach for renting risk and/or volatility products 510 to customers over a communications network such as the Internet using both “Specific Time Limit” and “Negotiated Time Limit with Intermediate” according to an embodiment. Referring also to FIG. 5 , after starting in step 601 , in step 602 , a consumers 511 enters into a rental agreement with providers 521 . In the present example, consumers 511 uses a generic web browser to access an Internet web site associated with providers 521 and enter into a rental agreement that specifies that consumers 511 may maintain a personal register of four risk products for 1 month (“Specific Time Limit” of 1 month). | According to a computer-implemented approach for renting, customizing, manufacturing, intermediating, and delivering risk and volatility product to customers, customers specify what risk or volatility product to rent using a plurality of risk and/or product selection parameters. According to the approach, customers provide a plurality of risk and/or volatility product selection parameters to a provider provides the risk and volatility product indicated by the plurality of risk and/or volatility product selection parameters to customer over a delivery channel. The risk and/or volatility product provider may be either centralized or distributed depending upon the requirements of a particular application. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new and useful improvements in machines for working sheet metal, particularly for closing sheet metal joints of the type commonly known as the "Pittsburgh Lock", and more particularly to an automatic machine for continuous application of a hammering force to the edge portion of a joint to be formed to fold such edge into a closed joint.
2. Description of the Prior Art
In the past, the formation of sheet metal joints in duct work has been done by hand or by complicated machinery for rolling and forming the desired seams or joints.
Lindgren U.S. Pat. No. 1,612,519 discloses an automatic seaming machine for sheet metal having rotary cams for folding and bending seams.
Brown U.S. Pat. No. 1,381,062 discloses a rotary brake for forming seams in sheet metal products.
McCann U.S. Pat. No. 1,625,269 discloses an automatic seaming device for cylindrical objects such as cans.
Flagler U.S. Pat. No. 2,950,697 discloses a rotary device for forming seams in sheet metal.
Tribe U.S. Pat. No. 3,130,770 discloses a rotary device for bending or folding the edges of sheet metal panels to form seams therein.
Gibson U.S. Pat. No. 2,810,420 discloses a rotary hammer for closing sheet metal joints of the type known as the "Pittsburgh Lock".
Kemp U.S. Pat. No. 3,638,596 discloses another type of rotary hammer for closing sheet metal joints of the type known as the "Pittsburgh Lock".
SUMMARY OF THE INVENTION
One of the objects of this invention is to provide a new and improved automatic closing machine for sheet metal joints and particularly for folding or closing joints known as the "Pittsburgh Lock".
Another object of this invention is to provide a new and improved automatic closing machine for sheet metal joints having a powered rotary hammer for continuous application of a joint-folding hammering force.
Another object of this invention is to provide an improved automatic closing machine for sheet metal joints having a rotary hammer and means for moving the hammer along the length of the joint to be formed and returning to the starting place.
Another object of the invention is to provide an improved automatic closing machine for sheet metal joints having vertical adjustment for varying the relative position of the edge of the duct in which the joint is to be formed and the rotary hammer.
Another object of the invention is to provide an improved automatic closing machine for sheet metal joints having stops to locate the sheet metal duct longitudinally in the machine to predetermine the location of the joint in relation to the location to the end connecting edges of the duct.
Another object of the invention is to provide an improved automatic closing machine for sheet metal joints having automatic controls for moving a rotary hammer a predetermined distance and then reversing direction.
Another object of this invention is to provide an improved automatic closing machine for sheet metal joints which may be used for joints in one piece and two piece sheet metal ducts.
Other objects of the invention will become apparent from time to time throughout the specification and claims as hereinafter related.
The foregoing objects and other objects of the invention are accomplished by an automatic closing machine for sheet metal joints in sheet metal ducts or the like which consists of a powered rotary hammer for continuous application of a hammering force to the edge portion of a joint to be formed to fold such edge into a closed joint.
The machine has a supporting frame with a vertically adjustable support for varying the relative vertical spacing of the edge of the duct in which the joint is to be formed and the rotary hammer. Stops locate the duct longitudinally in the machine to predetermine the length of the joint being folded in relation to the location of the end connecting edges of the duct. Pneumatic clamps or the like are provided to secure the duct accurately in position for formation of the joint by the rotary hammer.
A longitudinally extending track is provided on the machine on which the rotary hammer is supported for longitudinal movement and an automatic traversing mechanism is provided to move the rotary hammer along the track. Automatic controls are provided to actuate the traversing mechanism to move the rotary hammer along the track a predetermined distance and then to reverse direction.
Vertical frame adjustment is operable to locate the edge of the duct which is to be formed into a joint in proper position in relation to the path of movement of the rotary hammer for any selected duct size. Likewise, the controls for the traversing mechanism may vary the length of the path of movement of the rotary hammer for any selected duct length. The apparatus is useful for forming joints in one-piece ducts having a single joint and for forming joints in two-piece joints having two joints on opposite sides thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a preferred embodiment of an improved automatic closing machine for sheet metal joints.
FIG. 2 is a detail view in elevation showing the traversing mechanism for a rotary hammer in the embodiment of the invention shown in FIG. 1.
FIG. 3 is a sectional view showing the positioning of the traversing mechanism and supporting track for the rotary hammer and its relation to the clamping mechanism for the sheet metal in which a joint is to be closed.
FIG. 4 is an isometric view of the clamping mechanism showing an alternate form of clamp.
FIG. 5 is an end view of a half section of sheet metal having the edges bent to form a "Pittsburgh Lock", but prior to closing the edges into a locked position.
FIG. 6 is an end view showing two of the sheet metal sections, as shown in FIG. 5, assembled into a duct, but prior to closing the joints therein.
FIG. 7 is an end view of the sheet metal duct shown in FIG. 6 after bending the edges to close the "Pittsburgh Lock".
FIG. 8 is an end view of a one piece sheet metal duct having the "Pittsburgh Lock" in position for seaming or closing.
FIG. 9 is an end view of a one piece sheet metal duct having the "Pittsburgh Lock" bent over and closed.
FIG. 10 is an isometric view of the rotary hammer on the apparatus shown in FIGS. 1 to 3 in position bending over the edge of the sheet metal of a "Pittsburgh Lock".
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings by numerals of reference and more particularly to FIGS. 1 to 4, there is shown an automatic closing machine 10 for sheet metal joints in sheet metal ducts or the like. The machine 10 is particularly designed for bending and closing sheet metal seams of the type known as the "Pittsburgh Lock".
Machine 10 consists of a base frame 11 formed of end pieces 12 and 13 and side pieces 14 and 15 and center brace 16. Frame 11 is preferably formed of square tubing secured together by welding. Frame 11 also includes vertically extending supports 17 and 18 of square tubing or the like secured on the base support by welding.
At the upper end of vertical supports 17 and 18 there is provided a longitudinally extending, supporting track consisting of longitudinally extending bars or rails 19 and 20. Rails 19 and 20 are preferably of square tubing as is the rest of the structure. Rail 19 extends between vertical supports 17 and 18. Rail 20 extends between outwardly projecting legs 21 and 22 which are welded on rail 19. Rails 19 and 20 and leg 22 also function as supports for a small supporting plate or platform 23.
Just below the top of the frame, there are positioned a pair of outwardly extending supporting legs 24 and 25 which are welded to vertical supporting legs 17 and 18. A transversely extending square tubular member 26 is secured at one end to supporting leg 24 and at the other end to supporting leg 25. A cantilevered supporting member 27 is secured at one end to supporting leg 25 and is unsupported at its distal end 28. The upper portions of the frame, just described, support the clamping and automatic rotary hammer used in the apparatus as will be subsequently described.
The apparatus is provided with a vertically movable table or support 29 for supporting sheet metal duct work in operating relation to the rotary hammer carried on the upper portion of the frame. Table 29 is provided with a scissors type support which enables the table to be positioned accurately in any selected vertical position without shifting laterally. Scissors type support 30 consists of a pair of supporting arms 31 and 32 which are pivotally connected by pivot pins 33. The lower end of supporting arm 32 is pivotally supported on pivot 34.
The upper end of supporting arm 31 is pivotally supported on the underside of table 29 on a pivot 35 which is hidden but is the same type of pivot as pivot 34. The lower end of supporting arm 31 is provided with a supporting roller 36 which is movable along the upper surface of square tubing 14 at the bottom portion of frame 11. The upper end of supporting arm 32 is provided with a roller 37 which is hidden but which identical to roller 36 and rides along the under surface of supporting table 29.
The scissors type support 30 also includes parallel supporting arms which are supported on and ride on the square tubes 15 and 16 of the base portion of supporting frame 11. Supporting arm 32a is supported on pivot 34a and is provided with a roller at its upper end which corresponds to roller 37 on supporting arm 32. Supporting arm 31a has roller 36a at its lower end which rides on square tubing 16. Supporting arm 31a is connected to the underside of table 29 by a pivot which corresponds in position to pivot 35 for supporting arm 31. Supporting arms 31 and 32a are pivotally joined by a pivot pin corresponding to pivot pin 33 connecting arms 31 and 32.
Supporting arm 31b has a supporting roller 36b which rides on the upper surface of square tubing 15. Supporting arm 31b intersects and is pinned to a supporting arm which corresponds to supporting arms 32 and 32a. That supporting arm is hidden in the view shown in FIG. 1 but is pivotally connected on square tubing 15 on the base portion of supporting frame 11. Supporting arm 31b is pivotally connected to the underside of table 29 in the same manner as supporting arms 31 and 32a. A brace 38 is welded between supporting arms 31 and 31a. A second brace 39 is welded in place between supporting arms 31a and 31b. Another brace 40 is welded in place between supporting arms 31 and 31a. A further brace, which is hidden in this view, is welded in place between supporting arms 31a and 31b in a position representing substantially an extension of brace 40.
The scissors type support 30 for table 29 is operable to raise and lower table 29 by extension of the lower ends of arms 31, 31a and 31b which causes the support to lower the table and by retraction of arms 31, 31a and 31b causes the table to be raised in a vertical direction without any lateral deviation. The scissors support is operated by hydraulic cylinder 41 which is pivotally supported at its base on the pivot 34a and which has a piston 42 which is pivoted as at 43 to the middle supporting arm 31a of the scissors type support 30.
Hydraulic cylinder 41 is connected by hydraulic line 44 to a manual hydraulic pump 45 having an operating handle 46. The hydraulic pump and hydraulic cylinder 41 may, if desired, be double acting so that hydraulic pressure can be used for lowering as well as raising table 29. In most cases, however, a single acting pumping arrangement would be satisfactory since the table 29 can be lowered by gravity and allowing the hydraulic pressure to bleed back into the pumping cylinder 45. Table 29 is provided with an extension 47 with an indicator 48 movable along indicia 49 on vertical supporting arm 18. Indicator 48 reading on indicia 49 indicates the precise elevation of table 29 in English or metric units.
On the upper side of supporting table 29 there is affixed a stop member 50 which is of angle iron and has stop guides 51 and 52 at opposite ends. Stop member 50 is aligned and coplanar with supporting bar 26 on the upper portion of frame 11. A stop 53, hinged at 53a, is positioned on supporting bar 26 and is vertically aligned with stop 51 on stop member 50. Stops 51 and 53 locate the end of a sheet metal duct which is to be positioned in the apparatus for bending or closing a seam or joint therein. A pneumatic spring device 54 is supported on an abutment or flange 55 on support 26 and has an end plate 56 which is engageable with one end of a sheet metal duct which is to be positioned in the apparatus and is operable to force the duct into engagement with stop 53.
A pair of fluid operated cylinders 57 and 58 are supported on cantilevered supporting arm 27. Cylinders 57 and 58 may be pneumatically operated or hydraulically operated. If desired, cylinders 57 and 58 could be replaced by any suitable mechanical clamping mechanism. Cylinders 57 and 58 have pistons 59 and 60 which have secured on their outer ends a channel-shaped clamping member 61. Clamping member 61 is movable by cylinders 57 and 58 into clamping engagement with sheet metal which is to be clamped against the front vertical surface of supporting member 26. The connections from cylinders 57 and 58 to their source of fluid pressure and the controls for turning that pressure on and off are not shown but conventional connections and controls are used.
On the upper part of the frame 11 there is provided a carriage 62 which supports a rotary hammer 63, seen in greater detail in FIGS. 2, 3 and 10. Supporting carriage 62 has an upper, channel-shaped housing 64 which extends laterally between upper supporting rails 19 and 20. Channel-shaped housing 64 is provided with wheels 65 and 66 which roll along the upper surface of supporting rail 19 and wheels 67 and 68 which roll along the upper surface of supporting rail 20 and outwardly extending wheels or rollers 69 ride on the vertical face or surface of supporting rail 20 and a corresponding set of wheels or rollers 70 ride on the vertical face or surface of supporting rail 19.
A lower channel-shaped carriage housing 71 supports rotary hammer 63 and is secured to upper housing 64 as seen in FIGS. 2 and 3. Lower houding 71 is provided with two pairs of wheels 72 which ride on the lower surface of supporting rail 19 and two pairs of wheels 73 which ride on the lower surface of supporting rail 20. The wheels of carriage 62 surround the supporting rails 19 and 20, respectively, on three sides and prevent the carriage from becoming derailed. Rotary hammer 63 is supported on bottom carriage housing 71 by bracket 74.
Rotary hammer 63 consists of motor 75, with guard 75a, which is preferably a fluid actuated motor although an electrically powered motor could be used if desired. Motor 75 is provided with rotary shaft 76 which supports a rotary disc 77 having a plurality of hammer abutments 78 thereon. Hammer abutments 78 are preferably cylindrical studs which are threaded into supporting plate 77 and having rounded head portions 79 in operation, motor 75 rotates shaft 76 and disc 77 at a high rate of speed and causes hammer abutments 78 to strike continuous and sequential hammer blows for bending a sheet metal edge to close a "Pittsburgh Lock" joint as will be subsequently described.
At the right end of the machine, as seen in FIGS. 1 and 2, supporting plate 23 supports motor 80 which is preferably the same type of motor as the motor 74 for rotary hammer 63. Thus, if a pneumatic motor is used for rotary hammer 63, a pneumatic motor would likewise be used for motor 80. Motor 80 is connected by shaft 81 to gear box 82 which drives sprocket 83. At the other end of the machine, brackets 84 and 85 support sprocket 86. A drive chain 87 is positioned around and extends between sprockets 83 and 86. Chain 87 is secured to the upper housing portion 64 of carriage 62 as indicated at 88.
Control 89, with operating handle 90, is supported on supporting platform 23. Operation of handle 90 causes control 89 to energize motor 80 to operate chain 87 in a forward (clockwise) direction moving carriage 62 from right to left as seen in the apparatus. At the left end of the machine, a limit switch 91 is supported on supporting arm 19. When carriage 62 engages limit switch 91, motor 80 is switched to a reverse position, by a conventional control system of electric relays which are not shown. This causes motor 80 to rotate sprocket 83 in a counterclockwise direction and return carriage 62 from left to right to its place of origin. At the right end of the apparatus, limit switch 92 is engaged by carriage 62 on returning movement to turn off motor 80.
In FIG. 4, there is shown an alternate clamping arrangement for clamping sheet metal duct in position for closing a "Pittsburgh Lock" by use of the automatic rotary hammer described above. In this embodiment, cantilevered arm 27a is pivotally supported as indicated at 25a. Pressure operated cylinder 58 has its piston 60 operatively connected to supporting arm 26 so that operation of cylinder 58 will pivot arm 17a into or out of clamping engagement. Stops 53a and 53b are slidably adjustable on supporting arm 26 and are provided with set screws 26a and 26b.
OPERATION
In order to understand the operation of this automatic joint or seam closing machine, it is desirable to examine the nature of the "Pittsburgh Lock". In FIGS. 5 to 9, there are shown example of the "Pittsburgh Lock" as used in duct work of a one piece construction and a two piece construction, respectively. In FIG. 10, there is shown a detail, isometric view of the rotary hammer in the process of bending over the edge of the sheet material to close the "Pittsburgh Lock".
In FIG. 5, there is shown one piece 93 of sheet metal duct work with a "Pittsburgh Lock" formed therein for use in formation of a two piece sheet metal duct. The section 93 of duct work has two walls 94 and 95 joined by a right angle bend. Wall 94 has a small flange 96 bent at a right angle thereto. At the upper end of wall 95 there is provided the female section 97 of the "Pittsburgh lock". This female section 97 consists of portion 98 which rebent 180° into a tight bend and then rebent again as indicated at 99 to form a continuous slot 100 with a protruding sheet metal edge 101. In FIG. 6, two sections 93 are fitted together with flanges 96 inserted into the female recess 100 of "Pittsburgh Lock" 97 and the sheet metal edge 101 still extending in an unbent position. To complete the formation of the "Pittsburgh Lock" the protruding sheet metal edge 101 is bent over to the position shown in FIG. 7. This bending is usually accomplished by hand by means of a suitable hammer or occasionally by a portable powered hammering tool.
In FIGS. 8 and 9, there is shown a one piece sheet metal duct 102 having sides 103, 104, 105 and 106 bent in right angle bends as indicated. At the end of wall 106 there is a bent flange 107 which corresponds to flange 96 in FIG. 5. At the end of wall 103 there is a "Pittsburgh Lock" 108 which is of the same construction as shown in FIGS. 5, 6 and 7. This consists of rebent portion 99 having a female slot or recess 110 with extending sheet metal portion 111. To complete the formation of this joint, the protruding sheet metal edge 111 is bent over as shown in FIG. 9.
In FIG. 10, the rotary hammer 63 is shown as it moves along "Pittsburgh Lock" 108 to bend protruding edge 111 to a closed position. The rotation of disc 77 and hammer abutments 78 thereon causes the hammer abutments to engage protruding edge 111 sequentially and continuously to bend over the edge 111 to form a tightly closed lock as shown in FIG. 10.
In considering the operation of the apparatus described above, it should be noted that sheet metal duct work comes in a large variety of sizes depending upon the required capacity of the ducts. Thus, very small ducts may be used for low capacity heating or air conditioning systems or for systems having very high velocity air flows. Larger ducts may be used for larger capacity systems, for gravity circulation systems, and for return air ducts where a number of separate air flows may be combined into a single large duct returning to the furnace or heater or air conditioning unit. It should also be noted that duct work is usually made in sections of uniform length for ease of handling. The sections are designed to be assembled end to end. One particular method of assembly utilizes a projecting edge on two opposite sides of the duct which fits into a female fold on the rear end of the adjacent duct. The other two sides of each of the ducts are provided with reverse bends onto which there is driven a clamping sleeve. In forming sheet metal ducts, it is necessary that the duct be assembled accurately so that it is not crooked or skewed and the connecting portions are in a proper position for assembly of the ducts.
In using the equipment described above, the description of operation will first be given with respect to a one-piece duct of the type shown in FIGS. 8 and 9. In assembling a duct of this type, the duct is assembled to the position shown in FIG. 8 with the unbent edge 111 of the "Pittsburgh Lock" 108 protruding above the upper wall 106 of the duct. The supporting table 29 is raised to the desired elevation by actuation of handle 46 of hydraulic pump 45. Table 29 is raised to a position such that the rotation of disc 77 of rotary hammer 63 will cause hammer posts 78 to engage and bend over the protruding edge 111 of "Pittsburgh Lock" 108 to the bent position shown in FIG. 9. The adjustment of the level of table 29 is such that the posts 78 of rotary hammer 63 will just clear the surface of the bent over and closed "Pittsburgh LocK" as shown in FIGS. 9 and 10.
The duct in its unformed state as seen in FIG. 8 is placed on table 29 in preparation for bending and closing the "Pittsburgh Lock". At the start of the operation the carriage 62 which suppots rotary hammer 63 is in its normal starting position at the extreme right of the apparatus adjacent to limit switch 92. The clamping member 61 is retracted as seen in FIG. 1. The duct is slid into the space between clamping member 61 and the forward, vertical face of frame member 26. The bottom of the duct is slid along the surface of stop member 50 and into stop 52 at one end.
This movement brings the end of the duct into abutment with the end member 56 of pneumatic spring 54. The pneumatic spring 54 is retracted slightly by this movement and the other end of the duct is brought against the surface of stop member 50. The duct is then pushed by the force of pneumatic spring 54 to the point where the other end engages stop member 53 on frame member 26 and stop member 51 on the back stop 50. Stop 53 is hinged at 53a to be moved out of the way when the duct is inserted or removed. In this position, the end connecting portions of the duct are positioned squarely for formation of the tightly closed "Pittsburgh Lock" joint. At this point, fluid actuated cylinders 57 and 58 are operated to cause clamping member 61 to clamp the rear wall 103 of the duct against the forward vertical surface of frame member 26. The duct is held tightly by this clamp during the joint closing operation.
In the position just described, the rotary hammer 63 has a substantial clearance from the upper surface of frame member 26 but is positioned relative to the protruding edge 111 of "Pittsburgh Lock" 108 so that on rotation of disc 77 the hammer posts 78 will engage the protruding edge 111 sequentially and continuously to bend over and close the "Pittsburgh Lock". Lever 90 is then operated to energize motors 80 and 75.
Motor 80 actuates the traversing mechanism for moving the carriage 62 along the supporting track formed of rails 19 and 20. Motor 80 rotates drive sprocket 83 and causes drive chain 87 to move carriage 62 along the length of the track. Simultaneously, motor 75 rotates disc 77 and hammer posts 78 at a high rate of speed to provide a sequential and continuous hammering operation.
The movement of carriage 62 causes rotary hammer 63 to be moved along the length of the duct in accurate alignment with the corner of the duct where the "Pittsburgh Lock" joint is to be closed. The carriage 62 moves the rotary hammer 63 along the length of the duct and causes the "Pittsburgh Lock" joint to be closed as shown in FIG. 10. When carriage 62 reaches the end of its travel, it engages limit switch 91 which causes motor 80 to reverse and return carriage 62 to its starting point where the operation is stopped by engagement with limit switch 92.
At this point, fluid operated clamping cylinders 57 and 58 are deenergized causing clamping member 61 to retract and the finished duct is then removed manually from the apparatus. In this apparatus, table 29 is adjustable to accommodate various sizes of sheet metal ducts. The position of limit switch 91 is adjustable to vary the length of the path of movement of carriage 62. The stops 51 and 53 are also adjustable to accommodate various lengths of sheet metal duct work. In the alternate embodiment, shown in FIG. 4, a pivoted clamping arrangement is used which is advantageous for certain types of duct work.
When the apparatus is used for closing "Pittsburgh Lock" joints on two piece sheet metal ducts, the operation substantially the same as described above. The only difference is that two separate joint-clsoing operations are required. In forming a two piece sheet metal duct, one of the joints is fitted together somewhat in the manner of the arrangement shown in FIG. 6. The assembly would differ from that shown in FIG. 6 in that the joint in the lower left hand corner would be left loose when the partially assembled duct was placed in the apparatus for closing the joint in the upper right hand corner. After that joint is closed, the duct is removed from the clamps, the remaining joint assembled and put into the apparatus, and the joint formed as previously described.
While this invention has been described fully and completely with special emphasis upon two preferred embodiments, it should be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described and shown herein. | An automatic closing machine for sheet metal joints in sheet metal ducts or the like consists of a powered rotary hammer for continuous application of a hammering force to the edge portion of a joint to be formed to fold such edge into a closed joint. A supporting frame with a vertically adjustable support permits varying the relative vertical spacing of the edge of the duct and the rotary hammer. Stops locate the duct longitudinally to set the length of the joint relative to the location of the end connecting edges of the duct. Pneumatic clamps secure the duct accurately for forming the joint by the rotary hammer. A track supports the rotary hammer for longitudinal movement and an automatic traversing mechanism moves the rotary hammer therealong. The traversing mechanism automatically moves the rotary hammer back and forth along the track. The vertical adjustment locates the edge of the unformed duct properly relative to the path of movement of the rotary hammer for any selected duct size. Likewise, the traversing mechanism controls may vary the distance of movement of the rotary hammer for any selected duct length. The apparatus is satisfactory for forming both one-piece duct joints and two-piece duct joints. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an innovative polyhydroxyalkanoate (may hereinafter be abbreviated as PHA) and a method of producing the same. Particularly, the present invention relates to a polyhydroxyalkanoate having hydrophilic groups and a method of producing the same.
In addition, the present invention relates to a charge controlling agent for use in electrophotography, electrostatic recording, magnetic recording and the like, a toner binder, an electrostatic latent image developing toner, an image formation method using the toner, and an image forming apparatus for use therein. Particularly, the present invention relates to a charge controlling agent for use in electrophotography, electrostatic recording and electrostatic printing in a copying apparatus, a printer, a facsimile machine and the like for forming an image in such a manner that a toner image is previously formed on an electrostatic latent image carrier (hereinafter, referred to simply as image carrier) and thereafter the image is transferred onto an object transfer material, a toner binder, an electrostatic latent image developing toner, an image formation method using the toner and an image forming apparatus for use therein.
2. Related Background Art
So far, many methods have been known for electrophotography, and those methods are generally carried out in such a manner that an electric latent image is formed on an image carrier (photoconductor) by a variety of means using a photoconductive substance, the latent image is then developed with a toner to form a visible image, and the toner image is transferred onto an object transfer material such as a paper as necessary, followed by fixing the toner image on the object transfer material by heat and/or pressure or the like to obtain a copy. For the method for visualizing the electric latent image, a cascade development method, a magnetic brush development method, a pressurizing development method and the like are known. Further, a method using a magnetic toner and a rotary development sleeve with a magnetic pole placed at the center thereof in which the magnetic toner is caused to fly from the development sleeve onto the photoconductor by a magnetic field is also used.
Development systems for use in development of an electrostatic latent image include a two-component development system using a two-component type developer constituted by a toner and a carrier, and a one-component development system using a one-component type developer constituted only by a toner and using no carrier.
Here, the coloring fine particle generally called as a toner has a binder resin and a coloring material as essential components, and in addition thereto, magnetic powders and the like as necessary. For the method for imparting an electric charge to the toner, the electrifiability of the binder resin itself may be used without using a charge controlling agent, but in this method, charge stability with time and humidity resistance are compromised, thus making it impossible to obtain high quality images. Therefore, the charge controlling agent is usually added for the purpose of maintaining and controlling the charge of the toner.
Today, charge controlling agents known in the art include, for example, azo dye metal complexes, aromatic dicarboxylic-metal complexes and salicylic acid derivative-metal complexes for the negative friction charging agent. In addition, for the positive friction charging agent, nigrosine based dyes, triphenylmethane based dyes, various kinds of quaternary ammonium salts, and organic tin compounds such as dibutyl tin oxide are known, but toners containing these substances as the charge controlling agent do not necessarily fully satisfy quality characteristics required for the toner such as the electrifiability and stability with time depending on their compositions.
For example, a toner containing an azo dye metal complex known as a negative charge controlling agent has an acceptable charge level, but may have reduced dispersibility depending on the type of binder resin to be combined because the azo dye metal complex is a low-molecular crystal. In this case, the negative charge controlling agent is not uniformly distributed in the binder resin, the charge level distribution of the obtained toner is significantly lacking in sharpness, and the obtained image has a low gray-level, resulting in a poor image formation capability. In addition, the azo dye metal complex has a unique color tone, and is thus presently used only for toners having limited colors around black, and if the azo dye metal complex is used as a color toner, its lack in clarity as a coloring agent required for obtaining an image having a high level of requirement for the color tone is a serious problem.
In addition, examples of almost colorless negative charge controlling agents include aromatic dicarboxylic-acid metal complexes, but they may be disadvantageous due to the fact that they are not perfectly colorless, and that they have low dispersibility peculiar to low-molecular-weight crystals.
On the other hand, nigrosine based dyes and triphenylmethane based dyes are presently used only for toners having limited colors around black because they are colored themselves, and may be poor in time stability of toners for continuous copying. In addition, conventional quaternary ammonium salts may have insufficient humidity resistance when formed into toners, and in this case, the stability with time may be so poor that high quality images are not provided as they are repeatedly used.
In addition, in recent years, attention has been given worldwide to reduction of wastes and improvement of safety of wastes in terms of environmental protection. This problem applies to the field of electrophotography as well. That is, as imaging apparatuses have been widely used, the amounts of wastes of printed papers, discarded toners and copying papers have increased year by year, and the safety of such wastes is important from a viewpoint of protection of global environment.
Polyhydroxyalkanoate (PHA)
Resins that can be decomposed with time by the action of microorganisms and the like, namely biodegradable resins are under development in terms of environmental protection, and for example, many types of microorganism have been reported to produce biodegradable resins having polyester structures (polyhydroxyalkanoate: hereinafter abbreviated as PHA) and accumulate the resin in the cell (Non-patent Document 1). These polymers may be used for production of various kinds of products through melt processing as in the case of conventional plastics. In addition, these polymers have an advantage that owing to their biodegradability, they are fully decomposed by microorganism in the natural environment, and unlike many synthetic polymer compounds, they never remain in the natural environment to cause contamination. In addition, they are also excellent in biocompatibility, and are expected to be applied as medical flexible members and the like.
It is known that such PHA may various compositions and structures depending on the type of microorganism to be used for the production of the PHA, the culture medium composition and the culture condition, and hitherto studies have been conducted mainly on control of the composition and structure of PHA to be produced in terms of improvements of properties of PHA.
[1] First, the biosynthesis of PHA obtained by polymerizing a monomer unit with a relatively simple structure such as 3-hydroxybutyric acid (hereinafter abbreviated as 3HB) is exemplified as follows:
(a) those containing 3HB and 3-hydroxyvaleric acid (hereinafter abbreviated as 3HV) (see Patent Documents 1 to 4);
(b) those containing 3HB and 3-hydroxyhexanoic acid (hereinafter abbreviated as 3HHx) (see Patent Documents 5 and 6);
(c) those containing 3HB and 4-hydroxybutyric acid (hereinafter abbreviated as 4HB) (see Patent Document 7);
(d) those containing 3-hydroxyalkanoate having 6 to 12 carbon atoms (see Patent Document 8); and
(e) biosynthesis using a single aliphatic acid as a carbon source (the resulting product is almost same as those of (d)) (see Non-Patent Document 2).
They are all PHA composed of monomer units each having an alkyl group in the side chain, synthesized by β-oxidation of hydrocarbons and the like or synthesis of fatty acid from saccharides by microorganism, namely “usual PHA”.
Such PHA has already found considerable applications with proven performance particularly in the field of agriculture, the biodegradable resin is used in mulch files, horticulture materials, slow-releasable agricultural chemicals, fertilizers and the like. Also, in the leisure industry, the biodegradable resin is used in fishing lines, fishing tackles, golf requites and the like.
[2] However, if considering a wide range of application as a plastic, it cannot be the above described that PHA is fully usable in terms of properties in the present situation. For further expanding the range of application of PHA, it is important to conduct a wide range of studies on the improvement of properties, and for this purpose, development and search of PHA including monomer units of a variety of structures is prerequisite. On the other hand, PHA with a substituent group introduced in the side chain (“unusual PHA”) can be expected to be developed as a “functional polymer” with very useful functions and properties originating from the introduced substituent group by selecting the introduced substituent group according to desired characteristics and the like. That is, it is also an important challenge to conduct of development and search of excellent PHA enabling such functionality and biodegradability to be compatible with each other. Examples of substituent groups include groups containing aromatic rings (phenyl group, phenoxy group, etc.), unsaturated hydrocarbons, ester groups, allyl groups, cyano groups, halogenated hydrocarbons and epoxide. Among them, studies on PHA having an aromatic ring are particularly vigorously conducted.
(a) PHA Containing a Phenyl Group or its Partially Substituted Group
It is reported that Pseudomonas oleovorans produces PHA containing 3-hydroxy-5-phenylvaleric acid as a unit using 5-phenylvaleric acid as a substrate (see Non-Patent Documents 3 and 4).
It is reported that Pseudomonas oleovorans produces PHA containing 3-hydroxy-5-(4′-tolyl) valeric acid as a unit using 5-(4′-tolyl) valeric acid as a substrate (see Non-Patent Document 5).
It is reported that Pseudomonas oleovorans produces PHA containing 3-hydroxy-5-(2′,4′-dinitrophenyl) valeric acid and 3-hydroxy-5-(4′-nitrophenyl) valeric acid as a unit using 5-(2′,4′-dinitrophenyl) valeric acid as a substrate (see Non-Patent Document 6).
(b) PHA Containing a Phenoxy Group or its Partially Substituted Group
It is reported that Pseudomonas oleovorans produces a PHA copolymer of 3-hydroxy-5-phenoxyvaleric acid and 3-hydroxy-9-phenoxynonanoic acid using 11-pheoxyundecanoic acid as a substrate (see Non-Patent Document 7).
An invention relating to a homopolymer consisting of 3-hydroxy-5-(monofluorophenoxy) pentanoate (3H5(MFP)P) units or 3-hydroxy-5-(difluorophenoxyl) pentanoate (3H5(DFP)P) units, a copolymer containing at least (3H5(MFP)P) units or (3H5(DFP)P) units; Pseudomonas putida synthesizing these polymers; and a method of producing the above described polymers using Pseudomonas species is disclosed, and it is described that as an advantage of the above invention, a long chain aliphatic acid having substituent groups can be metabolized to synthesize a polymer having a phenoxy group substituted with 1 or 2 fluorine atoms at the side chain terminal, and stereoregularity and water repellency are provided while maintaining a high melting point and good processability (see Patent Document 9).
Studies are conducted on cyano-substituents and nitro-substituents in addition to the fluorine-substituent described above.
It is reported that PHA containing 3-hydroxy-p-cyanophenoxyhexanoic acid or 3-hydroxy-p-nitrophenoxyhexanoic acid as a monomer unit is produced with octanoic acid and p-cyanophenoxyhexanoic acid or p-nitrophenoxyhexanoic acid as substrates using a Pseudomonas oleovorans ATCC 29347 strain and a Pseudomonas putida KT 2442 strain (see Non-Patent Documents 8 and 9).
These reports are useful in obtaining polymers each having an aromatic ring in the side chain of PHA and having properties derived therefrom unlike general PHA whose side chain contains an alkyl group.
[3] In addition, as a new category, studies are conducted for producing PHA having an appropriate functional group in the side chain and using the functional group to create a new function, beyond mere modification of properties of PHA.
It is reported that PHA containing a unit having a vinyl group at the terminal of the side chain was synthesized, and was thereafter epoxidized, whereby PHA containing a highly reactive epoxy group at the side chain terminal could be synthesized (see Non-Patent Documents 10 and 11).
In addition, it is reported that PHA containing a unit having a vinyl group at the terminal of the side chain was synthesized, and thereafter benzoyl peroxide was used with per-O-acetyl-1-thio-β-maltose, whereby PHA containing a sugar chain could be synthesized, and that PHA containing a unit having a bromo group at the terminal of the side chain was synthesized, and thereafter diethyl amine was used with per-O-acetyl-1-thio-β-maltose, whereby PHA containing a sugar chain could be synthesized (see Non-Patent Document 12).
Application of Biodegradable Resin to Toner
Application of a biodegradable resin to a binder resin particularly in production of toners is proposed in the field of electrophotography as well. For example, U.S. Pat. No. 5,004,664 (Patent Document 10) discloses a toner having as its composition a biodegradable resin, particularly polyhydroxy butyric acid and polyhydroxy valeric acid, a copolymer thereof or a blend thereof. In addition, Japanese Patent Application Laid-Open No. 6-289644 (Patent Document 11) discloses an electrophotographic toner particularly for heated roll fixation characterized in that at least the binder resin contains a plant based wax and a biodegradable resin (e.g. polyester produced by microorganism, and natural polymer material of plant or animal origin), and the above described plant based wax is added in the above described binder in an amount of 5 to 50% by weight.
In addition, Japanese Patent Application Laid-Open No. 7-120975 (Patent Document 12) discloses an electrophotographic toner characterized by containing a lactic acid based resin as a binder resin. In addition, Japanese Patent Application Laid-Open No. 9-274335 (Patent Document 13) discloses an electrostatic latent image developing toner characterized by containing a polyester resin obtained by dehydrating polycondensation of a composition containing lactic acid and tri- or higher functional oxycarboxylic acid and a coloring agent.
In addition, Japanese Patent Application Laid-Open No. 8-262796 (Patent Document 14) discloses an electrophotographic toner containing a binder resin and a coloring agent, characterized in that the binder resin is composed of a biodegradable resin (e.g. aliphatic polyester resin), and the coloring agent is composed of non-water soluble pigments. In addition, Japanese Patent Application Laid-Open No. 9-281746 (Patent Document 15) discloses an electrostatic latent image developing toner characterized by containing an urethane-modified polyester resin obtained by cross-linking polylactic acid with a tri- or higher functional polyvalent isocyanate and a coloring agent.
Any one of the above described electrophotographic toners contains a biodegradable resin as binder resin, and is regarded to be effective to contribute to preservation of environments and the like.
However, reports of examples of using a biodegradable resin in the charge controlling agent have not been known, and there is a room for further improvement for contribution to preservation of environments.
In addition to the above described documents, the content of Japanese Patent Application Laid-Open No. 2001-178484 (Patent Document 16) is herein incorporated.
[Patent Document 1] Japanese Patent Publication No. 6-15604
[Patent Document 2] Japanese Patent Publication No. 7-14352
[Patent Document 3] Japanese Patent Publication No. 8-19227
[Patent Document 4] Japanese Patent Application Laid-Open No. 5-7492
[Patent Document 5] Japanese Patent Application Laid-Open No. 5-93049
[Patent Document 6] Japanese Patent Application Laid-Open No. 7-265065
[Patent Document 7] Japanese Patent Application Laid-Open No. 9-191893
[Patent Document 8] Japanese Patent No. 2642937
[Patent Document 9] Japanese Patent No. 2989175
[Patent Document 10] U.S. Pat. No. 5,004,664
[Patent Document 11] Japanese Patent Application Laid-Open No. 6-289644
[Patent Document 12] Japanese Patent Application Laid-Open No. 7-120975
[Patent Document 13] Japanese Patent Application Laid-Open No. 9-274335
[Patent Document 14] Japanese Patent Application Laid-Open No. 8-262796
[Patent Document 15] Japanese Patent Application Laid-Open No. 9-281746
[Patent Document 16] Japanese Patent Application Laid-Open No. 2001-178484
[Non-Patent Document 1] “Biodegradable Plastic Handbook” Biodegradable Plastic Research Associate, N.T.S. Co., Ltd., p. 178-197 (1995)
[Non-Patent Document 2] Appl. Environ. Microbiol, 58 (2), p. 746 (1992)
[Non-Patent Document 3] Makromol. Chem., 191, p. 1957-1965 (1990).
[Non-Patent Document 4] Macromolecules, 24, p. 5256-5260 (1991)
[Non-Patent Document 5] Macromolecules, 29, p. 1762-1766 (1996)
[Non-Patent Document 6] Macromolecules, 32, p. 2889-2895 (1999)
[Non-Patent Document 7] Macromol. Chem. Phys., 195, p. 1665-1672 (1994)
[Non-Patent Document 8] Can. J. Microbiol., 41, p. 32-43 (1995)
[Non-Patent Document 9] Polymer International, 39, p. 205-213 (1996)
[Non-Patent Document 10] Macromolecules, 31, p. 1480-1486 (1996)
[Non-Patent Document 11] Journal of Polymer Science: Part A: Polymer Chemistry, 36, p. 2381-2387 (1998)
[Non-Patent Document 12] Macromol. Rapid Commun., 20, p. 91-94 (1999)
As described above, researches are being conducted for creating a new function, but only few successful cases have been reported. In particular, 3-hydroxybutylic acid has an advantage that it is completely decomposed by microorganism in the nature, but it has a problem in terms of melt processability because of its high crystallinity, hardness and fragility. Therefore, PHA with improved melt processability has been desired.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an innovative polyhydroxyalkanoate with sulfonic group as a hydrophilic group or a derivative thereof introduced for improving melt processability, and a method of producing the same. In addition, the polyhydroxyalkanoate of the present invention is excellent in biocompatibility owing to its hydrophilic nature, and is expected to be applied as medical flexible members and the like.
In addition, for solving the above described problems, the present invention provides a negatively charged charge controlling agent being more contributable to preservation of environments and the like, and having high performance (high charge level, quick start of charge, excellent stability with time, and high environmental stability) and improved dispersibility in the aspect of functionality, a toner binder containing the charge controlling agent, an electrostatic latent image developing toner containing the charge controlling agent, and an image formation method and an image forming apparatus using the electrostatic latent image developing toner.
Thus, the inventors have devised the following invention as a result of vigorously conducting researches for development of an innovative polyhydroxyalkanoate with a hydrophilic group introduced, which is believed to be useful for improving melt processability. In addition, the inventors have vigorously conducted studies for developing a charge controlling agent having high performance and being substantially colorless, resulting in the achievement of the present invention.
That is, the outline of the present invention is as follows.
[1] A polyhydroxyalkanoate comprising a unit of formula (1):
wherein R is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 ane OC 2 H 5 ; A represents a substituted or unsubstituted aliphatic hydrocarbon structure; m is an integer number selected from 1 to 8; and in the case where a plurality of units exist in the same molecule, R, A and m in one unit can be different from them in another unit respectively.
[2] The polyhydroxyalkanoate according to item [1], comprising a unit of formula (2):
wherein R 1 is H or CH 3 ; R 2 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 ; B 1 and C 1 each represent a substituted or unsubstituted aliphatic hydrocarbon structure; m is an integer number selected from 1 to 8; and in the case where a plurality of units exist in the same molecule, R 1 , R 2 , B 1 , C 1 and m in one unit can be different from them in another unit respectively.
[3] The polyhydroxyalkanoate according to item [2], comprising a unit of formula (3):
wherein R 3 is H or CH 3 ; R 4 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 ; B 2 and C 2 each represent a straight-chain or branched alkylene group having 1 to 8 carbon atoms; m is an integer number selected from 1 to 8; and in the case where a plurality of units exist in the same molecule, R 3 , R 4 , B 2 , C 2 and m in one unit can be different from them in another unit respectively.
[4] The polyhydroxyalkanoate according to item [3], comprising a unit of formula (4):
wherein R 5 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 ; m is an integer number selected from 1 to 8; and in the case where a plurality of units exist in the same molecule, R 5 and m in one unit can be different from them in another unit respectively.
[5] The polyhydroxyalkanoate according to item [1], wherein m in formula (1) is an integer selected from the group consisting of 4, 6 and 8.
[6] The polyhydroxyalkanoate according to item [1], wherein m in formula (1) is an integer of 3 or 5.
[7] The polyhydroxyalkanoate according to item [1], comprising at least one of
a 3-hydroxy-ω-alkanoic acid unit of formula (5):
wherein n is an integer number selected from 1 to 8; R 6 contains a residue having a phenyl structure or a thienyl structure; and in the case where a plurality of units exist in the same molecule, n and R 6 in one unit can be different from them in another unit respectively and a 3-hydroxy-ω-cyclohexylalkanoic acid unit of formula (6):
wherein R 7 is a substituent group in the cyclohexyl group selected from the group consisting of H, CN, NO 2 , a halogen atom, CH 3 , C 2 H 5 , C 3 H 7 , CF 3 , C 2 F 5 and C 3 F 7 ; k is an integer number selected from 0 to 8; and in the case where a plurality of units exist in the same molecule, k and R 7 in one unit can be different from them in another unit respectively.
[8] The polyhydroxyalkanoate according to item [7], wherein R 6 in formula (5) is selected from the group consisting of the groups of the following formulas (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) and (17):
unsubstituted or substituted phenyl groups of formula (7):
wherein R 8a represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , CH 3 , C 2 H 5 , C 3 H 7 , CH═CH 2 , COOR 8b (R 8b represents any one selected from the group consisting of H, Na and K), CF 3 , C 2 F 5 and C 3 F 7 , and in the case where a plurality of units exist in the same molecule, R 8a in one unit can be different from that in another unit; unsaturated or saturated phenoxy groups of formula (8):
wherein R 9 represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , CH 3 , C 2 H 5 , C 3 H 7 , SCH 3 , CF 3 , C 2 F 5 and C 3 F 7 , and in the case where a plurality of units exist in the same molecule, R 9 in one unit can be different from that in another unit; unsubstituted or substituted benzoyl groups each of formula (9):
wherein R 10 represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , CH 3 , C 2 H 5 , C 3 H 7 , CF 3 , C 2 F 5 and C 3 F 7 , and in the case where a plurality of units exist in the same molecule, R 10 in one unit can be different from that in another unit; unsubstituted or substituted phenylsulfanyl groups of formula (10):
wherein R 11a represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , COOR 11b , SO 2 R 11c (R 11b represents any one selected from the group consisting of H, Na, K, CH 3 and C 2 H 5 , and R 11c represents any one selected from the group consisting of OH, ONa, OK, a halogen atom, OCH 3 and OC 2 H 5 ), CH 3 , C 2 H 5 , C 3 H 7 , (CH 3 ) 2 —CH and (CH 3 ) 3 —C, and in the case where a plurality of units exist in the same molecule, R 11a in one unit can be different from that in another unit; unsubstituted or substituted (phenylmethyl) sulfanyl groups of formula (11):
wherein R 12a represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , COOR 12b , SO 2 R 12c (R 12b represents any one selected from the group consisting of H, Na, K, CH 3 and C 2 H 5 , and R 12c represents any one selected from the group consisting of OH, ONa, OK, a halogen atom, OCH 3 and OC 2 H 5 ), CH 3 , C 2 H 5 , C 3 H 7 , (CH 3 ) 2 —CH and (CH 3 ) 3 —C, and in the case where a plurality of units exist in the same molecule, R 12a in one unit can be different from that in another unit; 2-thienyl group of formula (12):
2-thienylsulfanyl group of formula (13):
2-thienylcarbonyl group of formula (14):
unsubstituted or substituted phenylsulfinyl groups of formula (15):
wherein R 13a represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , COOR 13b (R 13b represents any one selected from the group consisting of H, Na, K, CH 3 and C 2 H 5 ), SO 2 R 13c (R 13c represents any one selected from the group consisting of OH, ONa, OK, a halogen atom, OCH 3 and OC 2 H 5 ), CH 3 , C 2 H 5 , C 3 H 7 , (CH 3 ) 2 —CH and (CH 3 ) 3 —C, and in the case where a plurality of units exist in the same molecule R 13a in one unit can be different from that in another unit; unsubstituted or substituted phenylsulfonyl groups of formula (16):
wherein R 14a represents a substituent group in the aromatic ring selected from the group consisting of H, a halogen atom, CN, NO 2 , COOR 14b (R 14b represents any one selected from the group consisting of H, Na, K, CH 3 and C 2 H 5 ), SO 2 R 14b (R 14c represents any one selected from the group consisting of OH, ONa, OK, a halogen atom, OCH 3 and OC 2 H 5 ), CH 3 , C 2 H 5 , C 3 H 7 , (CH 3 ) 2 —CH and (CH 3 ) 3 —C, and in the case where a plurality of units exist in the same molecule R 14a in one unit can be differend from that in another unit; and (phenylmethyl)oxy groups of formula (17):
, and in the case where a plurality of units exist in the same molecule, R 6 in one unit of formula (5) can be different from that in another unit.
[9] The polyhydroxyalkanoate according to item [1], wherein the number-average molecular weight is in the range of from 1000 to 1000000.
[10] A method of producing polyhydroxyalkanoate comprising a unit of formula (1), which comprises the step of:
reacting a polyhydroxyalkanoate comprising a unit of formula (18):
, wherein m is an integer number selected from 1 to 8, and in the case where a plurality of units exist in the same molecule, m in one unit can be different from that in another unit, with at least one type of compounds of formula (19):
HS-A 1 -SO 2 R 15 (19)
wherein R 15 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 and A 1 is a substituted or unsubstituted aliphatic hydrocarbon structure, and in the case where a plurality of types of compounds exist in the same molecule, R 15 and A 1 in one unit can be different from them in another unit respectively.
[11] A method of producing polyhydroxyalkanoate comprising a unit of formula (2), which comprises the step of:
reacting a polyhydroxyalkanoate comprising a unit of formula (18) with at least one type of compounds of formula (20):
wherein R 16 is H or CH 3 ; R 17 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 ; B 3 and C 3 are selected from substituted or unsubstituted aliphatic hydrocarbon structures; and in the case where a plurality of types of compounds exist in the same molecule, R 16 , R 17 , B 3 and C 3 in one unit can be different from them in another unit respectively.
[12] The method according to item [10], wherein the reacting step is carried out under basic condition.
[13] The method according to item [12], wherein at least one selected from the group consisting of dimetylamine, diethylamine, trimethylamine, triethylamine, dibutylamine, morpholine, piperidine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methylate and sodium ethylate is used as a basic catalyst in the reacting step.
[14] A charge controlling agent controlling the charged state of powder, the charge controlling agent containing polyhydroxyalkanoate comprising a unit of formula (1).
[15] The charge controlling agent controlling the charged state of powder according to item [14], the charge controlling agent containing polyhydroxyalkanoate comprising a unit of formula (2).
[16] The charge controlling agent controlling the charged state of powder according to item [15], the charge controlling agent containing polyhydroxyalkanoate comprising a unit of formula (3).
[17] The charge controlling agent controlling the charged state of powder according to item [16], the charge controlling agent containing polyhydroxyalkanoate comprising a unit of formula (4).
[18] The charge controlling agent according to item [14], comprising at least one of a 3-hydroxy-ω-alkanoic acid unit of formula (5) and a 3-hydroxy-ω-cyclohexylalkanoic acid unit of formula (6).
[19] The charge controlling agent according to item [18], wherein R 6 in chemical formula (5) is selected from the group consisting of formulae (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) and (17).
[20] The charge controlling agent according to item [14], wherein the powder is an electrostatic latent image developing toner.
[21] The charge controlling agent according to item [14], wherein the number-average molecular weight of the polyhydroxyalkanoate is in the range of from 1000 to 1000000.
[22] A toner binder for use in an electrostatic latent image developing toner, the toner binder containing the charge controlling agent according to item [14].
[23] An electrostatic latent image developing toner containing a binder resin, a coloring agent and the charge controlling agent according to item [14].
[24] A method for forming an image which comprises the steps of:
applying a voltage to an electrification member from the outside to electrify an electrostatic latent image carrier, forming an electrostatic latent image on the electrified electrostatic latent image carrier, developing the electrostatic latent image by an electrostatic latent image developing toner to form a toner image on the electrostatic latent image carrier, transferring the toner image on the electrostatic latent image carrier to a record material, and fixing the toner image on the record material by heat, wherein an electrostatic latent image developing toner according to item [23] is used.
[25] The method according to item [24], wherein the transferring step comprises a first transferring step of transferring the toner image on the electrostatic latent image carrier to an intermediate transfer body and a second transferring step of transferring the toner image on the intermediate transfer body to the record material.
[26] An image forming apparatus comprising a means for applying a voltage to an electrification member from the outside to electrify an electrostatic latent image carrier, a means for forming an electrostatic latent image on the electrified electrostatic latent image carrier, a means for developing the electrostatic latent image by an electrostatic latent image developing toner to form a toner image on the electrostatic latent image carrier, a means for transferring the toner image on the electrostatic latent image carrier to a record material, and a means for fixing the toner image on the record material by heat, wherein an electrostatic latent image developing toner according to item [23] is used.
[27] The image forming apparatus according to item [26], wherein the transferring means comprises a first transferring means for transferring the toner image on the electrostatic latent image carrier to an intermediate transfer body and a second transferring means for transferring the toner image on the intermediate transfer body to the record material.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a 1 H-NMR spectrum chart of polyhydroxyalkanoate (PHA) produced in Example 1;
FIG. 2 is a schematic explanatory view of an image forming apparatus used in Examples 23 to 40 and Comparative Examples 7 to 12;
FIG. 3 is a sectional view of a principal part of a development apparatus for a two-component developer used in Examples 23 to 40 and Comparative Examples 7 to 12;
FIG. 4 is a schematic explanatory view having a reuse mechanism of a toner used in Examples 41 to 43 and Comparative Examples 13 to 15;
FIG. 5 is a sectional view of a principal part of a development apparatus for a one-component developer used in Examples 41 to 43 and Comparative Examples 13 to 15;
FIG. 6 is an exploded perspective view of a principal part of a fixation apparatus used in the Example of the present invention;
FIG. 7 is an enlarged sectional view of a principal part showing a film state of the fixation apparatus used in the Example of the present invention at the time when it is not driven; and
FIG. 8 is a schematic view showing a blow-off charge level measuring apparatus for measuring the charge level of the toner.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The compound for use in the present invention has a basic skeleton as a biodegradability resin, and is therefore capable of being used for producing various kinds of products through melt-processing and the like as in the case of conventional plastics, and also has a remarkable characteristic such that it is decomposed by microorganism and involved in the material cycle in the natural world unlike synthetic polymers derived from oil.
The compound presented in the present invention, which is suitable as a charge controlling agent for use in an electrostatic latent image developing toner of the present invention will specifically be described. The compound for use in the present invention is a polyester resin having 3-hydroxyalkanoate as a monomer unit, namely polyhydroxyalkanoate having units each expressed by chemical formula (1).
Here, when such a compound is produced by a method comprising a step of producing the compound by microorganism, the compound presented in the present invention is an isotactic polymer composed only of a R configuration, but is not particularly limited to the isotactic polymer and can be used for an atactic polymer as long as the object of the present invention can be achieved in terms of both properties and functions.
The polyhydroxyalkanoate of chemical formula (1) desired in the present invention is produced by a reaction between polyhydroxyalkanoate containing 3-hydroxy-ω-bromoalkanoic acid units each expressed by chemical formula (18), which is used as a starting material, and at least one type of compound expressed by chemical formula (19).
[Method of Producing Polyhydroxyalkanoate Containing Units Each Expressed by Chemical Formula (18)]
The polyhydroxyalkanoate containing units each expressed by chemical formula (18) for use in the present invention can be produced using, but not limited to, a method of production by microorganism, a method of production by a gene-manipulated plant crop system and a method of production by chemical polymerization. Preferably, the method of production by microorganism is used.
A method of producing polyhydroxyalkanoate containing units each expressed by chemical formula (18) in the present invention in which microorganism is used will be described in detail.
If the production by microorganism in the present invention is used, any microorganism may be used as long as it is capable of producing a polyhydroxyalkanoate containing units each expressed by chemical formula (18) when cultured in a culture medium containing at least one type of compound expressed by chemical formula (21), and one example thereof is a microorganism belonging to the Pseudomonas genus.
(In the formula, p is an integer number selected from 1 to 8.)
More particularly, the microorganism includes Pseudomonas cichorii YN2 (FERM BP-7375), Pseudomonas cichorii H45 (FERM BP-7374), Pseudomonas jessenii P161 (FERM BP-7376) and Pseudomonas putida P91 (FERM BP-7373). These four types of microorganisms are deposited at International Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology (former National Institute of Biosciene and Human-Technology, Agency of Industrial Science and Technology) and described in Japanese Patent Laid-Open No. 2001-178484 (Patent Document 16).
These microorganisms are capable of producing PHA containing a corresponding ω-substituted-3-hydroxy-alkanoic acid as a monomer unit using as a raw material a ω-substituted-straight chain alkanoic acid substituted at the chain terminal with a six-membered ring atom group selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy group and a substituted or unsubstituted cyclohexyl group, or a ω-substituted-straight chain alkanoic acid substituted at the chain terminal with a five-membered ring atom group such as a thienyl group.
(Culture Process)
For usual culture of a microorganism for use in the method of producing PHA according to the present invention, for example, production of preservation strains and propagation to secure the number of cells and the level of activity required for production of PHA, a culture medium containing components required to propagate the microorganism to be used is appropriately selected. For example, as long as the growth and survival of microorganisms is not adversely affected, any type of culture medium such as a general natural medium (bouillon medium, yeast extract, etc.) and a synthetic medium with a nutrient source added therein may be used. Culture conditions including among other things temperature, ventilation and agitation conditions may be selected as appropriate depending on the type of microorganism to be used.
In the production method of the present invention, any culture medium may be used for the culture medium for use in the process of culturing a microorganism as long as the culture medium is an inorganic salt culture medium containing a phosphate and a nitrogen source such as an ammonium salt or nitrate, and in the process of producing PHA in the microorganism, the productivity of PHA can be improved by adjusting the concentration of the nitrogen source.
In addition, nutrients such as an yeast extract, polypeptone and a meat extract can be added to the culture medium as a matrix for, promoting the propagation of the microorganism. That is, peptides may be added as an energy source and a carbon source in the form of nutrients such as an yeast extract, polypeptone and a meat extract.
Alternatively, for the culture medium, saccharides, for example, aldoses such as glyceroaldehyde, erythrose, arabinose, xylose, glucose, galactose, mannose and fructose, alditols such as glycerol, erythritol and xylitol, aldonic acids such as gluconic acid, uronic acids such as glucuronic acid and galacturonic acid, and disaccharides such as maltose, sucrose and lactose may be used as an energy source and a carbon source consumed with propagation of the microorganism.
Instead of the above described saccharides, organic acids or salts thereof, more specifically organic acids involved in the TCA cycle and organic acids derived from a biochemical reaction with less steps by one or two steps than the TCA cycle, or water soluble salts thereof may be used. As the organic acid or salt thereof, hydroxycarboxylic acids and oxocarboxylic acids such as pyruvic acid, oxalacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid and lactic acid or water soluble salts thereof can be used. Alternatively, amino acids or salts thereof, for example amino acids such as asparaginic acid and glutamic acid or salts thereof can be used. When the organic acid or salt thereof is added, it is more preferable that one or more types are selected from a group consisting of pyruvic acid, oxalacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid and salts thereof, and are added to the culture medium and dissolved therein. Alternatively, when the amino acid or salt thereof is added, it is more preferable that one or more types are selected from a group consisting of asparaginic acid, glutamic acid and salts thereof, and are added to the culture medium and dissolved therein. At this time, as required, all or part thereof can be added in the form of a water soluble salt to be dissolved uniformly without affecting the pH of the culture medium.
It is desirable that the concentration of the above coexisting substrate added to the culture medium as a carbon source for growth of the microorganism and energy source for production of PHA is usually selected so that it is in the range of from 0.1 to 5% (w/v), more preferably 0.2 to 2% (w/v) per culture medium. That is, for peptides, yeast extracts, organic acids or salts thereof, amino acids or salts thereof, and saccharides that are used as the above coexisting substrates, one or more types thereof may be added, and at this time, it is desirable that the total concentration of these added substrates is with in the above described range of total concentrations.
It is desirable that the content of the matrix for production of desired PHA, namely the compound expressed by general formula (21) is selected so that it is in the range of from 0.0005 to 1% (w/v), more preferably 0.001 to 0.2% (w/v) per cultural medium.
Any temperature at which microorganism strains to be used can suitably be propagated may be selected as a culture temperature, and an appropriate temperature is usually in the range of from about 15 to 37° C., more preferably from about 20 to 30° C.
Any culture method such as liquid culture and solid culture may be used for the culture as long as it allows propagation of microorganism and production of PHA. In addition, any type of culture method such as batch culture, fed-batch culture, semi-continuous culture and continuous culture may be used. Forms of liquid batch culture include a method of supplying oxygen while shaking the microorganism in a shake flask, and a method of supplying oxygen adopting a stirring ventilation system with a jar fermenter.
For the method of making the microorganism produce and accumulate PHA, a two-step culture method in which the microorganism is cultured by two steps may be adopted other than the one-step culture method in which the microorganism is cultured in an inorganic salt culture medium containing a phosphate and a nitrogen source such as an ammonium salt or a nitrate with a matrix added therein in a predetermined concentration as described above. In this two-step culture method, the microorganism is once propagated sufficiently in the inorganic salt culture medium containing a phosphate and a nitrogen source such as an ammonium salt or a nitrate with a matrix added therein in a predetermined concentration as a primary culture, and thereafter cells obtained by the primary culture are relocated to a culture medium with a matrix added therein in a predetermined concentration after limiting the amount of nitrogen source such as ammonium chloride contained in the culture medium, and are further cultured as a secondary culture, thereby making the microorganism produce and accumulate PHA. Use of this two-step culture method may improve the productivity of desired PHA.
Generally, a produced PHA type polyester has reduced water solubility because of the presence of hydrophobic atom groups such as a bromoalkyl group derived from a 3-hydroxy-ω-bromoalakanoic acid unit in the side chain, and is accumulated in cells of the microorganism capable of producing PHA, and therefore can easily be separated from the culture medium by collecting cells propagated by culture and involved in production and accumulation the desired PHA type polyester. After the collected cells are washed and dried, the desired PHA type polyester can be collected.
In addition, PHA is usually accumulated in cells of such a microorganism capable of producing PHA. For the method of collecting desired PHA from these microorganism cells, a method that is usually used may be adopted. For example, extraction with organic solvents such as chloroform, dichloromethane and acetone is most convenient. Other than the above described solvents, dioxane, tetrahydrofuran and acetonitrile may be used. In addition, in a working environment in which use of any organic solvent is not preferred, a method in which in stead of solvent extraction, any one of a treatment by surfactants such as SDS, a treatment by enzymes such as lysozyme, a treatment by chemicals such as hypochlorites, ammonium and EDTA, an ultrasonic crashing method, a homogenizer method, a pressure crushing method, a bead impulse method, a grinding method, an immersion method and a freeze-thaw method is used to physically crush microorganism cells, followed by removing cell components other than PHA to collect PHA may be adopted.
As one example of inorganic salt culture media capable of being used in the production method of the present invention, the composition of the inorganic salt culture medium (M9 culture medium) used in Examples described later is shown below.
Composition of M9 Culture Medium:
Na 2 HPO 4 : 6.3
KH 2 PO 4 : 3.0
NH 4 Cl: 1.0
NaCl: 0.5
(by g/L, at pH=7.0).
Further, for ensuring satisfactory propagation of cells and associated improvement of productivity of PHA, an essential trace element such an essential trace metal element should be added in an appropriate amount to an inorganic salt culture medium such as the above described M9 culture medium, and it is very effective to add about 0.3% (v/v) trace component solution of which composition is shown below. The addition of such a trace component solution supplies a trace metal element for use in propagation of the microorganism.
Composition of Trace Component Solution
nitrilotriacetic acid: 1.5;
MgSO 4 : 3.0; MnSO 4 : 0.5; NaCl: 1.0;
FeSO 4 : 0.1; CaCl 2 : 0.1; CoCl 4 : 0.1;
ZnSO 4 : 0.1; CuSO 4 : 0.1; AlK(SO 4 ) 2 : 0.1;
H 2 BO 3 : 0.1; Na 2 MoO 4 : 0.1; NiCl 2 : 0.1
(g/L).
A matrix for producing desired PHA, namely at least one type of ω-substituted alkanoic acid compound expressed by chemical formula (22) or at least one type of ω-cyclohexylalkanoic acid compound expressed by chemical formula (23) in addition to ω-bromoalkanoic acids each expressed by chemical formula (21) are made to coexist in the culture, whereby PHA containing 3-hydroxy-ω-substituted alkanoic acid units each expressed by chemical formula (5) or 3-hydroxy-ω-cyclohexylalkanoic acid units from chemical formula (6) besides 3-hydroxy-ω-bromoalkanoic acid units from chemical formula (21) can be produced. The contents of ω-bromoalkanoic acid expressed by chemical formula (21), ω-substituted alkanoic acid compound expressed by chemical formula (22) and ω-cyclohexylalkanoic acid compound expressed by chemical formula (23) are selected so that they are in the range of from 0.0005 to 1% (w/v), more preferably from 0.001 to 0.2% (w/v) per culture medium, respectively.
(r is an integer number selected from 1 to 8; R 18 includes a residue having any one of a phenyl structure and a thienyl structure, and represents any one selected from the group consisting of formulas (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) and (17), and in the case where a plurality of types of compounds exists, R 18 and r in one unit can be different from them in another respectively.
(In the formula, R 19 represents a substituent group in the cyclohexyl group, and R 19 is selected from the group consisting of H, CN, NO 2 , a halogen atom, CH 3 , C 2 H 5 , C 3 H 7 , CF 3 , C 2 F 5 and C 3 F 7 , s is an integer number selected from 0 to 8.)
(Method of Producing Polyhydroxyalkanoate Expressed by Chemical Formula (1))
The reaction between the polyhydroxyalkanoate having units each expressed by the chemical formula (18) in the present invention and the compound expressed by chemical formula (19) will be described in detail.
The compound expressed by chemical formula (19) for use in the present invention is used in the amount in the range of from 0.1 to 50.0 times in mole, more preferably from 1.0 to 30.0 times in mole as large as the amount of unit expressed by chemical formula (18) to be used as a starting material.
The reaction in the present invention is preferably made to proceed under a basic condition. For the base, amines such as dimethyl amine, diethyl amine, trimethyl amine, triethyl amine, dibutyl amine, morpholine and piperidine, alkali hydroxide metals such as sodium hydrate and potassium hydrate, alkali carbonate metals such as sodium carbonate and potassium carbonate, alkali metal alcoholates such as sodium methylate and sodium ethylate, sodium hydride and the like may be used. Particularly, diethyl amine, triethyl amine and dibutyl amine are preferably used. The amount of base to be used is in the range of from 0.1 to 100.0 times in mole, more preferably from 0.5 to 50.0 times in mole as large as the amount of unit expressed by chemical formula (18).
A solvent may be used as required in the reaction of the present invention. Solvents to be used include hydrocarbons such as hexane, cyclohexane and heptane, ketones such as acetone, methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and trichloroethane, aromatic hydrocarbons such as benzene and toluene, and aprotic polar solvents such as N,N-dimethyl formamide and dimethyl sulfoxide. N,N-dimethyl formamide is particularly preferably used. The amount of solvent to be used may be determined as appropriate according to the type of starting material, the type of base, the reaction condition and the like.
In the method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of from 0° C. to the boiling point of the solvent. In the case where the reaction temperature is higher than a room temperature, however, the ester linkage of the main chain may be cut, and it is therefore more preferable that the reaction is made to proceed at a temperature of about 0 to 30° C.
In the method of the present invention, the reaction time cannot be determined unconditionally, but is usually in the range of from 1 to 48 hours.
In the present invention, the reaction solution containing the polyhydroxyalkanoate of chemical formula (1) produced in this way can be removed using distillation as a normal method. Alternatively, the reaction solution can be collected by mixing the reaction solution uniformly with a solvent insoluble in the polyhydroxyalkanoate expressed by chemical formula (1) to reprecipitate the desired polyhydroxyalkanoate expressed by chemical formula (1) using a solvent such as water, an alcohol such as methanol and ethanol, and an ether such as dimethyl ether, diethyl ether and tetrahydrofuran. The polyhydroxyalkanoate of chemical formula (1) obtained in this way may be isolated and purified if necessary. The isolation and purification method is not particularly limited, and a method in which a solvent insoluble in the polyhydroxyalkanoate expressed by chemical formula (1) is used to reprecipitate the polyhydroxyalkanoate, a method using column chromatography and a method using dialysis may be used.
Furthermore, in the reaction in the present invention, the reaction solvent, the reaction temperature, the reaction time and the purification method should not be limited to those described above.
In addition, the present invention is a charge controlling agent containing the above described polyhydroxyalkanoate, and further an electrostatic latent image developing toner containing the charge controlling agent. The present invention is further an image formation method comprising an charging step of applying a voltage to a charge member from the outside to uniformly charge an electrostatic latent image carrier for the above electrostatic latent image developing toner, a development step of forming a toner image on the electrostatic latent image carrier, a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material via or not via an intermediate transfer body, and a heat-fixation step of fixing by heat the toner image on the transfer material, and also an image forming apparatus comprising means corresponding to respective steps of the method, namely charging means, development means, transfer means and heat-fixation means.
The polyhydroxyalkanoate for use in the present invention has good compatibility with the binder resin and excellent compatibility particularly with polyester type binder resin. Since the toner containing the polyhydroxyalkanoate of the present invention has a high specific charge level and is excellent in stability with time, it provides clear images with stability in image formation with electrostatic recording even after being stored for a long time period, and the toner can be produced for both negatively charged black toners and color toners because of its colorlessness and negative-electrifiability.
In addition, by properly selecting the type and composition ratio of monomer units constituting the polyhydroxyalkanoate of the present invention, wide range compatibility control is made possible. If a resin composition in which the charge controlling agent is put in micro-phase separation state in a toner binder, no electric continuity is formed in the toner so that electric charge can stably be maintained. In addition, the polyhydroxyalkanoate of the present invention contains no heavy metals, and therefore when the toner is produced by suspension polymerization or emulsion polymerization, polymerization inhibition caused due to the presence of heavy metals, as found in the case of a metal-containing charge controlling agent, does not occur, thus making it possible to produce a toner with stability.
(Addition of PHA to Toner)
In the present invention, the method for adding the above compound to a toner may be a method of internal addition to the toner and a method of external addition to the toner. The addition amount of the internal addition is generally 0.1 to 50% by weight, preferably 0.3 to 30% by weight, and further preferably 0.5 to 20% by weight as the weight ratio of the toner binder and the charge controlling agent. If it is lower than 0.1% by weight, the improvement degree of the charging property of the toner is insignificant and thus not preferable. Whereas, if it is higher than 50% by weight, it is not preferably from an economical point of view. Further, in the case of the external addition, the weight ratio of the toner binder and the charge controlling agent is preferably 0.01 to 5% by weight, and it is particularly preferable that the compound is mechanochmically fixed on the surface of the toner. In addition, the compound presented in the present invention may be used in combination of a known charge controlling agent.
The number-average molecular weight of the above-described compound of the present invention is usually 1000 to 1000000, preferably 1000 to 500000. If it is less than 1000, the compound is completely compatible with the toner binder to make it difficult to form a discontinuous domain, resulting in an insufficient charge level, and the fluidity of the toner is adversely affected. Further, if it is higher than 1000000, dispersion in the toner becomes difficult.
The molecular weight of PHA of the present invention can be measured as a relative or absolute molecular weight. It can conveniently be measured by, for example, GPC (gel permeation chromatography). For the specific measurement process of GPC, PHA is dissolved in a solvent capable of dissolving the PHA in advance, and a measurement is made with a similar mobile phase. For the detector, a differential refraction detector (RI), an ultraviolet detector (UV) or the like may be used depending on the PHA to be measured. The molecular weight is determined as a relative comparison with a standard sample (polystyrene, polymethylmethacrylate, etc.). The solvent may be selected from solvents capable of dissolving a polymer such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), chloroform, tetrahydrofuran (THF), toluene, hexafluoroisopropanol (HFIP). In the case of a polar solvent, a measurement can be made by addition of salt. In addition, in the present invention, compounds presented in the present invention with the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number-average molecular weight (Mn) measured as described above being in the range of from 1 to 10 are preferably used.
In the present invention, the compound presented in the present invention has a melting point preferably in the range of from 20 to 150° C., especially preferably from 40 to 150° C., or has no melting point but a glass transition temperature in the range of from 20 to 150° C., especially preferably from 40 to 150° C. If the foregoing melting point is lower than 20° C. or the glass transition temperature with no melting point is lower than 20° C., the fluidity and the storage property of the toner are often adversely affected. Whereas if the foregoing melting point is higher than 150° C. or the glass transition temperature with no melting point is higher than 150° C., the charge controlling agent becomes difficult to be kneaded with the toner and the charge level distribution becomes broad in many cases.
To measure the melting point Tm and the glass transition temperature Tg in this case, a high precision and internally heating input compensation type differential scanning calorimeter, for example, DSC-7 manufactured by Perkin Elmer Co., may be employed.
Regarding the toner binder and the electrostatic latent image developing toner of the present invention, the weight ratio of the toner binder and the charge controlling agent is generally 0.1 to 50% by weight, preferably 0.3 to 30% by weight, and more preferably 0.5 to 20% by weight. Regarding the composition ratio of the electrostatic latent image developing toner of the present invention, generally the foregoing charge controlling agent is in the range of from 0.1 to 50% by weight, the toner binder is in the range of from 20 to 95% by weight, and a coloring material is in the range of from 0 to 15% by weight with respect to the weight of the toner and based on the necessity, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel and the like and a compound such as magnetite, hematite, ferrite and the like) functioning as a coloring material may be added in an amount not more than 60% by weight. Further, various additives [a lubricant (polytetrafluoroethylene, a lower molecular weight polyolefin, an aliphatic acid or its metal salt or amide, and the like) and other charge controlling agents (metal-containing azo dye, metal salcylate, etc.)] may be contained. In addition, in order to improve the fluidity of the toner, a hydrophobic colloidal silica fine powder may also be employed. The amounts of these additives are generally not more than 10% by weight on the bases of the toner weight.
In the toner of the present invention, it is preferable for at least some of the toner binder to form a continuous phase and at least some of the charge controlling agent to form discontinuous domain. As compared with the case where the charge controlling agent has complete compatibility with the toner binder without forming the discontinuous domain, the added charge controlling agent is easily exposed to the surface and effective even in a small amount. The dispersion particle diameter of the domain is preferably 0.01 to 4 μm and more preferably 0.05 to 2 μm. If it is bigger than 4 μm, the dispersibility becomes insufficient and the charge level distribution becomes broad and the transparency of the toner is deteriorated. Whereas, if the dispersion particle diameter is smaller than 0.01 μm, it becomes similar to the case where the charge controlling agent has complete compatibility with the binder without forming discontinuous domain, a large amount of the charge controlling agent is required to be added. That at least some of the foregoing charge controlling agent forms the discontinuous domain and the dispersion particle size can be observed by observing a specimen of the toner with a transmission electron microscope. In order clearly observe the interface, it is also effective to carry out observation of a toner specimen by electron microscope after the specimen is dyed with ruthenium tetraoxide, osmium tetraoxide and the like.
Further, for the purpose of reducing the particle diameter of the discontinuous domain formed by the compound presented in the present invention, a polymer compatible with the compound presented in the present invention and also with the toner binder may be added as a compatible agent. The compatibility enhancing agent is, among other things, a polymer comprising mutually graft- or block-polymerized polymer chains containing at least 50% by mol of monomers having practically similar structure to that of the constituent monomers of the compound presented in the present invention and polymer chains containing at least 50% by mol of monomers having practically similar structure to that of the toner binder. The amount of the compatible agent to be used is generally not more than 30% by weight and preferably 1 to 10% by weight, with respect to the compound presented in the present invention.
(Other Constituent Materials)
Other constituent materials constituting the electrostatic latent image developing toner of the present invention will be described below.
(Binder Resin)
At first, any resin may be used as the binder resin without any particular restrictions if it is generally used for production of a toner. Also, the charge controlling agent of the present invention may previously be mixed with the binder resin to be used as a toner binder composition of the present invention having charge controlling capability before production of the toner. For example, styrene-based polymers, polyester-based polymers, epoxy-based polymers, polyolefin-based polymers, polyurethane-based polymers and the like can exemplify the binder resin, and they are used alone or while being mixed with one another.
The styrene-based polymers may be styrene(meth)acrylic acid ester copolymers and copolymers of these copolymers with other monomers copolymerizable with them; copolymers of styrene with diene type monomers (butadiene, isoprene and the like) and copolymers of these copolymers with other monomers copolymerizable with them; and the like. The polyester-based polymers may be condensation polymerization products of aromatic dicarboxylic acid and aromatic diol alkylene oxide addition products and the like. The epoxy-based polymers may be reaction products of aromatic diols and epichlorohydrin and their modified products. The polyolefin-based polymers may be polyethylene, polypropylene, and copolymer chains of these polymers with monomers polymerizable with them. The polyurethane-based polymers may be addition polymerization products of aromatic diisocyanates and aromatic diol alkylene oxide addition products and the like.
Practical examples of the binder resin to be employed in the present invention are polymers of the following polymerizable monomers or their mixtures, or copolymerization products produced from two or more kinds of the following polymerizable monomers. Such polymers are more particularly, for example, styrene-based polymers such as styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer and the like; polyester-based polymers; epoxy-based polymers; polyolefin-based polymers; and polyurethane-based polymers and they are preferably used.
Practical examples of the polymerizable monomers are styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, and the like; ethylenic unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene and the like; unsaturated polyenes such as butadiene and the like; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride and the like; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and the like; α-methylene aliphatic monocarboxylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and the like; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and the like; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone, and the like; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide and the like; esters of the above-described α,β-unsaturated acid; diesters of bibasic acid; dicarboxylic acids such as maleic acid, methyl maleate, butyl maleate, dimethyl maleate, phthalic acid, succinic acid, terephthalic acid, and the like; polyols compounds such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxyethylene-modified bisphenol A and the like; isocyanates such as p-phenylene diisocyanate, p-xylylene diisocyanate, 1,4-tetramethylene diisocyanate, and the like; amines such as ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane, monoethanolamine, and the like; epoxy compounds such as diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A glycidyl ether, hydroquinone glycidyl ether, and the like.
(Cross-Linking Agent)
In the case of producing the binder resin to be employed in the present invention, based on the necessity, the following cross-linking agent may be used. Examples of a bifunctional cross-linking agent are divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, respective diacrylates of polyethylene glycol #200, #400, #600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate, and those obtained by changing these exemplifying acrylates into corresponding methacrylates.
Examples of bi- or higher polyfunctional cross-linking agent are pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylates or methacrylates, 2,2-bis(4-methacryloxy polyethoxyphenyl)propane, diallyl phthalate, triallyl cyanurate, triallyl azocyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate, and the like.
Polymerization Initiator
In the case of producing the binder resin to be employed for the present invention, the following polymerization initiators may be used based on the necessity: for example, tert-butyl peroxy-2-ethylhexanoate, cumine perpivalate, tert-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,2′-azobis isobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,4-bis(tert-butylperoxycarbonyl)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl 4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-tert-butyldiperoxy isophthalate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, di-tert-butylperoxy-α-methylsuccinate, di-tert-butyl peroxydimethylglutarate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, diethylene glycol bis(tert-butylperoxycarbonate), di-tert-butyl peroxytrimethyladipate, tris(tert-butylperoxy)triazine, vinyltris(tert-butylperoxy)silane and the like. Each of these compounds may be used alone or in combination. The use amount of them is generally in 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) to 100 parts by weight of monomers.
(Other Biodegradable Plastics)
In addition, in the present invention, biodegradable plastics are preferably used. Examples of the biodegradable plastics are “Ecostar”, “Ecostar plus” (produced by Hagiwara Industries, Inc.), “Biopole” (produced by Monsant Co.), “Ajicoat” (Ajinomoto Co., Ltd.), “Placcel”, “Polycaprolactone” (produced by Daicel Chem., Ind., Ltd.), “Bionolle” (produced by Showa Highpolymer Co., LTD), “Lacty” (produced by Shimadzu Corporation), “Lacea” (produced by Mitsui Chemicals, Inc.) and the like.
It is preferable for the combinations of the binder resin and the charge controlling agent of the present invention that the structure of the polymers of the binder resin and the polymer structure of the polymer chain of the charge controlling agent are similar to each other as much as possible. If the structure of the polymers of the binder resin and the polymer structure of the polymer chain of the charge controlling agent are considerably dissimilar to each other, the charge controlling agent tends to be dispersed insufficiently in the binder resin.
The weight ratio of the charge controlling agent of the present invention to be internally added to the binder resin is generally 0.1 to 50% by weight, preferably 0.3 to 30% by weight, and more preferably 0.5 to 20% by weight. If the weight ratio of the charge controlling agent to be internally added is lower than 0.1% by weight, the charge level becomes low and if the weight ratio is higher than 50% by weight, the charge stability of the toner is deteriorated.
(Coloring Agent)
Any coloring agent generally used for production of a toner may be used as the coloring agent composing the electrostatic latent image developing toner of the present invention without particular restrictions. For example, carbon black, titanium white, and any other pigment and/or dye may be used. For example, in the case the electrostatic latent image developing toner of the present invention is used for a magnetic color toner, examples of the coloring agent to be employed are C.I. Direct Red 1, C.I. Direct Red 4, C.I. Acid Red 1, C.I. Basic Red 1, C.I. Mordant Red 30, C.I. Direct Blue 1, C.I. Direct Blue 2, C.I. Acid Blue 9, C.I. Acid Blue 15, C.I. Basic Blue 3, C.I. Basic Blue 5, C.I. Mordant Blue 7, C.I. Direct Green 6, C.I. Basic Green 4, C.I. Basic Green 6 and the like. Examples of the pigment are Chrome Yellow, Cadmium Yellow, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Yellow Lake, Chrome Orange, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red calcium salt, Eosine Lake, Brilliant Carmine 3B, Manganese Violet, Fast Violet B, Methyl Violet Lake, Prussian Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, chromium oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.
In the case the electrostatic latent image developing toner of the present invention is used for a two-component type full color toner, the following coloring agents can be used. For example, coloring pigments for magenta toners are C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. Pigment Violet 19, C.I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35 and the like.
In the present invention, the above-exemplified pigments may be used alone, but it is more preferable that they are used in combination with dyes for improving the clearness from the aspect of the full color image quality. In such a case, the examples of usable magenta dyes are oil-soluble dyes such as C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. Disperse Red 9, C.I. Solvent Violet 8, 13, 14, 21, 27, and C.I. Disperse Violet 1 and the like; and basic dyes such as C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28, and the like.
As other coloring pigments, examples of cyan coloring pigments are C.I. Pigment Blue 2, 3, 15, 16, 17, C.I. Vat Blue 6, C.I. Acid Blue 45, copper-phthalocyanine pigments having a phthalocyanine skeleton containing substituents of phthalimidomethyl groups in number of 1 to 5, and the like.
Examples of yellow coloring pigments are C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, C.I. Vat Yellow 1, 3, 20 and the like.
The above-described dyes and pigments may be used solely or may be used while being optionally mixed with one another to obtain desired hue of the toner. Incidentally, taking the environmental preservation and the safety to human being into consideration, a variety of edible coloring elements may preferably be used. The content of the coloring agents in the toner may widely altered depending on the desired coloration effects. Generally, in order to obtain the best toner properties, that is, in consideration of the printing coloration capability, the toner shape stability, and the toner leap, these coloring agents are used at a ratio in the range of from 0.1 to 60 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the binder resin.
Other Components of Toner
In the electrostatic latent image developing toner of the present invention may contain the following compounds other than the foregoing binder resin and the coloring agent components, to an extent (within a ratio less than the content of the binder resin) in which no undesired effect is caused in the present invention. Examples of such compounds include silicone resin; polyester; polyurethane; polyamide; epoxy resin; poly(vinyl butyral); rosin; modified rosin; terpene resin; phenolic resin; aliphatic or alicyclic hydrocarbon resin such as lower molecular weight polyethylene and lower molecular weight polypropylene; aromatic type petroleum resin; and chlorinated paraffin and paraffin waxes. Among them, preferable waxes to be used are practically lower molecular weight polypropylene and its byproducts, lower molecular weight polyester, and ester type wax and aliphatic derivatives. Among these waxes, waxes separated based on the molecular weight of the waxes by various methods are also preferably used in the present invention. Further, after separation, the waxes may be modified to control the acid values, block-copolymerized, or graft-modified.
Specially, in the electrostatic latent image developing toner of the present invention, in the case such wax components as described above are added and these wax components are found practically dispersed in the binder resin in spherical and/or elliptical island state by cross-sectional observation of the toner by a transmission electron microscope, the toner is provided with excellent properties.
Method of Producing Toners
Any conventionally known method may be employed for a practical method for producing an electrostatic latent image developing toner of the present invention having the constitution as described above. The electrostatic latent image developing toner of the present invention can be produced, for example, by a so-called pulverization method for obtaining a toner through the following steps. Specifically, the compound presented in the present invention described previously, resin materials such as binder resin, and a wax to be added as necessary are sufficiently mixed by a mixer such as a Henshel mixer, a ball mill and the like and then melted and kneaded using a thermally kneading apparatus such as heating rolls, a kneader, an extruder and the like to make the resin material compatible with one another, and as coloring agents, pigments, dyes, or magnetic materials and also additives such as metal compounds to be added as necessary are dispersed or dissolved in the resulting mixture, and after solidification of the mixture by cooling, the obtained solidified product is pulverized by a pulverizing apparatus such as a jet mill, a ball mill and the like and then classified to obtain an electrostatic latent image developing toner of the present invention with a desired particle size. In the above-described classification step, from an aspect of productivity, a multi-step classification apparatus is preferably used.
In addition, the electrostatic latent image developing toner of the present invention with a desired particle size can be obtained by mixing and stirring the binder resin and the compound of the present invention in a solvent (e.g., aromatic hydrocarbons such as toluene, xylene and the like; halogen compounds such as chloroform, ethylene dichloride, and the like; ketones such as acetone, methyl ethyl ketone, and the like; amides such as dimethylformamide and the like), and then adding the resulting mixture to water to re-precipitate the solid, then filtering and drying the solid, and further pulverizing it by a pulverizing apparatus such as a jet mill, a ball mill and the like, and finally classifying the pulverized matter. In the above-described classification step, from an aspect of productivity, a multi-step classification apparatus is preferably used.
In addition, the electrostatic latent image developing toner of the present invention can be produced by a so-called polymerization method as follows. That is, in this case, the compound of the present invention, a polymerizable monomer, and as coloring agents, pigments, dyes, or magnetic materials and also based on the necessity, additives such as a cross-linking agent, a polymerization initiator, waxes, and others are mixed and dispersed and in the presence of a surfactant or the like, the mixture is subjected to suspension polymerization to obtain a polymerizable and coloring resin particle, and after the obtained particle is separated by solid-liquid separation, the particle is dried and classified if necessary to obtain an electrostatic latent image developing toner of the present invention with a desired particle size.
Furthermore, a coloring fine particle containing no charge controlling agent is produced by the above-described manner and then either solely or together with an externally added agent such as colloidal silica, the compound presented in the present invention may be stuck and added to the surface of the particle by a mechanochemical method or the like.
(Externally Added Silica Agent)
In the present invention, a silica fine powder is preferably added externally to the toner produced in a manner as described above for improving the charge stability, development characteristic, fluidity and durability. The silica fine powder to be employed in this case can provide desirable effects if it has a specific surface area equal to or larger than 20 m 2 /g or higher (especially 30 to 400 m 2 /g) measured based on the nitrogen adsorption by BET method. The content of the silica fine powder to be added is preferably 0.01 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the toner particle. In this case, based on the necessity, the silica fine powder to be used in the case is preferably treated for the purpose of controlling the hydrophobility and charging property with silicone varnish, variously modified silicone varnish, silicone oil, variously modified silicone oil, a silane coupling agent, a silane coupling agent having a functional group, and other organosilicon compounds. These treatment agent may be used by mixing.
Inorganic Powder
Further, in order to improve the development capability and the durability, the following inorganic powder is preferably added. Examples of the powder are oxides of metals such as magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony and the like; compounded metal oxides such as calcium titanate, magnesium titanate, and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonates; clay minerals such as kaolin; phosphate compounds such as apatite; silicon compounds such as silicon carbide, and silicon nitride; and carbon powder such as carbon black and graphite. Among them, fine powders of zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, and magnesium titanate are preferably used.
Lubricant
Further, the following lubricant powder may be added to the toner. For example, fluoro resin such as Teflon, poly(vinylidene fluoride) and the like; fluoride compounds such as carbon fluoride; aliphatic acid metal salts such as zinc stearate; aliphatic acid derivatives such as aliphatic acid, aliphatic acid esters and the like; and molybdenum sulfide.
(Carrier)
The electrostatic latent image developing toner of the present invention having the above-described constitution is usable for a variety of conventionally known toners; solely as a non-magnetic mono-component developer, as a non-magnetic toner together with a magnetic carrier for composing a magnetic two-component developer, as a magnetic toner to be used solely for a magnetic mono-component toner. In this case, as the carrier to be used in the case of the two-component development, any conventionally known carrier may be used. More particularly, particles of surface-oxidized or non-oxidized metals such as iron, nickel, cobalt, manganese, chromium and rare earth metals, their alloys and oxides and having an average particle size of 20 to 300 μm may be used as the carrier particle. Further, the carrier to be used in the present invention are preferably the above-described carrier particle whose surface bears or is coated with a substance such as styrene-based resin, acrylic resin, silicone resin, fluoro resin, polyester resin and the like.
(Magnetic Toner)
The electrostatic latent image developing toner of the present invention may be a magnetic toner by adding a magnetic material to the toner particle. In this case, the magnetic material may take a role also as a coloring agent. The magnetic material to be used in this case may be iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel; alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium; and their mixtures. The magnetic material to be used in the present invention has an average particle size preferably 2 μm or less, more preferably 0.1 to 0.5 μm. The amount to be added to the toner is preferably 20 to 200 parts by weight to 100 parts by weight of the binder resin and especially preferably 40 to 150 parts by weight to 100 parts by weight of the binder resin.
In addition, in order to give high image quality, it is required to precisely develop very small latent image dots and for this purpose, for example, it is preferable that the weight average particle size of the electrostatic latent image developing toner of the present invention is controlled so that it is in the range of from 4 to 9 μm. That is, if the toner particle has a weight average particle size smaller than 4 μm, the transfer efficiency is decreased and a large amount of the transfer residual toner tends to remain on a photoconductor to result in an undesirable cause of uneven and irregular image formation attributed to fogging and transfer failures. Whereas, if the toner particle has a weight average particle size larger than 9 μm, letters and line images tend to be eliminated.
In the present invention, the average particle size and the particle size distribution of the toner are measured by using Coulter Counter TA-II model or Coulter Multisizer (manufactured by Coulter Co.) or the like to which an interface (manufactured by Nikka Machine Co.) for outputting the distribution by number, the distribution by volume and a PC9801 personal computer (manufactured by NEC) are connected. As an electrolytic solution to be used at that time, an aqueous 1% NaCl solution is prepared using first-grade sodium chloride. As the electrolytic solution, for example, a commercialized ISOTON R-II (produced by Coulter Scientific Japan Co.) may also be usable. A practical measurement method involves steps of adding 0.1 to 5 ml of a surfactant (preferably an alkylbenzenesulfonic acid salt is used) as a dispersant to 100 to 150 ml of the above-described aqueous solution, further adding 2 to 20 mg of a sample to the resulting solution to obtain a specimen to be measured. At the time of measurement, the electrolytic solution in which the specimen to be measured is suspended is treated for dispersion for 1 to 3 minutes by an ultrasonic dispersing apparatus and then the volume and the number of the toner particles of 2 μm or larger are measured by the foregoing Coulter Counter TA-II model using 100 μm apertures as apertures and the distribution by volume and the distribution by number are calculated. Then, the weight average particle size (D4) on the bases of the volume calculated from the distribution by volume according to the present invention and the length average particle size (D1) on the bases of the number calculated from the distribution by number are calculated.
(Charge Level)
In addition, the charge level of the electrostatic latent image developing toner of the present invention is preferably in the range of from −10 to −80 μC/g, more preferably from −15 to −70 μC/g per unit weight (two-component method) in improving the transfer efficiency in a transfer method using a transfer member with a voltage applied thereto.
The method of measuring an charge level (a two-component tribo) by the two-component method employed in the present invention will be described as follows. A charge level measuring apparatus illustrated in FIG. 8 is used for the measurement. At first, under a specified environment, EFV 200/300 (produced by Powder Tec Co.) is used as a carrier and a bottle made of a polyethylene with a capacity of 50 to 100 ml is charged with a mixture of 9.5 g of the carrier and 0.5 g of a toner, an object to be measured, set in a shaking apparatus so controlled as to keep the amplitude constant, and shaken for a prescribed period in the shaking conditions of an amplitude of 100 mm and a shaking speed of 100 time reciprocation per 1 minute. Then, 1.0 to 1.2 g of the above mixture is placed in a measurement container 42 made of metal having a 500-mesh screen 43 , and the measurement container 42 is covered with a metal lid 44 in the bottom of the charge level measuring apparatus shown in FIG. 8 . The total weight of the measurement container 42 at that time is measured and determined as W 1 (g). Next, the gas in the container is aspirated through a suction port 47 by an unillustrated aspirator (at least the portion contacting the measurement container 42 is made of an insulator) and an air ventilation adjustment valve 46 is controlled to control the pressure of the vacuum meter 45 to be 2,450 Pa (250 mmAq). Under such a state, aspiration is carried out for 1 minute to suck and remove the toner. The potential of a potentiometer 49 at that time is denoted as V (volt). The reference numeral 48 denotes a capacitor and the capacity is denoted as C (μF). The weight of the entire measurement container after the aspiration is weighed and denoted as W 2 (g). The friction charge level (μC/g) of the toner can be calculated according to the following equation from these measurement values.
Friction charge level (μ C/g )= C×V /( W 1 −W 2 )
(Molecular Weight Distribution of Binder Resin)
The binder resin for use in the constituent material of the electrostatic latent image developing toner of the present invention preferably has a peak within the range of from 3,000 to 15,000 in a low molecular weight region of the molecular weight distribution measured by GPC, especially, in the case of production by the pulverization method. That is, if the GPC peak exceeds 15,000 in the low molecular weight region, it sometimes becomes difficult to obtain a toner with a sufficiently improved transfer efficiency. Whereas if binder resin having a GPC peak of less than 3,000 is used, melting takes place easily at the time of surface treatment and therefore it is undesirable.
In the present invention, the molecular weight of the binder resin is measured by GPC (gel permeation chromatography). A practical GPC measurement method is carried out as follows: a toner previously extracted with THF (tetrahydrofuran) solvent for 20 hours using a Soxhlet extractor is used as a sample for measurement and using columns A-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko K. K. and calibration curves of standardized polystyrene resins, the molecular weight distribution is measured. Further, in the present invention, it is preferable that the binder resin with the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number-average molecular weight (Mn) measured as described above being in the range of from 2 to 100 is used.
(Glass Transition Temperature of Toner)
Further, the toner of the present invention is preferably adjusted by using a proper material so as to have a glass transition temperature Tg in the range of from 40 to 75° C., more preferably 52 to 70° C., from a viewpoint of fixation and storage stability. In this case, the measurement of the glass transition temperature Tg may be carried out using a high precision and internally heating input compensation type differential scanning calorimeter, for example, DSC-7 manufactured by Perkin Elmer Co., may be employed. The measurement method is carried out according to ASTM D3418-82. In the present invention, in the case of measuring the glass transition temperature Tg, it is preferable that a measurement sample is once heated to cancel the entire hysteresis and then quenched and again heated at a heating rate of 10° C./min to employ the DSC curve measured during the heating from 0 to 200° C.
(Image Formation Method)
The electrostatic latent image developing toner of the present invention having the configuration described above is particularly preferably applied to an image formation method comprising at least an charging step of applying a voltage to a charge member from the outside to charge an electrostatic latent image carrier, a step of forming an electrostatic latent image on the charged electrostatic latent image carrier, a development step of developing the electrostatic latent image by the toner to form a toner image on the electrostatic latent image carrier, a transfer step of transferring the toner image on the electrostatic latent image carrier to an object recording material, and a heat-fixation step of heat-fixing the toner image on the object recording material, or an image formation method with the transfer step consisting of a first transfer step of transferring the toner image on the electrostatic latent image carrier to an intermediate transfer body and a second transfer step of transferring the toner image on the intermediate transfer body to the object recording material.
The present invention provides an innovative polyhydroxyalkanoate with a sulfonic group as a hydrophilic group and its derivative introduced therein and a method of producing the same. In this way, the innovative polyhydroxyalkanoate is excellent in melt-processability, and also excellent in biocompatibility owing to its hydrophilic nature, and can thus be expected to be applied as medical flexible members and the like.
In addition, as described above and below, according to the present invention, addition of one or more types of compounds presented in the present invention to an electrostatic latent image developing toner composition as a charge controlling agent makes it possible to provide an electrostatic latent image developing toner having an excellent electrifiability, improving the dispersibility of the compound in the toner resin and the spent characteristic thereof, causing no image fog even when the image is outputted in the image forming apparatus, and being excellent in transferability and highly applicable to an electrophotographic process. In addition, because the charge controlling agent for use in the present invention is colorless or only weakly colored, any coloring agent can be selected according to the color required for the color toner, and the original color of a dye or pigment is not hindered.
EXAMPLES
The present invention will be described further in detail below with reference to Examples, although the method of the present invention should not be limited to the Examples.
First, the method of producing sodium 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate of formula (24)
as one of compounds each expressed by chemical formula (19) will be described.
15.2 g of 2-acrylamide-2-methylpropanesulfonic acid, 2.8 g of sodium hydrate and 0.01 g of benzoyl peroxide were dissolved in 48.5 g of methanol at a room temperature, and gas in the system was replaced with nitrogen. Then, 26.7 g of thioacetic acid was added while maintaining the temperature in the system at 15 to 19° C., and the mixture was thereafter left under reflux for 4 hours, holding the system at the temperature of 45 to 60° C. After cooling, 600 g of isopropyl ether was added to wash the mixture. The insoluble matter was dried so that the weight thereof was reduced to 22 g. The obtained insoluble matter was dissolved in 66 g of methanol at a room temperature, and gas in the system was replaced with nitrogen, 0.76 g of sodium hydrate was added, and was stirred for 3 hours with the temperature in the system being kept at 39 to 41° C. After cooling, 1.2 g of acetic acid was added, and thereafter the solvent was distilled away to obtain thiolated 2-acrylamide-2-methylpropanesulfonic acid. Furthermore, the 1 H-NMR spectrum was used to ensure that the thiolation had been done in a quantitative manner.
The following Examples 1 to 4 are examples of methods of producing the polyhydroxyalkanoate of the present invention using as a raw material 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate obtained in the above manner and the polyhydroxyalkanoate produced by the method of production by microorganism described previously. However, the polyhydroxyalkanoate and the method of producing the same should not be solely dependent on the above raw materials.
Example 1
Method (1) of Producing Polyhydroxyalkanoate Containing Units Expressed by Chemical Formulas (25) and (26)
900 mg of polyhydroxyalkanoate (average molecular weight: Mn=36000, Mw=66000 (measured by gel permeation chromatography (GPC); Tosoh HLC-8220, column: Tosoh TSK-GEL SuperHM-H, solvent: chloroform, polystyrene equivalent)) containing 9.5 mol % in total of 3-hydroxy-8-bromooctanoic acid unit and 3-hydroxy-6-bromohexanoic acid unit, 89.1 mol % of 3-hydroxy-5-phenylvaleric acid and 1.4 mol % of other components (straight-chain 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and straight-chain 3-hydroxyalka-5-enoic acid having 10 or 12 carbon atoms) was dissolved in 12 ml of N,N-dimethylformamide at a room temperature, and gas in the system was replaced with nitrogen. Then, while holding the system at a room temperature, 825 mg of sodium 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate dissolved in 18 ml of N,N-dimethylformamide was added, and 330 μl of diethylamine was further added, and was stirred at a room temperature for 24 hours.
After the reaction was completed, the mixture was put in 300 ml of diethyl ether to allow reprecipitation for removing N,N-dimethylformamide as a reaction liquid. The resulting precipitate was collected by centrifugal separation.
This precipitate was put in 300 ml of water, stirred and washed. The precipitate obtained at this time was collected by carrying out centrifugal separation. This precipitate was dried under reduced pressure to obtain 244 mg of polyhydroxyalkanoate.
This PHA was analyzed using nuclear magnetic resonance apparatus under the following conditions.
Measuring Apparatus
FT-NMR: Bruker DPX400
resonance frequency: 1 H=400 MHz
Measuring Apparatus
nuclear species to be measured: 1 H
solvent used: DMSO-d6
reference: capillary-encapsulated DMSO-d6
measuring temperature: 40° C.
The 1 H-NMR spectrum chart is shown in FIG. 1 , and the composition of PHA calculated from the results obtained by the 1 H-NMR spectrum is shown in Table 1.
TABLE 1
Content of each unit
(mol %)
Chemical formulas (25) and (26)
4.8
Chemical formula (27)
93.0
Other polyhydroxyalkanoate
2.2
From the results, this polyhydroxyalkanoate was found to contain 4.8 mol % in total of units expressed by chemical formulas (25) and (26) and 93.0 mol % of 3-hydroxy-5-phenylvaleric acid unit expressed by chemical formula (27).
The molecular weight of the obtained PHA was measured by gel permeation chromatography (GPC; Tosoh HLC-8220, column: Tosoh TSK-GEL SuperHM-H, solvent; chloroform, polystyrene equivalent) and found as follows: Mn=10000 and Mw=19400.
Example 2
Method (2) of Producing Polyhydroxyalkanoate Containing Units Expressed by Chemical Formulas (25) and (26)
869 mg of polyhydroxyalkanoate (average molecular weight: Mn=30800, Mw=65200 measured by the gel permeation chromatography described in Example 1) containing 7.4 mol % in total of 3-hydroxy-8-bromooctanoic acid unit and 3-hydroxy-6-bromohexanoic acid, 87.1 mol % of 3-hydroxy-5-phenoxyvaleric acid and 5.5 mol % of other components (straight-chain 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and straight-chain 3-hydroxyalka-5-enoic acid having 10 or 12 carbon atoms) was dissolved in 9 ml of N,N-dimethylformamide at a room temperature, and gas in the system was replaced with nitrogen. Then, while holding the system at a room temperature, 2080 mg of sodium 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate dissolved in 16 ml of N,N-dimethylformamide was added, and 206 μl of diethylamine was then added, and was stirred at a room temperature for 24 hours.
After the reaction was completed, N,N-dimethylformamide as a reaction liquid was once distilled away by a rotary evaporator, and the mixture was again dissolved in 3 ml of N,N-dimethylformamide, and was thereafter put in 300 ml of pure water to allow reprecipitation. The resulting precipitate was collected by centrifugal separation. This precipitate was suspended again with 50 ml of pure water, and subjected to centrifugal separation to collect the precipitate for washing. This washing operation was conducted three times, followed by drying the precipitate under reduced pressure to obtain 819 mg of polyhydroxyalkanoate.
For this PHA, measurements were carried out using the nuclear magnetic resonance apparatus under the same condition as Example 1.
The composition of PHA calculated from the results obtained by the 1 H-NMR spectrum is shown in Table 2.
TABLE 2
Content of each unit
(mol %)
Chemical formulas (25) and (26)
4.0
Chemical formula (28)
91.0
Other polyhydroxyalkanoate
5.0
From the results, this polyhydroxyalkanoate was found to contain 4.0 mol % in total of units expressed by chemical formulas (25) and (26) and 91.0 mol % of 3-hydroxy-5-phenoxyvaleric acid unit expressed by chemical formula (28).
The molecular weight of the obtained PHA was measured by the method described in Example 1 using gel permeation chromatography and found as follows: Mn=3100 and Mw=9100.
Example 3
Method (1) of Producing Polyhydroxyalkanoate Containing Units Expressed by Chemical Formulas (29), (30) and (31)
449 mg of polyhydroxyalkanoate (average molecular weight: Mn=48000, Mw=111000 measured by the gel permeation chromatography described in Example 1) containing 7.1 mol % in total of 3-hydroxy-11-bromoundecanoic acid unit, 3-hydroxy-9-bromononanoic acid unit and 3-hydroxy-7-bromoheptanoic acid, 79.3 mol % of 3-hydroxy-5-phenoxyvaleric acid and 13.7 mol % of other components (straight-chain 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and straight-chain 3-hydroxyalka-5-enoic acid having 10 or 12 carbon atoms) was dissolved in 6 ml of N,N-dimethylformamide at a room temperature, and gas in the system was replaced with nitrogen. Then, while holding the system at a room temperature, 265 mg of sodium 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate dissolved in 8 ml of N,N-dimethylformamide was added, and 106 μl of diethylamine was then added, and was stirred at a room temperature for 24 hours.
After the reaction was completed, N,N-dimethylformamide as a reaction liquid was once distilled away by a rotary evaporator, and the mixture was again dissolved in 2 ml of N,N-dimethylformamide, and was thereafter put in 200 ml of pure water to allow reprecipitation. The resulting precipitate was collected by centrifugal separation. This precipitate was suspended again with 50 ml of pure water, and subjected to centrifugal separation to collect the precipitate for washing. This washing operation was conducted three times, followed by drying the precipitate under reduced pressure to obtain 389 mg of polyhydroxyalkanoate.
For this PHA, measurements were carried out using the nuclear magnetic resonance apparatus under the same condition as Example 1.
The composition of PHA calculated from the results obtained by the 1 H-NMR spectrum is shown in Table 3.
TABLE 3
Content of each unit
(mol %)
Chemical formulas (29),
2.1
(30) and (31)
Chemical formula (28)
85.3
Other polyhydroxyalkanoate
12.6
From the results, this polyhydroxyalkanoate was found to contain 2.1 mol % in total of units expressed by chemical formulas (29), (30) and (31) and 85.3 mol % of 3-hydroxy-5-phenoxyvaleric acid unit expressed by chemical formula (28).
The molecular weight of the obtained PHA was measured by the method described in Example 1 using gel permeation chromatography and found as follows: Mn=3400 and Mw=14500.
Example 4
Method (2) of Producing Polyhydroxyalkanoate Containing Units Expressed by Chemical Formulas (29), (30) and (31)
300 mg of polyhydroxyalkanoate containing 22.0 mol % in total of 3-hydroxy-11-bromoundecanoic acid unit, 3-hydroxy-9-bromononanoic acid unit and 3-hydroxy-7-bromoheptanoic acid, 69.0 mol % of 3-hydroxy-5-(phenylsulfonyl)valeric acid and 9.0 mol % of other components (straight-chain 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and straight-chain 3-hydroxyalka-5-enoic acid having 10 or 12 carbon atoms) was dissolved in 4 ml of N,N-dimethylformamide at a room temperature, and gas in the system was replaced with nitrogen. Then, while holding the system at a room temperature, 446 mg of sodium 2-(2′-mercaptoethyl)amide-2-methylpropanesulfonate dissolved in 6 ml of N,N-dimethylformamide was added, and 180 μl of diethylamine was then added, and was stirred at a room temperature for 18 hours.
After the reaction was completed, N,N-dimethylformamide as a reaction liquid was once distilled away by a rotary evaporator, and the mixture was again dissolved in 2 ml of N,N-dimethylformamide, and was thereafter put in 200 ml of pure water to allow reprecipitation. The resulting precipitate was collected by centrifugal separation. This precipitate was suspended again with 50 ml of pure water, and subjected to centrifugal separation to collect the precipitate for washing. This washing operation was conducted three times, followed by drying the precipitate under reduced pressure to obtain 227 mg of polyhydroxyalkanoate.
For this PHA, measurements were carried out using the nuclear magnetic resonance apparatus under the same condition as Example 1.
The composition of PHA calculated from the results obtained by the 1 H-NMR spectrum is shown in Table 4.
TABLE 4
Content of each unit
(mol %)
Chemical formulas (29),
2.7
(30) and (31)
Chemical formula (32)
70.6
Other polyhydroxyalkanoate
26.7
From the results, this polyhydroxyalkanoate was found to contain 2.7 mol % in total of units expressed by chemical formulas (29), (30) and (31) and 70.6 mol % of 3-hydroxy-5-(phenylsulfonyl)valeric acid unit expressed by chemical formula (32).
The PHA obtained in Examples 1 to 3 described above, which was classified into exemplary compounds (1) to (3) as shown in Table 5, was used as a charge controlling agent to produce various kinds of toners, and evaluations were carried out (Examples 5 to 44).
TABLE 5
Exemplary compound (1)
PHA of Example 1
Exemplary compound (2)
PHA of Example 2
Exemplary compound (3)
PHA of Example 3
Example 5
First, an aqueous Na 3 PO 4 solution was added in a 2 liter four-necks flask equipped with a high-speed stirring apparatus TK-Homomixer, and was heated at 60° C. with the number of rotations kept at 10,000 rpm. An aqueous CaCl 2 solution was slowly added therein to prepare an aqueous dispersing medium containing a very small water slightly soluble dispersant Ca 3 (PO 4 ) 2 .
On the other hand, the following compositions were dispersed for 3 hours using a ball mill, followed by adding therein 10 parts by weight of release agent (ester wax) and 10 parts by weight of 2,2′-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator to prepare a polymerizable monomer composition.
styrene monomer
82 parts by weight
ethylhexyl acrylate monomer
18 parts by weight
divinylbenzene monomer
0.1 parts by weight
cyan coloring agent (C. I. Pigment Blue 15)
6 parts by weight
oxidized polyethylene resin (molecular weight 3200,
5 parts by weight
acid number 8)
exemplary compound (1)
2 parts by weight
Then, the polymerizable monomer composition obtained as described above was put in the aqueous dispersing medium prepared previously to carry out the granulation with the number of rotations being kept at 10,000 rpm. Thereafter, the composition was made to undergo a reaction at 65° C. for 3 hours while being stirred with a paddle stirring blade, and was thereafter polymerized at 80° C. for 6 hours to complete the polymerization reaction. After the reaction was completed, the suspension was cooled, and an acid was added therein to dissolve the water slightly soluble dispersant Ca 3 (PO 4 ) 2 , followed by filtering, rinsing and drying the solution to obtain blue polymerized particles (1). The particle size of the obtained blue polymerized particles (1) measured using Coulter Counter Multisizer (manufactured by Coulter Co.) was 7.1 μm as a weight average particle size, and the ratio of fines (the abundance ratio of particles with the size of 3.17 μm or smaller in the number distribution) was 5.5% by number.
As a fluidity improver, 1.3 parts by weight of hydrophobic silica fine powder (BET: 270 m 2 /g) treated with hexamethyl disilazane were externally added to 100 parts by weight of blue polymerized particles (1) prepared as described above through dry-mixing by a Henshel mixer, whereby a blue toner (1) of this Example was obtained. In addition, 7 parts by weight of blue toner (1) were mixed with 93 parts by weight of resin-coated magnetic ferrite carrier (average particle size: 45 μm) to prepare a two-component type blue developer (1) for magnetic brush development.
Examples 6 and 7
Blue toners (2) and (3) of Examples 6 and 7 were obtained in the same manner as Example 5 except that 2.0 part by weight of exemplary compounds (2) and (3) are used, respectively, in place of exemplary compound (1). In addition, two-component type blue developers (2) and (3) were obtained, respectively, in the same manner as Example 5 using the blue toners (2) and (3) and the above described resin-coated magnetic ferrite carrier. For these blue toners (2) and (3) as well as the two-component type blue developers (2) and (3), the properties of toners were measured in the same manner as Example 5, and the results thereof are shown in Table 6.
Comparative Example 1
A blue toner (4) of Comparative Example 1 was obtained in the same manner as Example 5 except that no charge controlling agent was used. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 6. In addition, a two-component type blue developer (4) of Comparative Example 1 was obtained in the same manner as Example 5 using this toner.
Evaluation
For the two-component type blue developers (1) to (3) obtained in the Examples 5 to 7 and the two-component type blue developer (4) obtained in the Comparative Example 1, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels. Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 6.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 6
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Blue
(μm)
number)
seconds
seconds
seconds
seconds
5
1
7.1
5.5
A
A
A
A
6
2
7.2
5.3
A
A
A
A
7
3
7.0
5.1
B
A
B
A
Comparative
4
7.0
5.2
D
D
D
D
Example 1
Examples 8 to 10
Yellow toners (1) to (3) were obtained in the same manner as Example 5 except that 2.0 parts by weight of exemplary compounds (1) to (3) were used, and a yellow coloring agent (Hansa yellow G) was used in place of the cyan coloring agent. The properties of these toners were measured in the same manner as Example 5, and the results thereof are shown in Table 7. In addition, two-component type yellow developers (1) to (3) were obtained in the same manner as Example 5 using these toners.
Comparative Example 2
A yellow toner (4) of Comparative Example 2 was obtained in the same manner as Example 5 except that no charge controlling agent was used, and that the yellow coloring agent (Hansa yellow G) was used in place of the cyan coloring agent. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 7. In addition, a two-component type yellow developer (4) of Comparative Example 2 was obtained in the same manner as Example 5 using this toner.
Evaluation
For the two-component type yellow developers (1) to (3) obtained in the Examples 0.8 to 10 and the two-component type yellow developer (4) obtained in the Comparative Example 2, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels.
Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 7.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 7
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Yellow
(μm)
number)
seconds
seconds
seconds
seconds
8
1
7.0
5.4
A
A
A
A
9
2
7.2
5.3
A
A
A
A
10
3
6.9
5.5
B
A
B
B
Comparative
4
7.2
4.9
D
D
D
D
Example 2
Examples 11 to 13
Black toners (1) to (3) of were obtained in the same manner as Example 5 using 2.0 parts by weight of exemplary compounds (1) to (3) except that a carbon black (DBP oil absorption 110 mL/100 g) was used in place of the cyan coloring agent. The properties of these toners were measured in the same manner as Example 5, and the results thereof are shown in Table 8. In addition, two-component type black developers (1) to (3) were obtained in the same manner as Example 5 using these toners.
Comparative Example 3
A black toner (4) of Comparative Example 3 was obtained in the same manner as Example 5 except that no charge controlling agent was used and that the carbon black (DBP oil absorption 110 mL/100 g) was used in place of the cyan coloring agent. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 8. In addition, a two-component type black developer (4) of Comparative Example 3 was obtained in the same manner as Example 5 using this toner.
Evaluation
For the two-component type black developers (1) to (3) obtained in the Examples 11 to 13 and the two-component type black developer (4) obtained in the Comparative Example 3, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels. Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 8.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 8
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Black
(μm)
number)
seconds
seconds
seconds
seconds
11
1
7.0
5.3
A
A
A
A
12
2
7.1
5.4
A
A
A
A
13
3
6.9
5.2
B
B
B
B
Comparative
4
6.9
5.3
D
C
D
C
Example 3
Example 14
stylene-butylacrylate copolymer resin
100 parts by weight
(glass transition temperature 70° C.)
magenta pigment (C. I. Pigment Red 114)
5 parts by weight
exemplary compound (1)
2 parts by weight
The above described compositions were mixed and melt-kneaded by a biaxial extruder (L/D=30). The resulting mixture was cooled and then roughly ground by a hammer mill, and finely being ground by a jet mill. The resultant powder was classified to obtain magenta coloring particles (1). The weight average particle size and the ratio of fines of the magenta coloring particles (1) were 7.0 μm and 5.2% by number.
As a fluidity improver, 1.5 parts by weight of hydrophobic silica fine powder (BET: 250 m 2 /g) treated with hexamethyl disilazane were dry-mixed with 100 parts by weight of the magenta coloring particles (1) by a Henshel mixer, whereby a magenta toner (1) of this Example was obtained. In addition, 7 parts by weight of the resulting magenta toner (1) were mixed with 93 parts by weight of resin-coated magnetic ferrite carrier (average particle size: 45 μm) to prepare a two-component type magenta developer (1) for magnetic brush development. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 9.
Examples 15 and 16
Magenta toners (2) and (3) of Examples 15 and 16 were obtained in the same manner as Example 14 except that 2.0 parts by weight of each of exemplary compounds (2) and (3) were used in place of exemplary compound (1). The properties of these toners were measured in the same manner as Example 5, and the results thereof are shown in Table 9. In addition, two-component type magenta developers (2) and (3) were obtained in the same manner as Example 14 using these toners.
Comparative Example 4
A magenta toner (4) of Comparative Example 4 was obtained in the same manner as Example 14 except that no charge controlling agent was used. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 9. In addition, a two-component type magenta developer (4) of Comparative Example 4 was obtained in the same manner as Example 14 using this toner.
Evaluation
For the two-component type magenta developers (1) to (3) obtained in the Examples 14 to 16 and the two-component type magenta developer (4) obtained in the Comparative Example 4, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels. Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 9.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 9
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Red
(μm)
number)
seconds
seconds
seconds
seconds
14
1
7.0
5.2
A
A
A
A
15
2
7.1
5.1
A
A
A
A
16
3
6.9
5.3
B
A
B
A
Comparative
4
7.1
5.1
D
C
D
C
Example 4
Examples 17 to 19
Black toners (5) to (7) were obtained in the same manner as Example 14 using 2.0 parts by weight of exemplary compounds (1) to (3) except that a carbon black (DBP oil absorption 110 mL/100 g) was used in place of the magenta pigment. The properties of these toners were measured in the same manner as Example 5, and the results thereof are shown in Table 10. In addition, two-component type black developers (5) to (7) were obtained in the same manner as Example 14 using these toners.
Comparative Example 5
A black toner (8) of Comparative Example 5 was obtained in the same manner as Example 14 except that no charge controlling agent was used and that the carbon black (DBP oil absorption 110 mL/100 g) was used in place of the magenta pigment. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 10. In addition, a two-component type black developer (8) of Comparative Example 5 was obtained in the same manner as Example 14 using this toner.
Evaluation
For the two-component type black developers (5) to (7) obtained in the Examples 17 to 19 and the two-component type black developer (8) obtained in the Comparative Example 5, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels. Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 10.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 10
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Black
(μm)
number)
seconds
seconds
seconds
seconds
17
5
7.1
5.4
A
A
A
A
18
6
7.0
5.3
A
A
A
A
19
7
6.9
5.2
B
A
B
B
Comparative
8
7.0
5.7
D
C
D
D
Example 5
Example 20
polyester resin
100 parts by weight
carbon black (DBP absorption 110 ml/100 g)
5 parts by weight
exemplary compound (1)
2 parts by weight
The polyester resin was synthesized as follows: 751 parts of bisphenol A propylene oxide 2 mol adduct, 104 parts of terephtalic acid and 167 parts of trimellitic anhydride were polycondensed with two parts of dibutyltin oxide as a catalyst to obtain a polyester resin having a softening point of 125° C.
The above described compositions were mixed and melt-kneaded by a biaxial extruder (L/D=30). The resulting mixture was cooled and then roughly ground by a hammer mill, and finely ground by a jet mill. The resultant powder was classified to obtain black coloring particles (9). The weight average particle size and the ratio of fines of the black coloring particles (9) were 7.7 μm and 5.0% by number.
As a fluidity improver, 1.5 parts by weight of hydrophobic silica fine powder (BET: 250 m 2 /g) treated with hexamethyl disilazane were dry-mixed with 100 parts by weight of the black coloring particles (9) by a Henshel mixer, whereby a black toner (9) of this Example was obtained. In addition, 7 parts by weight of the resulting black toner (9) were mixed with 93 parts by weight of resin-coated magnetic ferrite carrier (average particle size: 45 μm) to prepare a two-component type black developer (9) for magnetic brush development. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 11.
Examples 21 and 22
Black toners (10) and (11) of Examples 21 and 22 were obtained in the same manner as Example 20 except that 2.0 parts by weight of each of exemplary compounds (2) and (3) were used in place of exemplary compound (1). The properties of these toners were measured in the same manner as Example 5, and the results thereof are shown in Table 11. In addition, two-component type black developers (10) and (11) were obtained in the same manner as Example 20 using these toners.
Comparative Example 6
A black toner (12) of Comparative Example 6 was obtained in the same manner as Example 20 except that no exemplary compound (1) was used. The properties of this toner were measured in the same manner as Example 5, and the results thereof are shown in Table 11. In addition, a two-component type black developer (12) of Comparative Example 6 was obtained in the same manner as Example 20 using this toner.
Evaluation
For the two-component type black developers (9) to (11) obtained in the Examples 20 to 22 and the two-component type black developer (12) obtained in the Comparative Example 6, the charge levels of toners after stirring for 10 and 300 seconds were measured under conditions of normal temperature and normal humidity (25° C., 60% RH) and high temperature and high humidity (30° C., 80% RH) using the previously described method of measuring charge levels. Then, measurement values of two-component blow-off charge levels were rounded off to the first decimal place, and the resultant values were evaluated according to the following criteria. The results are shown together in Table 11.
Electrifiability
A: Excellent (−20 μC/g or lower)
B: Good (−19.9 to −10.0 μC/g)
C: Usable (−9.9 to −5.0 μC/g)
D: Unusable (−4.9 μC/g or higher)
TABLE 11
Particle size
Electrifiability
distribution
Normal temperature
Weight
and normal
High temperature
average
Ratio of
humidity (Q/M)
and high humidity (Q/M)
Toners
particle
fines
Stirring
Stirring
Stirring
Stirring
Number:
size
(% by
for 10
for 300
for 10
for 300
Examples
Black
(μm)
number)
seconds
seconds
seconds
seconds
20
9
7.7
5.0
A
A
A
A
21
10
7.6
4.9
A
A
A
A
22
11
7.4
5.2
B
B
B
A
Comparative
12
7.5
4.9
D
C
D
C
Example 6
Examples 23 to 40 and Comparative Examples 7 to 12
First, an image forming apparatus used in the image formation methods of Examples 23 to 40 and Comparative Examples 7 to 12 will be described. FIG. 2 is a schematic explanatory view of the cross section of an image forming apparatus for carrying out the image formation methods of Examples and Comparative Examples of the present invention. A photoconductor drum 1 shown in FIG. 2 has a photosensitive layer 1 a having an organic photo semiconductor on a substrate 1 b , and is configured to rotate in the direction indicated by the arrow, and its surface is electrically charged at a potential of about −600 V by a charge roller 2 being a charge member situated opposite to the photoconductor drum 1 and contacting and rotating with the drum. As shown in FIG. 2 , the charge roller 2 has a cored bar 2 b covered with a conductive elastic layer 2 a.
Next, the photoconductor drum 1 with its surface electrically charged is exposed to light 3 and at this time, on/off operations are performed on the photoconductor by a polygon mirror according to digital image information, whereby an electrostatic latent image with the potential of the exposed area being −100 V and the potential of the dark area being −600 V is formed. Subsequently, this electrostatic latent image on the photoconductor drum 1 is reverse-developed and thereby actualized using a plurality of development apparatuses 4 - 1 , 4 - 2 , 4 - 3 and 4 — 4 , and thus a toner image is formed on the photoconductor drum 1 . At this time, the two-component type developers obtained in Examples 5 to 22 and Comparative Examples 1 to 6 were individually used as developers to form a toner image with a yellow toner, a magenta toner, a cyan toner or a black toner. FIG. 3 is an enlarged sectional view of principal parts of development apparatuses 4 for two-component type developers used at that time.
Then, the toner image on the photoconductor drum 1 is transferred to an intermediate transfer body 5 contacting and rotating with the photoconductor drum 1 . As a result, a four-color color combination developed image is formed on the intermediate transfer body 5 . A non-transferred toner remaining on the photoconductor drum 1 without being transferred is collected in a container 9 for residual toners by a cleaner member 8 .
The intermediate transfer body 5 is constituted by a cored bar 5 b as a support and an elastic layer 5 a provided thereon as shown in FIG. 2 . In this Example, the intermediate body 5 having the cored bar 5 b coated with the elastic layer 5 b with a carbon black as a conductivity producer sufficiently dispersed in nitrile-butadiene rubber (NBR) was used. The degree of hardness of the elastic layer 5 b measured in accordance with “JIS K-6301” was 30 degrees, and the volume resistivity was 1×10 9 Ω·cm. The level of transfer current required for transferring the image from the photoconductor drum 1 to the intermediate transfer body 5 is about 5 μA, and this level of current was obtained by adding a voltage of +500 V to the cored bar 5 b.
The four-color toner color combination latent image formed on the intermediate transfer body 5 is transferred to an object transferring material such as a paper by a transfer roller 7 , and is thereafter fixed by a heat-fixation apparatus H. The transfer roller 7 is provided thereon the core metal 7 b with the outside diameter of 10 mm on which an elastic layer 7 a is formed by coating of a foam of ethylene-propylene-diene based tridimensional copolymer (EPDM) dispersing carbon sufficiently therein as a conductivity producing material. The layer had a volume specific resistance of 1×10 6 Ω·cm and a hardness degree of 35° as measured in accordance with “JIS K-6301”. In addition, a voltage was applied to this transfer roller 7 to pass a transfer current of 15 μA therethrough.
In the apparatus shown in FIG. 2 , a fixation apparatus of heated roll type having no oil coating mechanism shown in FIGS. 6 and 7 was used in the heat-fixation apparatus H. The both upper and lower rollers of the fixation apparatus used here had surface layers made of fluorine based resin. In addition, the diameter of the roller was 60 mm. The fixation temperature for fixation was 160° C., and the nipping width was set at 7 mm. Furthermore, a transfer residual toner on the photoconductor drum 1 , which was collected by cleaning, was transported to a developing device by a reuse mechanism for reuse.
Evaluation
Two-component type developers produced using the toners of Examples 5 to 22 and two-component type developers produced using toners of Comparative Examples 1 to 6 were used, respectively, to perform printout testing at a printout rate of 8 sheets (A4 size) per minute while the developer was supplied one after another in a monochromatic intermittent mode (namely a mode in which the developing device is stopped for 10 seconds for each printout to accelerate the degradation of a toner in a preliminary operation during restart of the device) at a normal temperature and normal humidity (25° C., 60% RH) and a high temperature and high humidity (30° C., 80% RH) under the conditions described above, and resulting printout images were evaluated for the following items. The evaluation results are shown together in Table 12.
Evaluation of Printout Images
1. Image Density
Images were printed out on a predetermined number of normal copying papers (75 g/m 2 ), and the image density was evaluated according to the level at which the density of the image from the final printout was retained with respect to the density of the initial image. Furthermore, for the measurement of image density, a Macbeth reflective densitometer (manufactured by Macbeth Co., Ltd.) was used to measure a density relative to that of the printout image on a white ground with the density of original copy equal to 0.00.
A: Excellent (image density from the final printout is 1.40 or greater) B: Good (image density from the final printout is 1.35 or greater and lower than 1.40) C: Usable (image density from the final printout is 1.00 or greater and lower than 1.35) D: Unusable (image density from the final printout is lower than 1.00)
2. Image Fog
Images were printed out on a predetermined number of normal copying papers (75 g/m 2 ), and the image fog was evaluated with a solid white image from the final printout. Specifically, the evaluation was made as follow: the worst value of the reflective density of the white ground after printing and the average reflective density of the paper before printing, as measured using a reflective densitometer (Reflectometer ODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), were defined as Ds and Dr, respectively, (Ds-Dr) was calculated from these values as a fog level to make an evaluation according to the following criterion.
A: Excellent (fog level is 0% or higher and lower than 1.5%) B: Good (fog level is 1.5% or higher and lower than 3.0%) C: Usable (fog level is 3.0% or higher and lower than 5.0%) D: Unusable (fog level is 5.0% or higher)
3. Transferability
Solid black images were printed out on a predetermined number of normal copying papers (75 g/m 2 ), and the image dislocation level of the image from the final printout was visually observed to make an evaluation according to the following criterion.
A: Excellent (almost not observed) B: Good (slightly observed) C: Usable D: Unusable
In addition, in Examples 23 to 40 and Comparative Examples 7 to 12, occurrences of scares and sticking residual toners on the surfaces of the photoconductor drum and intermediate transfer body, and their influence on printout images (matching with the image forming apparatus) were visually evaluated after 5000 images were outputted, and as a result, scars and sticking residual toners on the surfaces of the photoconductor drum and intermediate transfer body were not observed, and thus matching with the image forming apparatus was excellent for the system using two-component type developers of Examples 23 to 40. For the system using two-component type developers of Comparative Examples 7 to 12, on the other hand, sticking toners were observed on the surface of the photoconductor drum in all cases. In addition, for the system using two-component type developers of Comparative Examples 7 to 12, sticking toners and surface scars could be observed on the surface of the intermediate transfer body, and there was a problem in matching with image formation apparatus such that longitudinally striped defects occurred on the image.
TABLE 12
Two-
Normal temperature and
High temperature and
component
normal humidity
high humidity
type
Image
Image
Image
Image
Examples
developer
density
fog
Transferability
density
fog
Transferability
23
Blue 1
A
A
A
A
A
A
24
Blue 2
A
A
A
A
A
A
25
Blue 3
B
A
A
B
B
A
26
Yellow 1
A
A
A
A
A
A
27
Yellow 2
A
A
A
A
A
A
28
Yellow 3
B
A
A
B
B
A
29
Black 1
A
A
A
A
A
A
30
Black 2
A
A
A
A
A
A
31
Black 3
A
B
B
B
B
B
32
Red 1
A
A
A
A
A
A
33
Red 2
A
A
A
A
A
A
34
Red 3
A
A
B
B
B
B
35
Black 5
A
A
A
A
A
A
36
Black 6
A
A
A
A
A
A
37
Black 7
B
A
A
B
B
A
38
Black 9
A
A
A
A
A
A
39
Black 10
A
A
A
A
A
A
40
Black 11
B
B
B
B
B
B
Comparative
Blue 4
D
D
D
D
D
D
Example 7
Comparative
Yellow 4
D
D
D
D
D
D
Example 8
Comparative
Black 4
C
C
D
C
D
D
Example 9
Comparative
Red 4
C
C
D
C
D
D
Example 10
Comparative
Black 8
C
C
D
D
D
D
Example 11
Comparative
Black 12
C
C
D
C
D
D
Example 12
Examples 41 to 43 and Comparative Examples 13 to 15
For carrying out the image formation methods of Examples 41 to 43 and Comparative Examples 13 to 15, the toners obtained in Examples 5, 8 and 11 and Comparative examples 1 to 3 were used, respectively, as developers. In addition, for means for forming an image, an image forming apparatus with a commercially available laser beam printer LBP-EX (manufactured by Canon Inc.) modified so that it was provided with a reuse mechanism and reset as shown in FIG. 4 was used. That is, the image forming apparatus shown in FIG. 4 is provided with a system in which a non-transferred toner remaining on the photoconductor drum 20 after the transfer process is scraped off by an elastic blade 22 of a cleaner 21 abutting against the photoconductor drum 20 , then sent into the cleaner 21 by a cleaner roller, passed through a cleaner reuse 23 , and returned to the development device 26 via a hopper 25 by a supply pipe 24 with a carrier screw mounted thereon, and the toner collected in this way is reused.
In the image forming apparatus shown in FIG. 4 , the surface of the photoconductor drum 20 is electrically charged by a primary charge roller 27 . A rubber roller (diameter 12 mm, abutment pressure 50 g/cm) coated with a nylon resin and having conductive carbon dispersed therein was used for the primary charge roller 27 , and an electrostatic latent image with a dark area potential VD of −700 V and a light area potential VL of −200 V was formed on the electrostatic latent image carrier (photoconductor drum 20 ) by laser exposure (600 dpi, not shown). As a toner carrier, a development sleeve 28 having a roughness degree Ra of 1.1 with the surface coated with a resin having a carbon black dispersed therein was used.
An enlarged sectional view of the principal part of the development apparatus for one-component type developers used in Examples 41 to 43 and Comparative Examples 13 to 15 is shown in FIG. 5 . For conditions for developing electrostatic latent images, the speed of the development sleeve 28 was set at a speed 1.1 times as high as the movement speed of the surface of the photoconductor drum 20 opposite thereto, and the space a between the photoconductor drum 20 and the development sleeve 28 (between S and D) was 270 μm. For the member for controlling the thickness of the toner, an abutting urethane rubber blade 29 was used. In addition, the set temperature of the heat-fixation apparatus for fixing a toner image was 160° C. Furthermore, for the fixation apparatus, a fixation apparatus shown in FIGS. 6 and 7 was used.
As described above, under the condition of normal temperature and normal humidity (25° C., 60% RH), images were printed out on up to 30,000 sheets at a printout rate of 8 sheets (A4 size) per minute while the toner was supplied one after another in a continuous mode (namely, a mode in which the development device is not stopped, and thereby consumption of the toner is promoted), and the densities of resulting printout images were measured to evaluate the durability of the image according to the following criterion. In addition, the image from the 10,000 th printout was observed to make an evaluation about image fog according to the following criterion. At the same time, situations of the components constituting the image forming apparatus after the durability testing were observed to evaluate matching between each component and the above described toner. The results thereof are shown together in Table 13.
Change in Image Density During Endurance
Images were printed out on a predetermined number of normal copying papers (75 g/m 2 ), and the image density was evaluated according to the level at which the density of the image from the final printout was retained with respect to the density of the initial image. Furthermore, for the measurement of image density, a Macbeth reflective densitometer (manufactured by Macbeth Co., Ltd.) was used to measure a density relative to that of the printout image on a white ground with the density of original copy equal to 0.00.
A: Excellent (image density from the final printout is 1.40 or greater) B: Good (image density from the final printout is 1.35 or greater and lower than 1.40) C: Usable (image density from the final printout is 1.00 or greater and lower than 1.35) D: Unusable (image density from the final printout is lower than 1.00)
Image Fog
Images were printed out on a predetermined number of normal copying papers (75 g/m 2 ), and the image fog was evaluated with a solid white image from the final printout. Specifically, the evaluation was made as follow: the worst value of the reflective density of the white ground after printing and the average reflective density of the paper before printing, as measured using a reflective densitometer (Reflectometer ODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), were defined as Ds and Dr, respectively, (Ds-Dr) was calculated from these values as a fog level to make an evaluation according to the following criterion.
A: Excellent (fog level is 0% or higher and lower than 1.5%) B: Good (fog level is 1.5% or higher and lower than 3.0%) C: Usable (fog level is 3.0% or higher and lower than 5.0%) D: Unusable (fog level is 5.0% or higher)
Evaluation of Matching With Image Forming Apparatus
1. Matching with Development Sleeve
After the printout testing was completed, the situation of residual toners sticking to the surface of the development sleeve and their influence on the printout image were visually evaluated.
A: Excellent (not observed) B: Good (almost not observed) C: Usable (sticking residual toners are observed but the influence on the image is not significant) D: Unusable (sticking of residual toners is significant, causing unevenness in the image)
2. Matching With Photoconductor Drum
Occurrences of scars and sticking residual toners on the surface of the photoconductor drum and their influence on the printout image were evaluated visually.
A: Excellent (not observed) B: Good (slightly observed but no influence on the image) C: Usable (sticking residual toners and scars are observed but the influence on the image is not significant) D: Unusable (sticking of residual toners is significant, causing longitudinal striped defects in the image)
3. Matching with Fixation Apparatus
The surface situation of the fixation film was observed, and the results of surface characteristics and occurrences of sticking residual toners were collectively averaged to evaluate the durability of the film.
(1) Surface Characteristics
Occurrences of scares and flaking on the fixation film were visually observed and evaluated after the printout testing was completed.
A: Excellent (not observed) B: Good (almost not observed) C: Usable D: Unusable
(2) Situation of Sticking Toners
The situation of residual toners sticking to the surface of the fixation film was visually observed and evaluated after the printout testing was completed.
A: Excellent (not observed) B: Good (almost not observed) C: Usable D: Unusable
TABLE 13
Evaluation of matching with
Evaluation of printout image
other apparatus
Change in image density
10
Fixation
during endurance
thousands
apparatus
10
30
fogged
Development
Photoconduct
Surface
Toner
Examples
Toner
Initial
Thousand
thousands
thousands
images
sleeve
or drum
characteristic
fixation
41
Blue 1
A
A
A
A
A
A
A
A
A
42
Yellow 1
A
A
A
A
A
A
A
A
A
43
Black 1
A
A
A
A
A
A
A
A
A
Comparative
Blue 4
C
D
D
D
D
D
D
D
D
Example 13
Comparative
Yellow 4
C
D
D
D
D
D
D
D
D
Example 14
Comparative
Black 4
B
C
D
D
D
D
D
D
D
Example 15
Example 44
Printout testing was performed while the blue toner (1) of Example 5 was supplied one after another in a continuous mode (namely, a mode in which the development device is not stopped, and thereby consumption of the toner is promoted) in the same manner as Example 41 except that the toner reuse mechanism of the image forming apparatus of FIG. 4 was removed and that the printout rate was set at the level of 16 sheets (A4 size) per minute. The resulting printout images and the matching with the image evaluating apparatus used were evaluated for the same items as Examples 41 to 43 and Comparative Examples 13 to 15. As a result, satisfactory results were obtained for all the items. | A polyhydroxyalkanoate comprises a unit of formula (1): —(O—CH((CH 2 ) m SASO 2 R)CH 2 C(═O))— wherein R is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 ; A represents a substituted or unsubstituted aliphatic hydrocarbon structure; m is an integer number selected from 1 to 8; and in the case where a plurality of units exist in the same molecule, R, A and m in one unit can be different from them in another unit respectively. A method of producing the polyhydroxyalkanoate comprises the step of reacting a polyhydroxyalkanoate comprising a unit of formula (18): —(O—CH((CH 2 ) m Br)CH 2 C(═O))—, wherein m is an integer number selected from 1 to 8, and in the case where a plurality of units exist in the same molecule, m in one unit can be different from that in another unit, with at least one type of compounds of formula (19): HS-A 1 -SO 2 R 15 wherein R 15 is selected from the group consisting of OH, a halogen atom, ONa, OK, OCH 3 and OC 2 H 5 and A 1 is a substituted or unsubstituted aliphatic hydrocarbon structure, and in the case where a plurality of types of compounds exist in the same molecule, R 15 and A 1 in one unit can be different from them in another unit respectively. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel derivatives of acylnorbornanone acetals, a process for preparing the same, and a perfume composition containing the same.
2. Description of the Prior Art
A variety of compounds having the norbornane ring has been heretofore prepared. For example, U.S. Pat. No. 3,860,635 discloses vinyl norbornanones, and U.S. Pat. No. 3,748,344 discloses cyclic acetals of norbornanone carboxaldehydes. However, no compounds are known in which the cyclic acetal moiety is linked through the spiro carbon atom with the norbornane ring. In addition, spiro cyclic type compounds are unknown which have an acyl group attached to the norbornane ring.
SUMMARY OF THE INVENTION
It has been found during the course of synthesis of compounds having the norbornane ring that a compound having an acyl group and a cyclic acetal linked through the spiro carbon atom with the norbornane ring has a woody fragrance and is useful as a component of perfume compositions. The present invention was completed on the basis of this finding.
Thus, the present invention includes acylnorbornanone acetals represented by the following general formula (I): ##STR3## (wherein R 1 is a saturated hydrocarbon group having 2 to 7 carbon atoms and R 2 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); a process for preparing the same; and a perfume composition containing the same.
The compounds in accordance with the present invention may be prepared by the following reaction scheme; ##STR4##
The oxidation should be conducted under a neutral or basic condition without causing the decomposition of the acetal linkage and collapsing the molecule in the oxidation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The α-hydroxyalkylnorbornanone acetals represented by the above formula (IV) which can be used as raw materials in accordance with the present invention can be prepared by introducing the hydroxyl group into the α-position by means of a reaction such as hydroboration, oxymercuration, oxythallation or epoxidation of alkenylnorbornanone acetals represented by the following general formula (V): ##STR5## (wherein R 1 is a saturated hydrocarbon group having 2 to 7 carbon atoms, and R 3 and R 4 are independently a hydrogen atom or a hydrocarbon group such that the total number of carbon atoms when taken together is between 1 and 9) or alkylidenenorbornanone acetals represented by the following general formula (VI): ##STR6## (wherein R 5 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 1 has the same meaning as above).
Thus, the methods of introducing the hydroxyl group into the α-position of the compound represented by formula (V) or (VI) involve the addition to the unsaturated bond of the compound represented by either of the formulas, reduction and then hydrolysis. The methods may include:
(1) a method via oxymercuration which involves the reaction of a mercuric salt such as mercuric acetate with the compound of formula (V) to thereby add the mercuric salt to the unsaturated bond followed by demercuration and hydrolysis;
(2) a method via oxythallation which involves the same reaction as represented hereinabove using a thallium salt such as thallium nitrate;
(3) a method via hydroboration which involves the addition of a borane or the like to the unsaturated bond of the compound as represented by formula (IV) followed by oxidation and hydrolysis; and
(4) a method via epoxidation which involves the addition of oxygen to the unsaturated bond by use of a peracid, a peroxide or molecular oxygen in the presence of a catalyst, reduction of the resultant epoxide, and hydrolysis.
These methods allow selective introduction of the hydroxyl group into the α-position of the double bond in a high yield and minimize side reactions such as isomerization. The methods also cause little decomposition of the acetal moiety of the raw material, norbornanone acetals, because all of the methods are carried out under non-acidic conditions.
In the method via oxymercuration represented as (1) above, the addition of a mercuric salt such as mercuric acetate, mercuric trifluoroacetate or mercuric nitrate to the alkenylnorbornanone acetal is carried out in a solvent such as water or a mixture thereof with tetrahydrofuran, acetonitrile, ethyl ether, methanol or ethanol at a temperature in the range of 5° to 130° C., preferably 15° to 80° C. The reaction is usually conducted under ambient pressure, but it may be conducted under a slightly reduced or elevated pressure. The amount of the mercuric salt to be used may be in the range of 0.5 to 2.0 moles with respect to one mole of an olefin to be added.
Then, the reductive elimination of mercury and the concurrent hydrolysis are conducted using sodium boron hydride, sodium hydroxide or sodium-liquid ammonia, thereby giving the α-hydroxyalkylnorbornanone acetal represented by formula (IV). The reaction is carried out at a temperature in the range of 0° to 50° C., preferably 0° to 30° C. The reaction pressure is usually ambient pressure, although it may be slightly reduced or elevated.
The method via oxythallation represented as (2) above can be carried out in the same manner as in the method via oxymercuration as set forth hereinabove, with the exception that a thallium salt such as thallium acetate, thallium trifluoroacetate or thallium nitrate is used in place of the mercuric salt.
In the method via hydroboration represented as (3) above, diborane or a substituted boron compound such as disiamylborane, dicyclohexylborane, thexylborane, diisopinocampheylborane, 9-borabicyclo[3.3.1]nonane, dichloroborane or the like is first added to the alkenyl- or alkylidenenorbornane acetal. The amount of the borane compound to be used may range from 0.1 to 1.0 mole for the diborane and from 0.5 to 2.0 moles for the substituted borane compound with respect to one mole of the olefin. As a solvent, an ether may be employed such as tetrahydrofuran, ethyl ether, dimethylcarbitol, diethylcarbitol or the like. The reaction temperature may range from -15° to 230° C., preferably from -5° to 60° C., and the reaction is usually conducted under ambient pressure, although the pressure may be slightly reduced or elevated. Then, the oxidative hydrolysis is effected in an aqueous solution or a solution of dimethylcarbitol, diethylcarbitol, tetrahydrofuran or ethyl alcohol containing a hydrogen peroxide-sodium hydroxide or an organic peracid-sodium hydroxide. The temperature for this reaction may range from 0° to 80° C., preferably from 5° to 50° C.
In the method via epoxidation represented as (4) above, the alkenyl- or alkylidene-norbornanone acetal epoxide is first produced by using a peracid or the like, separated by means of distillation or the like, and then reduced. The resulting product is then hydrolyzed.
In the reaction of producing the epoxide, there may be employed as a solvent a halogenated hydrocarbon such as chloroform, methylene chloride, carbon tetrachloride or the like; an aromatic hydrocarbon such as benzene, toluene, xylene or the like; an aliphatic hydrocarbon such as hexane, pentane, heptane or the like; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or the like; an ester such as ethyl acetate, ethyl propionate or the like; or an ether such as ethyl ether, tetrahydrofuran or the like. In these solvents, the epoxide can be provided by means of an organic peracid such as peracetic acid, trifluoroperacetic acid, perbenzoic acid, performic acid, m-chloroperbenzoic acid, permaleic acid, perphthalic acid, perlauric acid or the like; an organic peroxide and the oxide of a transition metal such as molybdenum, vanadium or the like; hydrogen peroxide and an organic nitrile or oxygen in the presence of a catalyst of metals of the silver series, thallium series or palladium series. In the vapor phase reaction where the silver series, thallium series or palladium series metal catalyst is used, the reaction system may be diluted with an inert gas such as nitrogen gas or the like. The amount of the organic peracid or the like may range from 0.5 to 2.0 moles with respect to one mole of the olefin. The reaction may be carried out at a temperature in the range of -15° to 100° C., preferably -5° to 70° C., and under ambient pressure or under a slightly reduced or elevated pressure.
The epoxides prepared as hereinabove are then separated by means of distillation, extraction or the like and subjected to reduction and then hydrolysis. The reduction is effected in an ether such as ethyl ether, tetrahydrofuran, dimethylcarbitol, diethylcarbitol or the like; an aromatic hydrocarbon such as benzene, toluene, xylene or the like; or an aliphatic hydrocarbon such as hexane, pentane or the like; and with a variety of metal hydrides such as lithium aluminum hydride, lithium borohydride, sodium borohydride, aluminum hydride, dichloro-aluminum hydride, diisobutyl-aluminum hydride, diborane, cyanosodium borohydride, triethoxylithium aluminum hydride, tri-tertiary-butoxy-aluminum hydride, sodium aluminum hydride, disiamylborane or the like. The reduction is carried out at a temperature in the range of -80° to 100° C., preferably -70° to 50° C. After reduction, the hydrolysis is effected with methanol, ethanol, isopropanol, water or the like to provide the α-hydroxylalkylnorbornanone acetal.
For example, a vinylnorbornanone acetal as the alkenylnorbornanone acetal of formula (V) or a ethylidenenorbornanone acetal as the alkylidenenorbornanone acetal of formula (VI) can be produced from a Diels-Alder adduct between cyclopentadiene and butadiene according to the following reaction scheme: ##STR7##
In the above scheme, RCOOH may include, for example, formic acid, acetic acid, propionic acid and the like, and the OH-R 1 -OH to be employed for the last-mentioned acetals may include, for example, 1,2-diol or 1,3-diol.
The term "1,2-diol" referred to herein means a compound in which two hydroxyl groups are attached respectively to two adjacent carbon atoms of a saturated hydrocarbon. The term "1,3-diol" referred to herein means a compound in which two hydroxyl groups are attached respectively to two carbon atoms of a saturated hydrocarbon, with another carbon atom interposed between the said two carbon atoms.
Representatives of the 1,2-diols stated hereinabove may be ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-, 2,3- or 3,4-hexanediol, 1,2- or 2,3-pentanediol, 1,2-cyclohexanediol, methylcyclohexane-1,2-diol and the like.
Illustrative of the 1,3-diols may be 1,3-propane diol, 1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 1,3-cyclohexanediol, methylcyclohexane-1,3-diol and the like.
In the reaction in which the corresponding acetals are formed, the diols represented hereinabove may be used singly or in a mixture thereof.
Where the acetals are produced with a 1,2-diol, a 1,3-dioxolane ring is formed, and where the acetals are prepared with a 1,3-diol, a 1,3-dioxane ring is formed.
The compounds represented by formula (V) or (VI) obtainable from the 5-vinyl- or ethylidene-2-norbornene as the aforesaid alkenyl- or alkylidene-norbornene in the manner as represented hereinabove may be, for example, spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)], spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-nobornane)], spiro[1,3-dioxane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)], spiro[5,5'-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)], spiro[4-methyl-1,3-dioxane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)], spiro[5,5-diethyl-1,3-dioxane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)], spiro[4,5-tetramethylene-1,3-dioxolane-2,2'- or 2,3'-(5'-vinyl- or ethylidene-norbornane)] and the like.
The oxidation of the α-hydroxyalkylnorbornanone acetals then provides the corresponding acylnorbornanone acetals.
The oxidation to be practiced in the present invention should be effected under a neutral or basic condition without decomposing the acetal linkage and causing the cleavage of the molecule by the oxidation.
Accordingly, the oxidation method to be employed herein may be a method of oxidation with a ketone such as acetone, methyl ethyl ketone or quinone in the presence of an aluminum alkoxide such as aluminum triisopropoxide or the like (Oppenauer oxidation); a method of oxidation using, for example, pyridine-chromic anhydride complex; a method of oxidation with a chromate, a dichromate, a permanganate or the like; a method of oxidation with molecular oxygen in the presence of a copper series catalyst; a method of oxidation with a peroxide in a neutral or basic medium; or the like.
Among the methods of oxidation represented hereinabove, the Oppenauer oxidation employs an alkali metal alkoxide such as aluminum triisopropoxide, aluminum tri-tertiary-butoxide, aluminum triphenoxide or the like in an amount of 0.25 to 3 moles with respect to one mole of the alcohol in the presence of a large excess of an oxidizing agent such as a ketone, e.g., acetone, cyclohexanone, methyl ethyl ketone, benzophenone, parabenzoquinone or the like. The solvent to be employed may be, for example, an aromatic hydrocarbon such as benzene, toluene or xylene. The reaction may be carried out at a temperature in the range of 0° to 200° C., preferably 30° to 150° C., for 10 minutes to 68 hours, usually 15 minutes to 24 hours. In the reaction represented hereinabove, the oxidizing agent such as the ketone, e.g., acetone, is converted to an alcohol such as isopropylalcohol. Accordingly, the oxidation is accomplished in a better yield when it is carried out while distilling off the alcohol formed.
Where pyridine-chromic anhydride complex is used for the oxidation, pyridine or a chlorinated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride or the like may be employed as a solvent. The oxidation may be carried out at a temperature ranging from 0° to 80° C., preferably 5° to 50° C., under ambient pressure or a slightly reduced or elevated pressure.
A method of oxidation with chromic acid which does not exert any influence on the acetal linkage can be carried out in a solvent such as acetic anhydride, acetic acid whose acidity is weakened with an alkali acetate, a benzene-acetic acid mixture, or a weakly basic solvent such as dimethylformamide or the like.
Vapor phase or liquid phase oxidation can be effected with molecular oxygen in the presence of the copper series catalyst. In the vapor phase oxidation, an inert gas such as nitrogen gas may be employed as a diluent.
In any case, any arbitrary solvent may be chosen for the oxidation reaction as long as it does not affect the oxidation reaction.
After the oxidation is conducted in the manner as set forth hereinabove, the solvent is distilled off to leave a residual material which is purified in the usual way to give the acylnorbornanone acetals.
The α-hydroxyalkylnorbornanone acetals in accordance with the present invention as represented by formula (IV) above have two structural isomers represented by the following formula (IVa) or (IVb): ##STR8##
The acylnorbornanone acetals represented by formula (I) above also have two structural isomers as represented respectively by formulas (II) and (III) corresponding to formulas (IVa) and (IVb): ##STR9##
In these formulas, the symbol R 1 is a saturated hydrocarbon group having 2 to 7 carbon atoms.
The compounds to be represented by the above formula are, for example, spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)], spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)], spiro[1,3-dioxane-2,2'- or 2,3'-(5-acetyl-norbornane)], spiro[5,5'-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)], spiro[4-methyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)], spiro[5,5-diethyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)] and spiro[4,5-tetramethylene-1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)].
The compounds represented by formula (I) above which are the compounds in accordance with the present invention have stereoisomers, the endo- and exo-forms, corresponding to each of the structural isomers represented hereinabove. They may be represented for the 5-acetyl-2-norbornanone ethylene acetal or spiro[1,3-dioxolane-2,2'-(5'-acetyl-norbornane)] as follows: ##STR10##
In accordance with the present invention, any of these stereoisomers are effective for perfume compositions. Accordingly, the compounds obtainable in the manner as set forth hereinabove may be employed in a mixture of stereoisomers as fragrance components, or they may naturally be employed as single compounds.
The compounds represented by formula (I) above are in a colorless, transparent liquid form, favorable in compatibility in any arbitrary amount with a solvent to be usually employed for a perfume, and mix with other solid perfume materials well.
These compounds are stable against oxidation and the like and do not undergo any transformations during storage for a long period of time. They cause no irritation upon contact with the skin and are nontoxic in use.
As they have the properties as stated hereinabove, the compounds as represented by formula (I) above in accordance with the present invention can be employed as compound perfumes useful for general fragrant cosmetics such as soaps, detergents, creams, toilet water and the like, and as fragrance materials for other daily commodities.
The acylonorbornanone acetals represented by formula (I) in accordance with the present invention may be synthesized, in addition to the methods as hereinabove stated, by the methods such as:
(A) a method utilizing the Diels-Alder reaction;
(B) a method utilizing the Friedel-Crafts reaction; and
(C) a method employing a dialkylcadmium, a lithiumdialkylcuprate.
The method (A) is a method involving the addition of an acylethylene such as methyl vinyl ketone to cyclopentadiene by means of the Diels-Alder reaction to give the acylnorbornene; the addition thereto of an acid; hydrolysis; oxidation; and acetalization.
The method (B) is one which involves the addition of an acyl halide to a 5-norbornene-2- or 3-one by means of the Friedel-Crafts reaction using a catalyst such as aluminum chloride, and the conversion of the resultant acylnorbornanone to the corresponding acetal.
The method (C) is a method involving the addition of an organic acid or sulfuric acid to a halogeno-norbornene such as 5-chloro-2-norbornene; hydrolysis; oxidation to give the norbornanone halide which in turn is converted into the norbornanone acetal halide; treatment of the acetal halide with a cadmium halide to give the dialkylcadmium or with an alkyl lithium and a copper halide to give the lithium dialkyl cuprate where the alkyl group mentioned above indicates substituted norbornyl group; and then reaction with an acyl halide.
In order to further explain the technical content of the present invention, it is illustrated by way of a preparation example and working examples as reference examples. The present invention should not be construed to be restricted to the working examples which follow, because they are chosen from many working examples. The present invention can be practiced by varying its working embodiments in an arbitrary manner as long as they do not deviate from the spirit and scope of the present invention.
The following illustrates examples for preparing the compounds represented by the formulas above and embodiments of the present invention by way of the working examples.
Preparation Example
Synthesis of spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-α-hydroxyethyl-nornornane)]
Spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-α-hydroxyethylnorbornane)] was prepared from spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-vinyl-norbornane)] by means of oxymercuration.
For this process, 12.0 g (0.067 mole) of spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-vinyl-norbornane)] was dropwise added at room temperature to a mixture of 21.2 g (0.067 mole) of mercuric acetate, 60 ml of water and 60 ml of tetrahydrofuran. After the dropwise addition was completed, the mixture was stirred for about 10 minutes to give a colorless, clear solution to which was added 65 ml of an aqueous solution containing 8.2 g of sodium hydroxide, and then 65 ml of an aqueous solution of 1.4 g of sodium borohydride and 8.2 g of sodium hydroxide was added. After the mixture was stirred for 1 hour at room temperature, mercury was removed from the reaction mixture and sodium chloride was added thereto to a level of saturation. The resulting solution was extracted three times with a benzene-ether mixture, and the resulting organic layer was washed with a small amount of a sodium chloride saturated aqueous solution to remove the alkali material and dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residual material was distilled under reduced pressure to leave 10.5 g of a colorless viscous liquid (yield, 79.1%; boiling point 104°-105° C./0.25 mmHg; n D 22 =1.4970).
ir (neat method): ˜3,500 cm -1 (stretching vibration of O-H); the stretching vibration of the vinyl group C═C at 1,630 cm -1 disappeared.
nmr (CDCl 3 ): 6.1 τ (singlet, 4H), 6.2-6.4 τ (multiplet, 1H), 7.6 τ (broad singlet), 7.3-8.9 τ (multiplet, 12H).
______________________________________Elemental analysis (as C.sub.11 H.sub.19 O.sub.3): C % H %______________________________________Calculated: 66.3 9.5Found: 66.5 9.6______________________________________
EXAMPLE 1
Synthesis of spiro[1,3- dioxolane-2,2'- or 2,3'- (5'-acyl-norbornane)]
13.3 g (0.067 mole) of spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-α-hydroxyethyl-norbornane)] was dissolved in 250 ml of dry toluene. To this mixture was added 100 ml of freshly distilled cyclohexanone, and 100 ml of a toluene solution of 7.2 g (0.036 mole) of aluminum triisopropoxide was dropwise added thereto. After the dropwise addition was completed, the reaction mixture was heated under reflux for 2 hours and then cooled to room temperature. Then, the mixture was poured into 100 ml of a sodium potassium tartrate saturated aqueous solution. After the organic layer was separated, the aqueous layer was extracted with a benzene-ether mixture. The extract was then combined with the organic layer previously separated and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residual material was distilled under reduced pressure to give the title colorless liquid (12.7 g; yield, 96.7%; boiling point 86° C./0.30 mmHg) having a floral woody fragrance.
ir (neat method): ˜1,710 cm -1 (stretching vibration of C═O). The stretching vibration of O-H at ˜3,500 cm -1 disappeared.
nmr (CDCl 3 ): 6.1 τ (singlet, 4H), 7.9 τ (singlet, 3H), 7.4-8.8 τ (multiplet, 9H).
______________________________________Elemental analysis (as C.sub.11 H.sub.17 O.sub.3): C % H %______________________________________Calculated: 67.3 8.2Found: 67.6 8.3______________________________________
Gas chromatography (filler, Silicone SE-30; column material, stainless steel; column size, 0.25 cm (diameter×90 m; column temperature, 150° C.) revealed that spiro[1,3-dioxolane-2,2'-(5'-acetyl-norbornane)] amounted to 70% of the total, with the remainder being spiro[1,3-dioxolane-2,3'-(5'-acetyl-norbornane)], and that the ratio of the endo-form to the exo-form was about 30:70.
It was also observed that, in Examples 2 to 4 which follow, gas chromatography revealed substantially the same ratio in the corresponding structural isomers and stereoisomers as in Example 1.
EXAMPLE 2
Synthesis of spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)]
Spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-α-hydroxyethyl-norbornane)] was reacted in the same manner as in Example 1 to give the title spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)].
Yield: 94.5%
Boiling point: 102° C./0.8 mmHg
ir (neat method): ˜1,710 cm -1 (stretching vibration of C═O); the stretching vibration of O-H at ˜3,500 cm -1 disappeared.
nmr (CDCl 3 ): 6.0-6.2 τ (quartet, 2H), 7.9 τ (singlet, 3H), 7.0-8.7 τ (multiplet, 9H), 8.8-9.0 τ (triplet, 6H).
______________________________________Elemental analysis (as C.sub.13 H.sub.20 O.sub.3): C % H %______________________________________Calculated: 69.6 8.9Found: 69.3 8.7______________________________________
EXAMPLE 3
Synthesis of spiro[1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)]
Spiro[1,3-dioxane-2,2'- or 2,3'-(5'-α-hydroxyethyl-norbornane)] was reacted in the same manner as in Example 1 to give the title spiro[1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)].
Yield: 95.0%
Boiling point: 107° C./0.2 mmHg
ir (neat method): ˜1,715 cm -1 (stretching vibration of C═O); the stretching vibration of O-H at ˜3,500 cm -1 disappeared.
nmr (CDCl 3 ): 6.1-6.3 τ (triplet, 4H), 7.9 τ (singlet, 3H), 7.0-8.8 τ (multiplet, 11H).
______________________________________Elemental analysis (as C.sub.12 H.sub.18 O.sub.3): C % H %______________________________________Calculated: 68.5 8.6Found: 68.7 8.2______________________________________
EXAMPLE 4
Synthesis of spiro[5,5-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)]
Spiro[5,5-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-α-hydroxylethyl-norbornane)] was reacted in the same manner as in Example 1 to given the title spiro[5,5-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)].
Yield: 96.5%
Boiling point: 93° C./0.2 mmHg
ir (neat method): ˜1,715 cm -1 (stretching vibration of C═O); the stretching vibration of O-H at ˜3,500 cm -1 disappeared.
nmr (CDCl 3 ): 6.1 τ (singlet, 4H), 7.9 τ (singlet, 3H), 7.2-8.8 τ (multiplet, 9H), 9.1 τ (singlet, 6H).
______________________________________Elemental analysis (as C.sub.14 H.sub.22 O.sub.3): C % H %______________________________________Calculated: 70.6 9.3Found: 70.1 9.5______________________________________
EXAMPLE 5
The spiro[1,3-dioxolane-2,2'- or 2,3'-(5'-acetylnorbornane)] prepared in Example 1 was formulated in the following composition. The formulation was suitable for a perfume base for men in fougere note.
______________________________________Oakmoss Oil, (Texas) 2 gBergamot Oil, (Bourbon) 10 gLavender Oil, (England) 13 gRhodinol 10 gβ-Phenylethyl alcohol 6 gPatchouli Oil (Ceylon) 3 gGeranium Oil, (France) 4 gMethylionone 12 gCyclopentadecanolide 1 gPetitgrain Oil, (Paraguay) 5 gCoumarin 10 gMusk ketone 6 gHeliotropine 6 gPhenylethyl salicylate 3 gJasmone 3 gBenzyl salicylate 3 gAcetal prepared in Example 1 3 gTotal 100 g______________________________________
EXAMPLE 6
The spiro[4,5-dimethyl-1,3-dioxolane-2,2'- or 2,3'-(5'-acetyl-norbornane)] prepared in Example 2 was formulated into the following composition to provide a perfume composition in muguet note having the fragrance of lily of the valley. This composition was suitable for perfumes in soaps and toiletries.
______________________________________Citronellol 24 gRhodinol 10 gβ-phenylethyl alcohol 25 gHydroxycitronellal 13 gBenzyl acetate 6 gJasmone 4 gα-Amylcinnamic aldehyde 4 g10% Indole.ethanoic solution 2 gLinalool 5 gCyclopentadecanolide 1 g10% ethylvanillin.ethanolic solution 1 gAcetal prepared in Example 2 5 gTotal 100 g______________________________________
EXAMPLE 7
The spiro[1,3-dioxane-2,2'- or 2,3'-[5'-acetylnorbornane)] prepared in Example 3 was formulated into the following composition to provide a perfume composition of cypress base in floral bouquet note. The composition was suitable for hair oil, hair spray, hand creams and the like.
______________________________________Oakmoss Oil, (French) 5 gPatchouli Oil, (Bourbon) 3 gVetiver Oil, (Bourbon) 6 gSandal Wood Oil, (Mysore) 5 gBergamot Oil, (Madagascar) 17 gMethylionone 6 gLinalool 5 gJasmone 2 gMethyldihydrojasmonate 2 gRose Absolute, (Burgalia) 4 g10% Vanillin ethanolic solution 3 gHeliotropine 3 gIsoamyl salicylate 2 gLily aldehyde 5 gLabdonum Oil, (Lebanon) 3 gβ-Phenylpropyl alcohol 5 gCoumarin 5 g10% indole.ethanolic solution 5 gBenzyl acetate 9 gAcetal prepared in Example 3 5 gTotal______________________________________
EXAMPLE 8
The spiro[5,5-dimethyl-1,3-dioxane-2,2'- or 2,3'-(5'-acetyl-norbornane)] was formulated into the composition to provide a citrus fragrance in combination with bergamot aroma. This formulation was suitable for a perfume base in toilet water, eau de Cologne and soaps.
______________________________________Orange Oil, (Japan) 7 gBergamot Oil, (Zanzibal) 25 gLemon Oil, (California) 5 gLinalyl acetate 6 gSandal Wood Oil, (Mysore) 7 gPatchouli Oil, (Bourbon) 8 gLavender Oil, (England) 5 gβ-Phenylethyl alcohol 4 gMethyldihydrojasmonate 2 g10% indole.ethanolic solution 0.5 gBenzoin 3 g0.3% Tongkining Musk Tincture 2 g2% vanillin.ethanolic solution 5 gCoumarin 8 g10% ethylenebrassylate.ethanolic solution 3 gLinalool 4 gMethyl anthranilate 0.5 gDimethylbenzylcarbinyl acetate 1 gAcetal prepared in Example 4 4 gTotal 100 g______________________________________ | An acylnorbornanone acetal is represented by the formula: ##STR1## (wherein R 1 is a saturated hydrocarbon group having 2 to 7 carbon atoms and R 2 is a hydrogen atom or a hydrocabon group having 1 to 10 carbon atoms). The acylnorbornanone acetal is prepared by oxidizing an α-hydroxyalkylnorbornanone acetal represented by the formula: ##STR2## (wherein R 2 is a hydrogen atom or a hydrocarbon group having 2 to 7 carbon atoms). The perfume composition contains as a perfume component the acylnorbornanone acetal as represented above. | 2 |
BACKGROUND OF THE INVENTION
The present invention concerns a flyer with two flyer arms and with an enclosed guide duct comprising a straight guide tube for a roving, which at a spinning position of a spinning preparatory machine is guided from a drafting arrangement through the guide duct over a presser finger, which at its free end is provided with a yarn guide.
From British Pat. No. 380,745 a flyer is known, in which two flyer arms are formed by steel tubes, and which is provided with two additional auxiliary arms. The lower ends of these four arms are stiffened by a hoirzontal ring. As seen from the point of view of solidity or strength, this flyer can achieve high rotational speeds. In this flyer, however, no presser finger is provided, and thus the deposition of the roving onto the bobbin tube is uncontrolled and thus is effected with insufficient exactness. Furthermore, the duct for the roving is partially open, which detrimentally influences the roving quality.
In a flyer design known from German Pat. No. 1,685,910 the flyer is designed as an open flyer. The flyer arm guiding the roving, or both flyer arms, comprise an inner steel tube, which is surrounded by aluminium, stiffening of the flyer being aimed at mainly when using this arrangement. For the presser finger used for guiding the roving a special presser rod is provided. This presser rod adds an additional weight, which (for symmetry reasons) is to be compensated for at the other arm and thus is doubled. The lack of the horizontal ring in this second mentioned known arrangement implies the disadvantage that the mutual distance of the lower ends of the flyer arms increases at high rotational speeds of the spinning flyer. In consequence of this the quality of the roving suffers and it is no longer properly and evenly wound onto the bobbin tube. Enlargement of the distance between the flyer arms furthermore creates the danger of flyer breakages and thus the danger of injuries to the personnel.
SUMMARY OF THE INVENTION
These disadvantages are to be avoided according to the present invention. The invention is characterized in that the bottom ends of the flyer arms are connected with a ring, that the straight guide tube is supported in an upper and in a lower pivoting bearing and is supported to be rotatable about its longitudinal axis, and that the presser finger is rigidly connected with the guide tube.
Obviously, noticeably less weight is added to the flyer if the horizontal ring is provided, than must be added for stiffening the flyer arms if these are not provided with a horizontal ring. Based on the fact that the guide tube does not exert any support function, a further advantage is seen in that the guide tube can be made from any suitable desired material, e.g. also partially from a ceramic material.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a section of a flyer seen from its side; and
FIG. 2 is a horizontal section along line II--II of FIG. 1 in an enlarged view.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In both Figures, identical structure has been designated with the same reference characters.
The flyer shown in FIG. 1 comprises a hollow cylinder 12 provided with a bore 11, the hollow cylinder 12 being rotatably supported in a bearing (not shown). From this cylinder 12 there extends an arm portion 14 comprising a tubular supply duct 13. This arm portion 14 together with a vertical arm portion 15, which is not visible in FIG. 1 because it is located behind a guide tube 22 depicted in FIG. 1 but is shown in FIG. 2, forms, as a rigid unit, one arm 14,15 of the flyer. From the hollow cylinder 12 there furthermore extends a second flyer arm 16 consisting of an inclined portion and a vertical portion.
The bottom ends of the arm 14,15 and of the arm 16 are connected with a horizontal ring 17. In the embodiment shown, the arm 16 is rigidly connected with the ring 17 using a threaded bolt or screw 18, but any type of mounting, such as e.g. also the casting in one piece is considered within the scope of the present invention.
The aforementioned guide tube 22, which is located in front of the vertical arm portion 15 in the showing of FIG. 1, is supported in an upper pivoting bearing 20 and in a lower pivoting bearing 21. The upper pivoting bearing 20 is mounted onto the arm portion 14. The lower pivoting bearing 21, as shown in the embodiment illustrated, is built into the ring 17. The bearings 20,21 are arranged with respect to the guide tube 22 in such a manner that pivoting of the guide tube 22 is effected about its longitudinal axis 23. Advantageously, the supply duct 13 is provided with a short tubular extension, which for forming the upper bearing 20 extends into the guide tube 22. The lower bearing 21 also, instead of being built into the ring 17 as shown in FIG. 1, can be arranged, e.g. on a member extending towards the location of the bearing 21, which member is located at the lower end of the bottom arm portion 15.
A presser finger 25 is rigidly connected with the guide tube 22. It is equipped at its free end with a yarn guide 26 for the roving, which is provided with an eyelet 27. A bent tube 30 forms an extension of the guide tube 22. Its free end is directed towards the roving guide 26. The bore 11, the supply duct 13, the guide tube 22 and the bent tube 30 together form a guide duct for the roving being produced during operation of the flyer. The tube 30, in the design example illustrated, is mounted upon the presser finger 25.
For the spinning process spindle (not shown) is provided at each spinning position, the rotational axis of which coincides with the rotational axis 31 of the corresponding flyer. Using a pre-tensioning element formed by a helical spring 32 the guide tube 22 and together with it the presser finger 25, rigidly mounted thereon, are subject to a constantly acting pre-tension directed towards the axis 31, i.e. towards the spindle (not shown).
The guide tube 22 furthermore is connected with a counterweight 33, which also is pivotable together with the guide tube 22 about the lengthwise or longitudinal axis 23 thereof. While the flyer rotates, the counterweight 33 is subject to a centrifugal force directed towards the outside. Thus a torque momentum is generated, which is opposed to the one generated by the presser finger 25. In this manner the presser finger 25 is pressed onto the spindle by the counterweight 33 in the same sense of rotation as effected by the helical spring 32. The torque momentum torque generated by the counterweight 33 and the pre-tension generated by the spring 32 tend to rotate the guide tube, as shown in the view of FIG. 2, clockwise. A stop 34 limits the extent of such movement. It is formed in the embodiment shown as a screw mounted upon the vertical arm portion 15. By rotating the screw 34 the end or terminal position of the pivoting movement of the presser finger 25 thus can be set as desired.
During operation the roving is guided from a drafting arrangement (not shown), through the guide duct, which comprises, as already mentioned, the bore 11, the supply duct 13, the guide tube 22 and the bent tube 30. At the same time twist is imparted permanently to the roving supplied by the drafting arrangement by the rotation of the flyer, in such a manner that at the exit end or outlet of the tube 30 a roving emerges, which, using the presser finger 25, is wound up as a roving onto the spindle, arranged concentrically with the axis 31, as mentioned above but not shown. During the spinning process also the spindle is rotated constantly about its axis which coincides with the rotational axis 31. Additionally, the spindle moves up and down with respect to the flyer. During this process the presser finger 25 constantly is pre-tensioned or pressed against the spindle, or against a bobbin tube placed thereon, and places roving wraps onto it as layers. It is to be mentioned in this context, that in the patent claims the term "roving" is used for simplicity in expression, even if in reality a spinning process is considered, in which immediately after emerging from the drafting arrangement, i.e. before entering the bore 11, a roving provided with a determined twist is not yet present.
After emerging from the bent tube 30 the roving is wound about the presser finger 25, one or a plurality of wraps being formed, and subsequently is transferred via the eyelet 27 onto the bobbin tube placed onto the spindle, or onto the winding layers already present thereon. The inventive flyer shows the further advantage that the roving rotating about the axis 31 is located practically over the total part of its path in an enclosed duct, and that thus blowing-off of the fibres due to the extraordinarily high rotational speeds practically does not occur. Thus, also the formation of fibre fly waste in the spinning room is considerably reduced. For these reasons it proves advantageous to choose a relatively long length of the bent tube 30, as in this manner the roving portion exposed in the free room is shortened further again. Furthermore, the wraps about the presser finger become narrower if the distance between the free end of the tube 30 from the eyelet 27 is shorter in such a manner that, applying less wraps on the presser finger 25 the same braking force which is decisive for the density of the bobbin package is obtained on the roving than with more wraps spread over a greater length. It thus proves advantageous if the bent tube 30 extends to over half the length of the presser finger 25. Of course the type of fibre material processed has an influence in this respect.
Furthermore, the inventive flyer proves very advantageous if applied in a machine with automatic bobbin change system, in which the roving bobbin package is doffed by lifting it up and off, and the new, empty bobbin tube is donned from above. For freeing the upward path, the flyer in these machines is tilted to an inclined position in such manner that the plane defined by the arms 14,15 and 16 is brought into an inclined position (with respect to the bobbin axis). Owing to the fact that the presser finger 25, activated by the spring 32, contacts the layers on the bobbin package also while the flyer is at a standstill, severing of the roving between the eyelet 27 and the layers while the bobbin package is moved up and off is effected very reliably and at the desired point. Also owing to the permanently pre-tensioned or pressed-on presser finger 25 secured catching of the roving end, or the roving beard respectively, held by the eyelet by the freshly donned bobbin tube, is ensured.
Finally, a further, important characteristic is to be mentioned. It is not a rare occurrence, that during operation of a roving frame certain spinning positions are to be shut off, i.e. are to be operated without fibre material. In this case the individual spindles of such a machine cannot be stopped individually as desired, but they continue rotating idle. The adjustable stop 34 permits adaption (of the movement) of the presser finger 25 in such manner, that an operation mode is possible without complications, in which the individual spinning positions not provided with fibre material and thus the corresponding spindles rotate idle, i.e. without a bobbin tube. The distance of the yarn guide 26 from the outer spindle surface in this arrangement is set by the adjustable stop 34 in such manner that these two elements show a small clearance between them, and thus mutual contact and wear of said elements is avoided.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. Accordingly, | The present invention concerns a flyer for roving frames. According to the invention the flyer arms (14,16) at their free ends are connected rigidly with a ring (17). Furthermore, an enclosed guide duct with a guide tube (22) is provided for the roving, which guide tube (22) is supported to be pivotable about its longitudinal axis and supports a presser finger (25). Thus, a flyer of relatively low weight results, but of high solidity, permitting high rotational speeds. The guide duct for the roving can be of enclosed shape over a maximum of its length. | 3 |
This application claims priority of Provisional Application Ser. No. 61/189,302 filed Aug. 18, 2008, the disclosure of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
“Blotting” or “electro-blotting” refers to the process used to transfer biological samples from a gel to a membrane under the influence of an electric field. The process requires a membrane that can immobilize biomolecular samples for subsequent detection. This places specific requirements on the membranes related to surface area, porosity, and protein binding capacity.
Western blotting is one modification of this technique that involves the immobilization of proteins on membranes before detection using monoclonal or polyclonal antibodies. Prior to protein immobilization on the membrane, sample proteins are separated using SDS polyacrylamide gel electrophoresis (SDS-PAGE) to separate native or denatured proteins. The proteins are then transferred or electro-blotted onto a membrane, where they are probed and ultimately detected using antibodies specific to a target protein. Western blotting membranes are typically made of nitrocellulose (NC) or polyvinylidene fluoride (PVDF). The specificity of the antibody-antigen interaction can enable a single protein to be identified among a complex protein mixture.
To summarize, Western blotting involves application of a protein sample (lysate) onto a polyacrylamide gel, subsequent separation of said complex mixture by electrophoresis, and transferal or “electro-blotting” of separated proteins onto a second matrix, generally a nitrocellulose or polyvinylidene fluoride (PVDF) membrane. Following the transfer, the membrane is “blocked” to prevent nonspecific binding of antibodies to the membrane surface. Many antibody labeling or tagging strategies are known to those skilled in the art. In the simplest protocols, the transferred proteins are incubated or complexed with a primary enzyme-labeled antibody that serves as a probe. After blocking non-specific binding sites a suitable substrate is added to complex with the enzyme, and together they react to form chromogenic, chemiluminescent, or fluorogenic detectable products that allow for visual, chemiluminescence, or fluorescence detection, respectively. The most sensitive detection schemes make use of chemiluminescent or fluorescent phenomena. In chemiluminescent detection, an enzyme-substrate complex produces detectable optical emissions (chemiluminescence). These emissions are recorded and measured using suitable detectors such as film or photonic devices. Absence or presence of signal indicates whether a specific protein is present in the lysate, and signal intensity is related to the level of the protein of interest, which in some cases may be quantifiable.
The use of nitrocellulose membranes is ubiquitous in immunodetection assay work, particularly in Western blotting. This is partially due to historical considerations, and partially due to ease of use. Nitrocellulose blotting membranes do not require an organic liquid pre-wet step, a requirement for working with hydrophobic membranes. Hydrophobic membranes require an alcohol pre-wet step followed by a water exchange step (for alcohol removal), before assembly within the blot-transfer assembly. Intrinsically hydrophobic membranes afford a limited time-frame for this assembly; the potential for the membrane to dry out is significant. Once dry, the membrane cannot be re-wet unless the pre-wet sequence is repeated. Once the membrane is contacted to the gel, removal prior to transfer can effectively ruin the gel and the separated protein samples contained. The pre-wet step is time consuming and can considerably impede workflow. A hydrophilic membrane will remain wet for a longer time interval, and can be re-wet with water if it does dry out before assembly.
Nitrocellulose blotting membranes are water wet-able and show satisfactory performance for most blotting applications. But nitrocellulose is not as mechanically or chemically stable as PVDF. PVDF will maintain its mechanical integrity over a long timeframe, whereas NC will become brittle and discolored. PVDF membrane blots can be stripped of antibodies and be re-probed. NC blots cannot. NC is prone to air oxidation, wherein it can become hazardous. It requires a separate waste stream, and when disposed of must be damped with a wetting agent, usually water.
Hydrophobic PVDF blotting membranes possess equivalent protein binding ability to NC blotting membranes, but exhibit superior blotting performance. Much lower sample concentrations can be detected under the same conditions on these PVDF membranes compared to NC. Low-background fluorescence hydrophobic PVDF blotting membranes exhibit the same enhanced sample detection while enabling the use of fluorescent detection schemes.
It therefore would be desirable to provide a hydrophilic PVDF membrane for immunodetection assays such as Western blotting, with performance characteristics that approach the lower sample detection limits and low background fluorescence that are characteristic of hydrophobic PVDF membranes. This invention addresses these requirements.
SUMMARY OF THE INVENTION
Those skilled in the art of surface modification for the purpose of altering substrate surface energies, and in particular with regard to surfaces intended for contact with biological systems, will concur that hydrophilic surface modifications traditionally exhibit low protein binding behavior. The embodiments disclosed herein build on the serendipitous and unexpected discovery that space polymers derived from certain monomeric acrylamide mixtures, and formed using free-radical polymerization reactions, can give rise to surface modifications that are not only hydrophilic, but also demonstrate a high level of protein binding.
Much of the prior art describes the use of hydroxyl containing monomers, usually carbonyl ester containing acrylate polymers, to produce membrane surface modifications having hydrophilic character and high resistance to protein binding. However, it is known that polymers from such monomers are not resistant to strong alkaline solutions. For example, a solution of 1.0 normal sodium hydroxide will hydrolyze the carbonyl containing acrylate polymers to acrylic acid containing polymers. Such acrylic acid containing polymers are ionically charged under certain pH conditions, and will attract and bind oppositely charged proteins or biomolecules, thus increasing sorption and membrane fouling. In addition, acrylic acid containing polymers swell in water to an extent that they constrict pore passages, thus reducing membrane permeability and productivity. Moreover, polymers from hydroxyl containing monomers, such as hydroxy acrylates, further react in strong alkaline solutions and degrade into soluble low molecular weight fragments, which dissolve away and expose the underlying substrate porous media or membrane.
Practitioners attempting to develop optimized membranes either for filtration or non-filtration applications in the pharmaceutical and biotechnology industries must overcome significant problems. Facing stringent cost, performance and safety requirements, a practitioner must use materials and develop manufacturing methods that produce membranes with not only optimized flow and retention characteristics, but be economical to produce, meet cleanliness criteria, be stable to the various chemical environments which are commonly encountered, and be very either very resistant to biomolecule adsorption, or very strongly adsorbing, depending upon the intended end-use. Thus, in this instance, it is very desirable to have a membrane modification that results in a hydrophilic, biomolecule adsorptive surface that is heat stable, which is resistant to degradation by any potential reagent solutions, and which has very low levels of material capable of being extracted there-from.
Protein binding results from early investigations into mixed-acrylamide polymeric surface modifications indicated that certain mixtures of hydrophilic bis-acrylamide crosslinking monomers and monofunctional neutral or charged acrylamides can, when copolymerized using UV-initiated or electron beam-initiated free-radical techniques, produce high protein-binding hydrophilic surface modifications. However, initial starting levels of each monomer had to be severely decreased before observing satisfactory dot blot morphology and blotting transfer performance.
The problems of the prior art have been overcome by the present embodiments, which provide a hydrophilic membrane particularly suited for blotting applications, preferably Western blotting. More specifically, a pre-wet hydrophobic membrane substrate, preferably made of PVDF, is contacted with a monomer solution and subjected to polymerizing conditions to render the substrate permanently hydrophilic.
The resulting membrane exhibits low background fluorescence, high protein binding, excellent retention of protein sample spot morphology, and extended dynamic range (high signal-to-noise ratio, enhanced sample detectability). Where chemiluminescence is used for detection, the level of background fluorescence inherent in the unmodified parent membrane is not as critical. The membrane demonstrates comparable or higher performance in Western blotting applications than conventional nitrocellulose blotting membranes, particularly for detection at low sample concentrations, and is directly water-wettable, eliminating the need for an alcohol pre-wet step prior to use. The membrane exhibits complete, instant, and uniform wetting upon contact with water, and exhibits delayed wetting when contacted with a saturated aqueous aluminum chloride solution. That is, when said membrane is placed on the surface of this saturated aqueous aluminum chloride solution, it wets through in a minimum time interval of not less than 1 second).
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1-3 are diagrams of Western blot results using treated membranes in accordance with certain embodiments.
DETAILED DESCRIPTION
The membranes hydrophilically modified in accordance with embodiments of the present disclosure provide immunodetection assay platforms that are comparable to, or exhibit superior blotting performance to nitrocellulose membranes, particularly with respect to expansion of the low end of the dynamic range of sample detectability. For example, in FIG. 1 , Western blotting results from a typical development run demonstrate the performance differences between the hydrophilic PVDF blotting membrane of this invention, and the controls (FL—hydrophobic PVDF membrane, and NC—Whatman/S&S BA-85 membrane). Each horizontal strip in the figure contains 5 separate Western transfer blots; three blots on hydrophilic PVDF development samples, and one blot on each of the control membranes. Each horizontal strip of 5 Western blots is the result from one electrophoresis and transfer experiment (5 gels followed by 5 blots were run in each experiment). By design, each experiment embodies identical conditions on each gel/blot with identical quantities of protein sample (applied in 4 lanes across each gel) before electrophoresis and transfer. The results shown are the recorded (chemiluminescent) transfer blots for the detection of 2 proteins (HSP70 and GAPDH) from a complex sample mixture (lysate), applied at decreasing sample concentrations, from left-to-right on each gel, and corresponding to: 5 ug, 2.5 ug, 1.25 ug, 0.67 ug.
Suitable porous membranes include those formed from aromatic sulfone polymers, polytetrafluoroethylene, perfluorinated thermoplastic polymers, polyolefin polymers, ultrahigh molecular weight polyethylene, polyamides including Nylon 6 and Nylon 66, and polyvinylidene fluoride, with polyvinylidene fluoride being particularly preferred. Porous membranes include both microporous membranes and ultrafiltration membranes, and are preferably in the form of sheets. Generally the average pore sizes include those between 0.001 and 10 microns. Blotting membranes are nominally 0.45 um pore size materials. Preferred starting membranes have a porosity (void volume) range specification of 68-73%. Blotting membranes are traditionally symmetric. However, the coating could be applied to an asymmetric membrane.
The polymeric coating can be a copolymer or terpolymer formed from at least one polyfunctional monomer modified with at least one hydrophilic functional group, said hydrophilic polyfunctional monomer(s) selected from the group consisting of polyfunctional acrylamides, polyfunctional methacrylamides and diacroylpiperazines, and formed from at least one monofunctional monomer modified with at least one hydrophilic functional group, said hydrophilic monofunctional monomer(s) selected from the group consisting of monofunctional acrylamides, monofunctional methacrylamides, and acryloyl piperazines.
It was found that a porous hydrophobic membrane, preferably one made of polyvinylidene fluoride coated with a crosslinked acrylamide-methylene-bis-acrylamide copolymer was rendered highly hydrophilic. Furthermore, at the copolymer level that was applied to the porous PVDF membrane samples in early iterations of this invention, IgG binding assays revealed protein binding levels to be in the neighborhood of 400 ug/cm 2 . This level is typical of the parent hydrophobic PVDF membrane and of conventional nitrocellulose membranes. The first surprising result was that membranes so prepared were both hydrophilic, and high protein-binding. However, the Western blotting performance of these initial samples (those that exhibited this high level of protein binding) was not satisfactory in terms of maintaining small sample blot size (blot morphology), and in terms of sample capture in blot transfers. By modifying the copolymer coating level, satisfactory blotting performance was realized. At these modified levels, protein binding levels were reduced to between 250 and 325(00) ug/cm 2 , but Western blotting performance rose to levels intermediate between nitrocellulose and the preferred parent hydrophobic PVDF membrane. Surprisingly, the present inventors found that the protein binding level is not the best or only predictor of Western blotting membrane performance. Sacrificing some protein binding ability by modifying the coating level on the substrate can result in improved blotting performance.
Thus, component levels and relative concentrations of the modifying formulation are critical to obtain acceptable immunodetection assay performance. A low overall solids concentration in a highly specific component ratio balances water-wetting performance against blotting performance. The very low background fluorescence level of the substrate membrane is preserved. If, however, the level of surface modification chemistry is too low, the result is a membrane that is not water-wettable to an acceptable extent. If the level of surface modification is too high the resulting membranes exhibit extremely high surface energies. As stated earlier, at higher levels of surface modifying chemistry, the measured protein binding capacity is roughly equivalent to nitrocellulose and hydrophobic PVDF membranes, but poor electro-blotting performance results.
In accordance with certain embodiments, the total solids level in the modifying/reactant solution is to be adjusted to between 0.90% and 1.10% by weight. A total solids concentration in this range with the specified component ratio results in optimal blotting performance. This formulation includes a UV-photoinitiator component.
Suitable amounts of the acrylamide monofunctional monomer and the bis-acrylamide crosslinking monomer in the reactant solution are to be between 0.20% and 2.00% by weight (each), preferably with amounts between 0.30% and 0.60% by weight (each), and most preferably between 0.40% and 0.50% by weight (inclusive, each). The preferred ratio of acrylamide to bis-acrylamide of the monomer reactant solution is about 1:1 (mass/mass). The preferred overall monomer concentration of acrylamide:methylene-bis-acrylamide monomer reactant solution is between 0.5% and 1.5% by mass. A suitable UV-photoinitiator component is present in 0.01% to 0.20% by weight preferably between 0.05 and 0.15% by weight, and most preferably between 0.09% and 0.11%, by weight. Suitable UV-photoinitiators include IRGACURE® 2959 (2-hydroxyl-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Ciba-geigy) 500, 754, 2959, and 819DW. Methods for preparation of the modified porous membrane substrate in accordance with certain embodiments include the steps of providing a porous membrane substrate, contacting the surface of the porous membrane substrate with a reactant solution comprising acrylamide and methylene-bis-acrylamide, and a suitable photoinitiator, removing the membrane from the solution, and polymerizing the coating in situ on the membrane substrate by exposing the same to radiation of a suitable wavelength and intensity for a suitable time interval. Preferably the porous membrane contacted with the reaction solution is irradiated with an ultraviolet light source. Filters may be used to reduce or eliminate undesirable wavelengths which may cause damage to the porous membrane. The amount of exposure time to the UV light and the intensity thereof should be familiar to those skilled in the art.
In the preferred embodiment of the invention, a laboratory-scale preparation of the reactant monomer solution is made by dissolving 1.00 g acrylamide, [H 2 C═CH—C(O)—NH 2 ] monofunctional monomer; 0.80 g methylene-bis-acrylamide, [H 2 C(—NH—C(O)CH═CH 2 ) 2 ] cross-linking monomer; and, 0.20 g Irgacure 2959 photo-initiator into 198.00 g of Milli-Q® water. An extended mixing interval of about 2 hours is required to fully dissolve the cross-linker and the photo-initiator.
More specifically, the porous hydrophobic starting membrane is pre-wet by immersion in an organic liquid or in an aqueous solution thereof that does not swell or dissolve the porous membrane, and which pre-wets the entire porous surface of the membrane.
The liquid may be a low molecular weight alcohol, or a mixture of water and a miscible organic liquid. Suitable liquids or compositions include methanol, ethanol, isopropanol, water mixtures thereof, acetone/water mixtures, and tetrahydrofuran/water mixtures of sufficiently low surface tension to affect wetting the entire membrane surface.
The purpose of this pre-wetting step is to assure that the entire membrane surface is rendered wettable by water, and subsequently by the aqueous reactant monomer solution. The pre-wetting step must be followed by a rigorous exchange step with water to eliminate the presence of the organic solvent. These pre-wetting solvents or water mixtures thereof can exert a negative influence upon the intended polymerization of the reactant monomers.
Subsequent immersion and gentle agitation of the water-wet porous membrane in the reactant solution allows the entire surface of the porous membrane to be wet with reactant solution. As long as excess water is removed from the membrane prior to immersion in the reactant solution, no significant dilution of the reactant solution will occur.
The sample is withdrawn after a short (two minute) time interval and excess reactant solution is removed from the membrane sample. The reactant solution-wetted membrane is anaerobically exposed to UV radiation to effect the polymerization directly onto the entire porous membrane surface. The resulting coated membrane exhibits: Immediate, complete, and thoroughly uniform wetting when contacted onto a water surface; A high level of Western blotting performance; A high level of protein binding (≧250 ug/cm 2 IgG) by radio-labeled assay; and, Low background fluorescence (about 2000 rfu @ 485 nm/535 nm excitation/emission wavelengths using a TECAN GENios FL fluorescence reader with detector gain set at 86, and running Magellan 5.0 software package), which is about twice the background fluorescence of the untreated (unmodified parent hydrophobic) membrane under the same measurement conditions. When placed on the surface of a saturated aqueous aluminum chloride solution, the membrane will wet through in a minimum time interval of not less than 1 second, and in a maximum time interval that may exceed 60 seconds.
EXAMPLE 1
Commercially available hydrophobic PVDF membrane from Millipore Corporation (IPFL00000) was immersed in methyl alcohol. The membrane was withdrawn and immersed in water with agitation to extract methanol for 1 minute. The membrane was withdrawn and immersed in fresh water for an additional 2-minute interval and then placed in fresh water before immersion in reactant monomer solution. Excess water was drained from the membrane and the membrane was then immersed in monomer reactant solution with gentle agitation for 2 minutes. Membrane was then exposed to UV radiation from both sides in a UV curing process at a line speed of 15 to 25 fpm. Membrane was recovered and placed into a water bath to remove unreacted monomer and non-adhering oligomers and polymer. Samples were dried either in air at room temperature overnight, or in a static forced-air oven between 60° C. and 80° C. for 10 minutes, or on an impingement dryer at 90-110° C. at a line speed of 15 to 25 fpm. Average membrane extractables as determined by an in-house TOC (Total Organic Carbon) method were measured to be about 1.44 ug/cm2, as shown in Table 1.
TABLE 1
Total Organic Carbon (TOC) - Five (5) 47 mm disks.
Requestor ID: ML6UJP37
Requestor: Antoni Peters
PVDF Hydrophillic IPFL Membrane Received
For Blotting and Immuno Assays Applications
Ext. for TOC Analysis
Extraction By: A. Pervez
TOC By: M. Santos-Rosa & A. Pervez
Date: Oct. 16-19, 2006
Ext. Temp.
Ext. Time
Ext. Vol.
Ext. Area
Ext. Solvent
[° C.]
[Hours]
[g]
[cm 2]
MilliQ Water
Ambient
24
40
86.75
Summary
Results
TOC Acid/Oxid
TOC
Corrected TOC
TOC
TOC
Sample ID
[μL/min]
[ppm C]
[ppm C]
[μg C]
[μg C/cm 2]
Water Blank
0.20/0.20
0.0639
T102 072806 A: -MBAM/AC/I-2959
0.75/1.00
3.29
3.23
129
1.49
T102 072806 B: -MBAM/AC/I-2959
0.75/1.00
2.91
2.85
114
1.31
T102 072806 C: -MBAM/AC/I-2959
0.75/1.00
3.33
3.27
131
1.51
Average extractable residual monomer levels were determined by HPLC. Values determined from 3 samples are provided in Table 2.
TABLE 2
Extractable Monomer Levels by HPLC -
Same samples as shown in Table 1.
Acrylamide
MBAM
Irgacure(R) 2959
Sample
(μg/cm2)
(μg/cm2)
(μg/cm2)
T102 072806A
0.002
0.105
N.D.
T102 072806B
0.005
0.091
N.D.
T102 072806C
0.011
0.094
N.D.
EXAMPLE 2
The procedure of Example 1 was used to treat PVDF membranes having the specifications, treatment conditions and reactant solutions shown in Tables 3A-D, 4A-D, and 5A-D.
TABLE 3A
MODIFICATION DATA for Hydrophilic PVDF Western Blotting Membrane
Membrane
Monomer
Starting
Casting
Starting Membrane Properties
Mix
Membrane
Dryer
Flow Time
Roll No.
Lot#
Lot Data
Temperature (F.)
Thick (um)
Porosity (%)
Bbl Pt (psi)
(seconds)
RUN R - No Mix Ajustment - Footage VS Monomer Mix Concentration
NA
NA
NA
NA
NA
NA
NA
NA
R01
R Mix 1
IPFL 071007 T214
300
112
72.8
9.4
56.0
R02
R Mix 1
IPFL 071007 T205
300
113
73.0
9.4
63.0
R03
R Mix 1
IPFL 071007 T205
300
113
73.0
9.4
63.0
R04
R Mix 1
IPFL 071007 T205
300
113
73.0
9.4
63.0
R05
R Mix 1
IPFL 071007 T205
300
113
73.0
9.4
63.0
R06
R Mix 1
IPFL 071007 T206
300
111
72.4
9.5
65.0
R07
R Mix 1
IPFL 071007 T206
300
111
72.4
9.5
65.0
R08
R Mix 1
IPFL 071007 T206
300
111
72.4
9.5
65.0
R09
R Mix 1
IPFL 071007 T206
300
111
72.4
9.5
65.0
R10
R Mix 1
IPFL 071007 T214
300
112
72.8
9.4
56.0
R11
R Mix 1
IPFL 071007 T214
300
112
72.8
9.4
56.0
R12
R Mix 1
IPFL 071007 T214
300
112
72.8
9.4
56.0
R12 End
NA
NA
300
NA
NA
NA
NA
TABLE 3B
MODIFICATION DATA for Hydrophilic PVDF Western Blotting Membrane
Monomer Mix Component Concentrations
Actual
Actual
Actual
Actual
Totalized
Monomer Mix
AC
MBAM
I-2959
Total Solids
Footage
Roll No.
Sample ID
Wt % (HPLC)
Wt % (HPLC)
Wt % (HPLC)
Wt % (HPLC)
By Roll
RUN R - No Mix Ajustment - Footage VS Monomer Mix Concentration
NA
R Mix 1 DRUM
0.5156
0.4214
0.1130
1.0500
0
R01
MM1 Start
0.5091
0.4042
0.1102
1.0235
0
R02
MM2
0.5105
0.3957
0.1094
1.0156
500
R03
MM3
0.5038
0.3837
0.1055
0.9931
800
R04
MM4
0.4996
0.3773
0.1001
0.9771
1100
R05
MM5
0.4948
0.3708
0.0999
0.9655
1250
R06
MM6
0.4935
0.3685
0.1020
0.9640
1550
R07
MM7
0.4868
0.3618
0.0995
0.9481
1850
R08
MM8
0.4868
0.3605
0.0974
0.9448
2150
R09
MM9
0.4777
0.3553
0.0956
0.9286
2300
R10
MM10
0.4721
0.3528
0.0956
0.9204
2600
R11
MM11
0.4673
0.3521
0.0932
0.9125
2900
R12
MM12
0.4682
0.3561
0.0918
0.9161
3200
R12 End
MM13 End
0.4574
0.3546
0.0879
0.8999
3300
TABLE 3C
MODIFICATION DATA for Hydrophilic PVDF Western Blotting Membrane
Nip
Nip
UV Chamber Conditions
Aisle
Wall
Line
N 2 Flow
Starting
Press
Press
Speed
Lamps
Lamps
Top/Bottom
UV P1
UV P3
UV P2
O 2 Level
Roll No.
psi
psi
ft/min
Type/No
Config
(SCFM)
Inch HWC
Inch HWC
Inch HWC
(ppm)
RUN R - No Mix Ajustment - Footage VS Monomer Mix Concentration
NA
NA
NA
NA
NA
NA
NA
1.0
1.6
1.0
90.0
R01
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
70.0
R02
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
56.7
R03
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
39.3
R04
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
33.0
R05
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
28.8
R06
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
27.8
R07
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
26.9
R08
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
26.4
R09
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
27.4
R10
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
25.2
R11
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
27.1
R12
20
20
20
H/4
Staggered
10/9.5
1.1
1.7
1.1
27.8
R12 End
NA
NA
NA
NA
NA
NA
1.1
1.7
1.1
25.2
TABLE 3D
MODIFICATION DATA for Hydrophilic PVDF Western Blotting Membrane
Water Wet
Water Wet
Water Wet
Salt Wet
Salt Wet
Salt Wet
Salt Wet
Fluores
QC Blotting
Western
Speed
Uniform
Through
Time
Time
Time
Time
BKG
Pass/Fail
Blotting
Roll No.
OK?
X-web?
OK?
Seconds
Seconds
Seconds
Seconds
RFU
Control
Live Lysate
RUN R - No Mix Ajustment - Footage VS Monomer Mix Concentration
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
≧NC
R01
Y
Y
Y
4.7
3.5
3.0
3.7
1750.57
Pass 9 Band
≧NC
R02
Y
Y
Y
1.4
2.4
2.4
2.1
N/Avail.
N/Avail.
≧NC
R03
Y
Y
Y
1.4
2.4
2.4
2.1
N/Avail.
N/Avail.
≧NC
R04
Y
Y
Y
2.1
2.2
2.5
2.3
N/Avail.
N/Avail.
≧NC
R05
Y
Y
Y
2.9
3.1
2.9
3.0
2015.63
Pass 9 Band
≧NC
R06
Y
Y
Y
2.2
2.3
2.3
2.3
N/Avail.
N/Avail.
≧NC
R07
Y
Y
Y
4.1
3.9
4.0
4.0
N/Avail.
N/Avail.
≧NC
R08
Y
Y
Y
2.3
3.7
3.2
3.1
N/Avail.
N/Avail.
≧NC
R09
Y
Y
Y
5.7
7.3
5.3
6.1
1927.95
Pass 9 Band
≧NC
R10
Y
Y
Y
5.4
7.1
5.4
6.0
N/Avail.
N/Avail.
≧NC
R11
Y
Y
Y
6.3
7.5
5.6
6.5
N/Avail.
N/Avail.
≧NC
R12
Y
Y
Y
8.5
7.8
7.6
8.0
1708.5
Pass 9 Band
≧NC
R12 End
Y
Y
Y
16.7
16.5
16.3
16.5
NA
NA
≧NC
TABLE 4A
MEMBRANE MODIFICATION DATA - Hydrophilic
PVDF Western Blotting Membrane
Heat Treat
Temperature
Membrane
Monomer
Starting
or Mod Line
Casting
Run
Mix
Membrane
Dryer
Dryer
Segment
Roll No.
Lot#
Lot Data
Temperature
Temperature
RUN S - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
NA
NA
NA
NA
Test
R01
S Mix 1
IPFL 071007 T203
205
300
S1
R02
S Mix 1
IPX 070907 R103
205
300
S1
R03
S Mix 1
IPX 091407 T103
205
310
S1
R04
S Mix 1
IPX 120307 T107
205
300
S1
R05
S Mix 1
IPX 091407 T102
205
310
S1
R06
S Mix 1
IPX 070907 R105
204
300
S2
R07
S Mix 1
IPX 120307 T107
200
300
S2
R08
S Mix 1
IPX 120307 T107
Transition
300
S2
R09
S Mix 1
IPX 120307 T107
205
300
S2
R10
S Mix 1
IPX 120307 T107
Transition
300
S2
R11
S Mix 1
IPX 120307 T107
210
300
S2
R12
S Mix 1
IPX 120307 T107
210
300
S2
R13
S Mix 1
IPX 120307 T107
210
300
Segment 1 Variation of starting membrane properties
Segment 2 Variation of line speed and dryer temperature
TABLE 4B
MEMBRANE MODIFICATION DATA - Hydrophilic PVDF Western Blotting Membrane
Monomer Mix Samples and Mix Component Concentrations
Monomer
Actual
Actual
Actual
Actual
Starting Membrane Properties
Mix
AC
MBAM
I-2959
Total Solids
Totalized
Run
Roll
Thick
Porosity
Bbl Pt
Flow Time
Sample
Wt %
Wt %
Wt %
Wt %
Footage
Segment
No.
(um)
(%)
(psi)
(seconds)
ID
(HPLC)
(HPLC)
(HPLC)
(HPLC)
By Roll
RUN S - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
NA
NA
NA
NA
NA
NA
MM1B
0.4979
0.3894
0.1005
0.9878
150
Test
R01
112
72.8
9.6
61.0
MM1C start
0.4926
0.3877
0.1005
0.9808
300
S1
R02
115
74.8
9.3
55.0
MM2B
0.4893
0.3849
0.0996
0.9738
450
S1
R03
115
66.4
9.6
59.0
MM3B
0.4812
0.3785
0.0971
0.9568
600
S1
R04
126
72.9
9.4
65.0
MM4B
0.4780
0.3760
0.0963
0.9503
750
S1
R05
122
66.2
11.1
78.3
MM5B
0.4761
0.3733
0.0954
0.9448
950
S1
R06
130
74.7
10.7
74.0
MM6B
0.4785
0.3757
0.0953
0.9495
1100
S2
R07
126
72.9
9.4
65.0
MM7B
0.4699
0.3678
0.0934
0.9311
1200
S2
R08
126
72.9
9.4
65.0
MM8B
0.4673
0.3656
0.0926
0.9255
1305
S2
R09
126
72.9
9.4
65.0
MM9B
0.4660
0.3644
0.0925
0.9229
1405
S2
R10
126
72.9
9.4
65.0
MM10B
0.4655
0.3637
0.0917
0.9209
1505
S2
R11
126
72.9
9.4
65.0
MM11B
0.4642
0.3619
0.0910
0.9171
1605
S2
R12
126
72.9
9.4
65.0
MM12B
0.4618
0.3598
0.0903
0.9119
1705
S2
R13
126
72.9
9.4
65.0
MM13B
Not
Not
Not
Not
1855
Available
Available
Available
Available
Segment 1 Variation of starting membrane properties
Segment 2 Variation of line speed and dryer temperature
TABLE 4C
MEMBRANE MODIFICATION DATA - Hydrophilic PVDF Western Blotting Membrane
Nip
Nip
UV Chamber Conditions
Aisle
Wall
Line
N 2 Flow
Starting
Run
Press
Press
Speed
Top/Bottom
UV P1
UV P3
UV P2
O 2 Level
Segment
Roll No.
psi
psi
ft/min
(SCFM)
Inch HWC
Inch HWC
Inch HWC
(ppm)
RUN S - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Test
R01
20
20
20
10/9.5
1.0
1.5
1.1
15.0
S1
R02
20
20
20
10/9.5
1.0
1.5
1.1
42.0
S1
R03
20
20
20
10/9.5
1.0
1.5
1.1
40.0
S1
R04
20
20
20
10/9.5
1.0
1.5
1.1
40.0
S1
R05
20
20
20
10/9.5
1.0
1.5
1.1
40.0
S1
R06
20
20
20
10/9.5
1.0
1.5
1.1
40.0
S2
R07
20
20
22
10/9.5
1.0
1.4
1.1
53.7
S2
R08
20
20
20
10/9.5
1.0
1.4
1.1
39.1
S2
R09
20
20
20
10/9.5
1.0
1.4
1.1
37.6
S2
R10
20
20
18
10/9.5
1.0
1.4
1.1
33.0
S2
R11
20
20
18
10/9.5
1.0
1.4
1.1
30.5
S2
R12
20
20
20
10/9.5
1.0
1.4
1.1
24.9
S2
R13
20
20
25
10/9.5
1.0
1.4
1.1
25.2
Segment 1 Variation of starting membrane properties
Segment 2 Variation of line speed and dryer temperature
TABLE 4D
MEMBRANE MODIFICATION DATA - Hydrophilic PVDF Western Blotting Membrane
Water Wet
Water Wet
Water Wet
Salt Wet
Salt Wet
Salt Wet
Salt Wet
Fluores
QC Blotting
Western
Run
Roll
Speed
Uniform
Through
Time
Time
Time
Time
BKG
Pass/Fail
Blotting
Segment
No.
OK?
X-web?
OK?
Seconds
Seconds
Seconds
Seconds
RFU
Control
Live Lysate
RUN S - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Test
R01
Y
Y
Y
8.2
8.8
4.9
7.3
N/Avail.
N/Avail.
≧NC
S1
R02
Y
Y
Y
26.2
15.2
5.3
15.6
N/Avail.
N/Avail.
≧NC
S1
R03
Y
Y
Y
4.2
4.2
2.9
3.8
N/Avail.
N/Avail.
≧NC
S1
R04
Y
Y
Y
5.4
13.6
10.3
9.8
N/Avail.
N/Avail.
≧NC
S1
R05
Y
N
N
7.8
4.6
5.7
6.0
N/Avail.
N/Avail.
≧NC
S1
R06
Y
Y
Y
12.7
8.0
9.9
10.2
N/Avail.
N/Avail.
≧NC
S2
R07
Y
Y
Y
>120*
90.0
25.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R08
Y
Y
Y
>120*
>120
40.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R09
Y
Y
Y
>120*
>120
30.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R10
Y
Y
Y
>120*
>120
55.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R11
Y
Y
Y
>120*
>120
80.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R12
Y
Y
Y
>120*
>120
80.0
Meaningless
N/Avail.
N/Avail.
≧NC
S2
R13
Y
Y
Y
>120
>120
55.0
Meaningless
N/Avail.
N/Avail.
≧NC
Segment 1 Variation of starting membrane properties
Segment 2 Variation of line speed and dryer temperature
TABLE 5A
MODIFICATION DATA FOR Hydrophilic PVDF Western Blotting Membrane
Heat Treat
Temperature
Membrane
Monomer
Starting
or Mod Line
Casting
Run
Mix
Membrane
Good
Dryer
Dryer
Segment
Roll No.
Lot#
Lot Data
Footage
Temperature
Temperature
RUN T - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
1
NA
010908M1DRUM
0
NA
NA
1
NA
010908M1-MM1 Tank
0
NA
NA
1
NA
010908M1-MM2 Tank Diluted
0
NA
NA
1
R01
010908M1
IPVH 050107 T101B
155
200
1
R02
010908M1
IPFL 071007 T203
90
200
300
2
R03
010908M1
IPX 120307 T109
90
200
300
2
R04
010908M1
IPX 120307 T109
90
200
300
2
R05
010908M1
IPX 120307 T109
90
Transition
300
2
R06
010908M1
IPX 120307 T109
90
220
300
2
R07
010908M1
IPX 120307 T109
90
215
300
2
R08
010908M1
IPX 120307 T109
90
215
300
2
R09
010908M1
IPX 120307 T109
90
Transition
300
2
R10
010908M1
IPX 120307 T109
90
220
300
3
R11
010908M1
IPX 091407 T101
10
205.4
300
3
R12
010908M1
IPX 071007 T213
90
205.5
300
3
R13
010908M1
IPX 120307 T104
90
205.8
300
3
R14
010908M1
IPX 070907 T105
90
206.1
300
3
R15
010908M1
IPX 070907 R102
90
205
300
3
R16
010908M1
IPX 070907 R106
90
205
300
3
R17
010908M1
IPX 120307 R110
90
205
300
3
NA
010908M1
NA
0
205
Segment 1 Diagnostic
Segment 2 Dryer Temperature & Linespeed Variation
Segment 3 Porosity and Thickness Variation - Starting Membrane
TABLE 5B
MODIFICATION DATA FOR Hydrophilic PVDF Western Blotting Membrane
Monomer Mix Samples and Component Concentrations
Actual
Monomer
Actual
Actual
Actual
Total
Starting Membrane Properties
Mix
AC
MBAM
I-2959
Solids
Totalized
Run
Roll
Thick
Porosity
Bbl Pt
Flow Time
Sample
Wt %
Wt %
Wt %
Wt %
Footage
Segment
No.
(um)
(%)
(psi)
(seconds)
ID
(HPLC)
(HPLC)
(HPLC)
(HPLC)
By Roll
RUN T - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
1
NA
NA
NA
NA
NA
DRUM
0.76
0.60
0.15
1.51
0
1
NA
NA
NA
NA
NA
MM1
0.75
0.58
0.15
1.48
0
1
NA
NA
NA
NA
NA
MM2 Start
0.51
0.40
0.10
1.00
0
1
R01
109-125
Not
Not
Not
Not Taken
NA
NA
NA
NA
375
Available
Available
Available
1
R02
112
72.8
9.6
61.0
Not Taken
NA
NA
NA
NA
675
2
R03
120
71.0
9.5
63.0
MM3
0.50
0.39
0.10
0.99
775
2
R04
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
875
2
R05
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
975
2
R06
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
1075
2
R07
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
1175
2
R08
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
1275
2
R09
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
1375
2
R10
120
71.0
9.5
63.0
Not Taken
NA
NA
NA
NA
1675
3
R11
118
66.7
8.3
46.7
MM4
0.48
0.38
0.09
0.96
1775
3
R12
116
72.3
9.0
56.0
Not Taken
NA
NA
NA
NA
1875
3
R13
119
72.4
9.7
66.0
Not Taken
NA
NA
NA
NA
1975
3
R14
130
74.7
10.7
74.0
Not Taken
NA
NA
NA
NA
2075
3
R15
134
73.4
9.9
65.0
Not Taken
NA
NA
NA
NA
2175
3
R16
114
72.4
9.7
67.0
Not Taken
NA
NA
NA
NA
2275
3
R17
113
70.2
9.4
61.0
Not Taken
NA
NA
NA
NA
2375
3
NA
NA
NA
NA
NA
MM5
0.47
0.37
0.09
0.94
2675
Segment 1 Diagnostic
Segment 2 Dryer Temperature & Linespeed Variation
Segment 3 Porosity and Thickness Variation - Starting Membrane
TABLE 5C
MODIFICATION DATA FOR Hydrophilic PVDF Western Blotting Membrane
Nip
Nip
UV Chamber Conditions
Aisle
Wall
Line
N 2 Flow
Starting
Run
Press
Press
Speed
Top/Bottom
UV P1
UV P3
UV P2
O 2 Level
Segment
Roll No.
psi
psi
ft/min
(SCFM)
Inch HWC
Inch HWC
Inch HWC
(ppm)
RUN T - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
1
NA
20
20
NA
NA
NA
NA
NA
NA
1
NA
20
20
NA
NA
NA
NA
NA
NA
1
NA
20
20
NA
NA
NA
NA
NA
NA
1
R01
20
20
18
10/9.5
0.9
1.4
1.0
52.0
1
R02
20
20
20
10/9.5
0.9
1.4
1.0
77.0
2
R03
20
20
22-20
10/9.5
0.9
1.4
1.0
78.0
2
R04
20
20
18
10/9.5
0.9
1.4
1.0
44.0
2
R05
20
20
18
10/9.5
0.9
1.4
1.0
32.0
2
R06
20
20
18
10/9.5
0.9
1.4
1.0
32.0
2
R07
20
20
22-20
10/9.5
0.9
1.4
1.0
30.0
2
R08
20
20
18
10/9.5
0.9
1.4
1.0
26.0
2
R09
20
20
18-20
10/9.5
0.9
1.4
1.0
20.0
2
R10
20
20
20
10/9.5
0.9
1.4
1.0
22.0
3
R11
20
20
20
10/9.5
0.9
1.4
1.0
38.0
3
R12
20
20
20
10/9.5
0.9
1.4
1.0
34.0
3
R13
20
20
20
10/9.5
0.9
1.4
1.0
41.0
3
R14
20
20
20
10/9.5
0.9
1.4
1.0
21.0
3
R15
20
20
20
10/9.5
0.9
1.4
1.0
21.0
3
R16
20
20
20
10/9.5
0.9
1.4
1.0
21.0
3
R17
20
20
20
10/9.5
0.9
1.4
1.0
21.0
3
NA
NA
NA
NA
NA
NA
NA
NA
NA
Segment 1 Diagnostic
Segment 2 Dryer Temperature & Linespeed Variation
Segment 3 Porosity and Thickness Variation - Starting Membrane
TABLE 5D
MODIFICATION DATA FOR Hydrophilic PVDF Western Blotting Membrane
Water
Water
Water
Opacity/
Salt
Salt
Salt
Salt
QC
Western
Wet
Wet
Wet
Speckle
Trans-
Wet
Wet
Wet
Wet
Fluores
Blotting
Blotting
Run
Roll
Speed
Uniform
Through
Level
lucence
Time
Time
Time
Time
BKG
Pass/Fail
Live
Segment
No.
OK?
X-web?
OK?
OK?
OK?
Seconds
Seconds
Seconds
Seconds
RFU
Control
Lysate
RUN T - POROSITY/THICKNESS, VMF4 DRYER TEMP, LINESPEED
1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
1
R01
Y
Y
Y
Y
Y
2.4/5.6
3.4/6.2
3.1/6.2
3.0/6.0
N/Avail.
N/Avail.
≧NC
1
R02
Y
Y
Y
Y
Y
2.9/12.6
3.2/11.4
2.9/2.9
3.0/9.0
N/Avail.
N/Avail.
≧NC
2
R03
Y
Y
Y
Y
Y
1.1/24.1
1.4/10.8
1.1/4.1
1.2/13.0
N/Avail.
N/Avail.
≧NC
2
R04
Y
Y
Y
Y
Y
1.2/14.5
1.5/19.9
1.3/5.6
1.3/13.3
N/Avail.
N/Avail.
≧NC
2
R05
Y
Y
Y
Y
Y
1.3/10.5
1.5/15.4
1.3/4.2
1.4/10.0
N/Avail.
N/Avail.
≧NC
2
R06
Y
Y
Y
Y
Y
1.3/24.7
1.4/9.5
1.3/4.0
1.3/12.7
N/Avail.
N/Avail.
≧NC
2
R07
Y
Y
Y
Y
Y
2.5/60.0
2.3/25.4
2.5/5.4
2.4/30.0
N/Avail.
N/Avail.
≧NC
2
R08
Y
Y
Y
Y
Y
2.1/9.7
2.6/14.0
2.6/5.5
2.8/9.7
N/Avail.
N/Avail.
≧NC
2
R09
Y
Y
Y
Y
Y
2.8/13.1
3.5/22.6
2.5/5.9
2.9/13.9
N/Avail.
N/Avail.
≧NC
2
R10
Y
Y
Y
Y
Y
3.1/28.7
3.5/15.7
2.5/7.1
3.0/17.2
N/Avail.
N/Avail.
≧NC
3
R11
Y
Y
Y
Y
Y
24.1
6.5
4.2
11.6
N/Avail.
N/Avail.
≧NC
3
R12
Y
Y
Y
Y
Y
47.1
35.7
8.6
30.5
N/Avail.
N/Avail.
≧NC
3
R13
Y
Y
Y
Y
Y
67.9
70.7
34.5
57.7
N/Avail.
N/Avail.
≧NC
3
R14
Y
Y
Y
N (HIGH)
N (White)
>180
>180
>180
>180
N/Avail.
N/Avail.
≧NC
3
R15
Y
Y
Y
N (HIGH)
N (White)
>180
>180
>180
>180
N/Avail.
N/Avail.
≧NC
3
R16
Y
Y
Y
N (HIGH)
Y
>180
57.3
16.4
>180
N/Avail.
N/Avail.
≧NC
3
R17
Y
Y
Y
Y
Y
19.3
40.8
5.1
21.7
N/Avail.
N/Avail.
≧NC
3
NA
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Segment 1 Diagnostic
Segment 2 Dryer Temperature & Linespeed Variation
Segment 3 Porosity and Thickness Variation - Starting Membrane
EXAMPLE 3
The protocol used for Western blotting and chemiluminescent detection is as follows:
Protein samples are electrophoretically separated using Bis:Tris (4˜12%) midi gradient gel (Invitrogen, WG1402BOX). Samples are electro-blotted at 45V for 1 hr 15 min using BioRad tank transfer apparatus (Criterion Blotter #165-6024) onto a hydrophilic membrane prepared as in Example 1. Blots are washed 2× (3 min each) in TBS-T (0.1% Tween) Blots are blocked for 1 hr at RT in TBS-T with 3% NFM (non-fat milk, Carnation). Blots are washed 2× (3 min each) in TBS-T (0.1% Tween) Blots are incubated with primary antibody in TBS-T for 1 hr. Blots are washed 3× (5 min each) in TBS-T (0.1% Tween) Blots are incubated with secondary antibody in TBS-T for 1 hr Blots are washed 4× (5 min each) in TBS-T (0.1% Tween) Protein bands are visualized using ECL (Millipore Immobilon-HRP) and x-ray film.
This protocol was used on the samples prepared in Example 2, and the blotting results are shown in FIGS. 1 , 2 , and 3 .
Western blotting results from a typical development run demonstrate the performance differences between the hydrophilic PVDF blotting membrane of this invention, and the controls (FL—hydrophobic PVDF membrane, and NC—Whatman/S&S BA-85 membrane). Each horizontal strip in the figure contains 5 separate Western transfer blots; three blots on hydrophilic PVDF development samples, and one blot on each of the control membranes. Each strip of 5 Western blots is the result from one electrophoresis and transfer experiment (5 gels were run in each experiment). By design, each experiment embodies identical conditions with identical quantities of protein sample (applied in 4 lanes across each gel) before electrophoresis and transfer. The results shown are the transfer blots for the detection of 2 proteins (HSP70 and GAPDH) from a complex sample mixture (lysate), applied at decreasing sample solids (concentrations), from left-to-right and corresponding to: 5 ug, 2.5 ug, 1.25 ug, 0.67 ug.
Note that in each row (the result of a single electrophoresis and electro-blotting experiment, three hydrophilic blotting membranes of the invention are compared to two control blotting membranes. One control consists of nitrocellulose blotting membrane (NC) and the other control is a hydrophobic PVDF blotting membrane (FL). In the case of each single experiment, the FL membrane demonstrates the highest signal intensity for the 4 titers of analyte protein solution, and the NC membrane demonstrates the lowest signal intensity. It can be seen, when comparing the signal strengths between NC control blotting membranes and hydrophilic PVDF blotting membranes of the invention, that at the highest analyte sample titers (left hand side of each blot), that the NC and the hydrophilic PVDF membranes exhibit similar signal strengths. However, as one progresses to lower and lower analyte sample titers (progressing from left-to-right), the signal strength falls off more rapidly for the NC membrane. This demonstrates that the hydrophilic PVDF membrane allows sample detection at lower protein concentrations than NC membrane does. | Hydrophilic membrane particularly suited for blotting applications, preferably Western blotting. A pre-wet hydrophobic membrane substrate, preferably made of PVDF, is contacted with a monomer solution and subjected to a UV-initiated free radical polymerization step to render the substrate permanently hydrophilic. The resulting membrane exhibits low background fluorescence, high protein binding, excellent retention of protein sample spot morphology, and extended dynamic range (high signal-to-noise ratio, enhanced sample detectability). The membrane demonstrates comparable or higher performance in Western blotting applications than conventional nitrocellulose Western blotting membranes, particularly for protein detection at low sample concentrations, and is directly water-wettable, eliminating the need for an alcohol pre-wet step prior to use. | 6 |
TECHNICAL FIELD
The present method and apparatus relate to the field of supports for pumps.
BACKGROUND
One method of treating waste water is by use of a septic system. The prior art septic system shown in FIG. 1 may include a tank 10 that may comprise a single chamber 11 . The tank may be capped with a lid 12 that has at least one access port 13 formed in it. The access port or ports 13 may be located proximate to an end of the lid 12 or may be centered in the lid 12 as desired. In FIG. 1 , the access port 13 is shown as located adjacent one end of the lid 12 . The tank 10 may be buried in the ground 14 .
Access to the septic tank 10 may be available through a septic tank cover 16 which may allow access to the septic tank through a conduit or septic tank riser 17 that may be mated to the access port 13 in the lid 12 of the septic tank 10 .
Two kinds of septic systems are currently in use: in one, the effluent flows out of the tank 10 under the influence of gravity. Alternatively, as shown in FIG. 1 , an electric pump 18 is used to pump the effluent up the discharge pipe 19 and out into the drain field (not shown).
As building codes and the like may require that the pump 18 be elevated above the bottom of the tank 10 , the current practice is to position a concrete paver or block 21 having a thickness, in some cases, of 4 inches (10 cm) or greater on the bottom of the tank 10 , and position the pump 18 on top of the block 21 . Unfortunately, the the block 21 is frequently mispositioned in the tank 10 , and correcting the positioning of the block 21 from the surface through the septic tank riser 17 can be difficult or impossible. If one or more of the legs of the pump are not seated on the paver or block 21 , the torque of the pump 18 starting up and shutting down may apply a tortional force to the discharge pipe 19 that may ultimately lead to its structural failure.
In addition, particulate matter may settle in the tank to form a layer of sludge 22 , the upper surface of which slopes generally up and away from the location of the pump 18 . When excessive sludge has accumulated, it may be necessary to pump the tank 10 out.
SUMMARY
A pump riser may be used to elevate a pump 18 above the bottom of a septic tank 10 or other support surface. Such a riser may frictionally engage the legs of a pump 18 to facilitate installation and removal. Legs of varying lengths may be provided or fabricated for the pump riser to adjust the height of the pump 18 above the support surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional schematic view of a prior art septic tank system buried in the ground.
FIG. 2 is an isometric view of a pump mounted on a pump riser, with an outlet pipe shown in phantom.
FIG. 3 is an isometric view of a pump riser.
FIG. 4 is a sectional view of the pump riser of FIG. 3 .
FIG. 5 is a top plan view of the pump riser of FIG. 3 .
FIG. 6 is a side elevation of the pump riser of FIG. 3 .
DETAILED DESCRIPTION
As shown in FIG. 2 many pumps 18 useable in septic systems may be formed with three generally-frustoconical legs 26 disposed about, and depending from, the housing 27 of the pump 18 . In one embodiment, the pump 18 may also include an inlet (not shown) at the bottom of the pump housing 27 through which effluent may be drawn, and an outlet 28 at one side of the pump that may be attached to an outlet pipe 29 (shown in phantom) such as the discharge pipe 19 shown in FIG. 1 .
In one embodiment, a pump 18 may be mounted on a pump riser 31 to support the inlet of the pump 18 above the bottom of a septic tank 10 , or paver or block 21 . The riser 31 may be made of any of a variety of materials, including polymeric materials such as PVC (polyvinylchloride) or ABS (acrylonitrile-butadiene-styrene) plastics. Referring to FIGS. 2 and 3 , a pump riser 31 may comprise a body 32 . Recesses 33 , such as the cylindrical recesses 33 in the upper surface 34 of the pump riser 31 , may be formed in the upper surface 34 of the body 32 of the riser 31 and may be spaced so that they are coaxial with the legs 26 of a pump 18 . The dimensions of the cylindrical recesses 33 may be chosen such that the legs 26 of the pump 18 are constrained from extending completely down into the recesses 33 , and so that the legs 26 of the pump 18 frictionally engage a wall or walls of the recess 33 . In one embodiment, the legs 26 of the pump may be frustoconical and the recesses 33 may be cylindrical. Other configurations of leg 26 and recess 33 shape and size may be chosen in other embodiments. Fasteners, clamps or the like might also be used to secure the pump 18 to the body 32 of the pump riser 31 , but this would add to the complexity of the riser 31 . The diameter of the recesses 33 may be such that the outer surfaces of the legs 26 engage the inner surface of the recesses 33 after a certain percentage, which may be 50%, of the length of each of the legs 26 has entered the recess 33 . In such an embodiment, the lower surface of the pump 18 may be supported above the level of the upper surface 34 of the pump riser 31 , providing a gap through which effluent may flow toward the inlet of the pump 18 .
In one embodiment, the engagement of the outer surface of the frustoconical legs 26 and the inner surface of the recesses 33 may be pushed into contact sufficient that the pump 18 and the pump riser 31 have a sufficient frictional engagement that lifting the pump 18 results in the riser 31 being lifted along with it.
Referring to FIGS. 2-6 , in an embodiment intended for use with a pump 18 that has three frustoconical legs, a pump riser 31 may be generally triangular in shape when viewed from above. Each of the sides 36 of the riser 31 may be generally planar and of equal height along its length. In one embodiment, a series of vents 37 may be provided. These vents 37 may be vertically oriented and spaced apart from one another along the length of the sides 37 . The upper ends 38 of the vcnts 37 vents 36 may be located at a position below the upper surface 34 of the pump riser 31 , and may extend downward toward the lower edge 39 of the sides 36 . The riser 31 may be provided with a shelf 41 that extends horizontally inward of the body 32 of the riser 31 at its lower edge 39 . In such case, the vents 37 may extend around the lower edge 39 of the riser 31 and extend across a portion of the shelf 41 .
Referring to FIGS. 2-6 , in an embodiment intended for use with a pump 18 that has three frustoconical legs, a pump riser 31 may be generally triangular in shape when viewed from above. Each of the sides 36 of the riser 31 may be generally planar and of equal height along its length. In one embodiment, a series of vents 37 may be provided. These vents 37 may be vertically oriented and spaced apart from one another along the length of the sides 37 . The upper ends 38 of the vents 36 may be located at a position below the upper surface 34 of the pump riser 31 , and may extend downward toward the lower edge 39 of the sides 36 . The riser 31 may be provided with a shelf 41 that extends horizontally inward of the body 32 of the riser 31 at its lower edge 39 . In such case, the vents 37 may extend around the lower edge 39 of the riser 31 and extend across a portion of the shelf 41 .
The vents 37 may have a width selected to restrict the flow of larger particulates into the pump 18 while still allowing the flow of effluent through them. In one embodiment, the width of the vents 37 may be selected as ¼ inches (0.64 cm). This may be varied according to the size of the particles intended to be blocked by the vents 37 . Such particles may comprise organic material such as clumps of tissue paper or inorganic material such as small pebbles. As is known in the art, such large particulates in effluent fed to a drain field may compromise the drain field. Such filtering may be particularly important as sludge builds up in a septic tank.
Referring particularly to FIGS. 2 and 4 , in one embodiment the riser 31 may be provided with legs 42 extending downward below the lower edge 39 of the body 32 of the riser 31 . These may support the body 32 of the riser 31 at a level above a support surface, such as the bottom of a septic tank 10 or paver or block 21 positioned at the bottom of a septic tank 10 . In one embodiment, the legs 42 may be made of short sections of polymeric pipe, such as ABS or PVC pipe, and may fit snugly into cylindrical channels or bores 43 in the body 32 of the riser 31 .
In another embodiment, as shown in FIG. 4 , the diameter of the bore 43 may be chosen such that the legs 42 fit snugly in them. The bores 43 may extend upward into the body 32 of the riser 31 . The bores 43 may be formed to be coaxial with cylindrical recesses 33 in the upper surface 34 of the body 32 of the riser 31 . In such case, in one embodiment, the bores 43 may have a diameter greater than that of the recesses 33 and a shoulder 44 may thus be formed that may limit the depth to which the legs 42 may be inserted into the bore 43 . In one embodiment, 1 inch PVC Schedule 40 pipe may be used for the legs 42 . This material is easily cut with hand tools to a desired length, and is sufficiently strong and rigid for this purpose. The lengths of the legs 42 may be selected such that the pump 18 may be supported above a support surface such as the bottom of a septic tank 10 . As PVC pipe is readily cut, the length of the legs 42 may be selected and the legs 42 may be cut in the field. Of course, the bores 43 and recesses 33 do not have to be coaxial, and their shapes need not be cylindrical.
As mentioned above, the dimensions of the bores 43 and legs 42 may be chosen such that they form a frictional engagement when assembled together. This frictional engagement may be sufficiently strong so that an assembly of pump 18 and riser 31 may be lowered into a septic tank 10 without the pump 18 disengaging from the body 32 of the riser 31 and without the legs 42 disengaging from the bores 43 in the body 32 of the riser 31 . Of course, the legs 42 could be secured by adhesive in the body 32 of the riser 31 if desired.
The body 32 of the riser 31 may be made by any of a variety of known techniques, such as by machining, fastening together of various components using fasteners or adhesives, and the like, but molding provides an inexpensive and rapid method for such manufacture.
Although the present invention has been described in considerable detail with reference to various embodiments, other embodiments are possible. Therefore, the spirit or scope of the appended claims should not be limited to the description of the embodiments contained herein. | A pump riser provided with recesses positioned and configured to receive and frictionally engage the legs of a septic system pump. The riser may support the pump above a support surface such as the bottom of the tank of a septic system. The riser body may include legs for supporting the riser body. The lower surface of a pump body may be supported above the upper surface of the riser body as the result of engagement between legs of a pump and the recesses. | 4 |
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 62/301,612 filed Feb. 29, 2016, the entire disclosure which is incorporated by reference herein.
FIELD OF THE DISCLOSURE
[0002] The present disclosure is generally related to contamination-proof hydrants that, when not in use, employ a self-contained reservoir to store water beneath a freeze line located below the surface of the earth.
BACKGROUND OF THE DISCLOSURE
[0003] Sanitary hydrants prevent harmful bacteria, such as Escherichia coli ( E. coli ), that may be in the groundwater or surrounding soil from contaminating the water source and/or water exiting the hydrant. Many states and local municipalities have adopted hydrant requirements to prevent such contamination, an example of which may be found in Rule 1057 of the American Society of Sanitary Engineers (ASSE). These requirements have forced municipalities, ranchers, camp sites, and other entities with outdoor operations to use contamination-proof “sanitary” hydrants as opposed to the “non-sanitary” hydrants previously employed to accommodate water delivery needs.
[0004] To prevent freeze-related damage, non-sanitary hydrants known in the art employ weep holes positioned below the frost line to drain water contained within the hydrant after the hydrant is shut off. Weep holes, however, do not always prevent freezing. Due to fluctuations in the degree of water saturation of the ground surrounding the hydrant (which may be caused at least in part due to frequent use of the hydrant), the drain water may not always percolate into the ground before it freezes. In addition, if the groundwater level rises above the weep hole, then groundwater may enter the hydrant through the weep hole. The groundwater may be contaminated. If so, each time the hydrant is turned on, the contaminated water in the operating pipe may mix with the water drawn from the water source, thereby causing spoiled water to be expelled by the hydrant and/or spoilage of the water source.
[0005] To prevent the backflow of water into the non-sanitary hydrant, a check valve is often employed. If, however, the check valve wears out or malfunctions, contaminated water may enter the hydrant, thus endangering crops, livestock, and humans.
[0006] One skilled in the art will appreciate that hydrants employing weep holes open to groundwater may be susceptible to deliberate contamination by a malfeasor, or even to accidental contamination by a careless actor. More specifically, it is easily seen how contaminants placed into the ground could infiltrate into a damaged hydrant and spoil a water supply. In addition, an ancillary problem with non-sanitary hydrants is that contaminated water may affect the food supply. For example, in 2006 an E. coli scare occurred in the United States, wherein people became sick or died after they consumed spinach that had been watered and/or cleaned by water from a source that had been polluted by E. coli . Hydrants that are isolated from the surrounding soil are thus more desirable than those that are open to the surrounding soil, at least because they substantially prevent water spoilage by natural and unnatural sources.
[0007] One way to address this concern is to provide a freezeless sanitary hydrant that does not include a path for water to exit (and therefore does not include a path for contaminated water to enter) the hydrant after shut-off. For example, U.S. Pat. No. 5,246,028 to Vandepas (“Vandepas”), which is incorporated by reference in its entirety herein, discloses a sanitary hydrant that includes an isolated reservoir that contains water below the frost line after the hydrant is shut off. When the hydrant is turned on, water from the reservoir is fed into the operating pipe along with the water from the source. Thus the water that previously drained from the operating pipe (e.g. the portion of the hydrant between the reservoir and the hydrant head) never has a chance to become contaminated. Vandepas employs a venturi that reduces the pressure of the water entering the hydrant, which suctions the stored water from the reservoir to be mixed with the inlet water. Venturi-dependent systems, however, require several parts (which add to the cost of such systems) and are often undesirable because they are difficult to fabricate, install and repair.
SUMMARY OF THE DISCLOSURE
[0008] The present disclosure describes a sanitary hydrant that addresses the long felt need in the field of sanitary yard hydrant technology to provide a system that is easier to incorporate, operate, and repair than known hydrants and that prevents both freeze-related damage and contamination. The improved freeze-proof sanitary yard hydrant employs an isolated reservoir below the freeze level. When the hydrant is turned off, water drains from the portions of the hydrant above the reservoir into the reservoir, thus protecting the hydrant from freeze damage. Additionally, hydrants according to the present disclosure employ a piston to evacuate water from the reservoir when the hydrant is turned on, and to draw water into the reservoir from the portions of the hydrant above the freeze level when the hydrant is turned off. These and other features of the hydrants described herein facilitate installation, operation, and repair thereof, while also protecting the hydrant from freeze damage and contamination.
[0009] It is thus one aspect of the present disclosure to provide a hydrant that evacuates water from portions of the hydrant above the freeze level when the hydrant is not in use.
[0010] It is another aspect of the present disclosure to isolate the interior of the hydrant from soil, groundwater, and other contamination sources, so as to provide a sanitary hydrant.
[0011] It is still another aspect of the present disclosure to provide a hydrant that may be installed without difficulty, operated easily, and repaired from above ground level while still installed.
[0012] [Insert Claims Prior to Filing]
[0013] Embodiments of the present disclosure provide a hydrant comprising an upper pipe interconnected to a lower pipe via a reservoir pipe that contains a piston and a housing. A reservoir defined by the inner diameter of the reservoir pipe, an upper surface of the piston and a lower surface of the housing, contains water from an operating pipe, which is positioned within the upper pipe and interconnected to a head of the hydrant, after the hydrant is shut-off. As the hydrant is turned on, the piston is forced downward within the reservoir, such that it pressurizes the water in the reservoir. The stored water then flows out of the reservoir into the operating pipe and out the head of the hydrant. As the piston reaches full stroke, it actuates a valve that allows water to flow from a water supply source through the operating pipe and out the head of the hydrant. The piston is drawn upward as the hydrant is turned off, thus expanding the reservoir and creating suction therein which draws the water from the operating pipe and the hydrant head into the reservoir. That is, the fluid that was flowing through the operating pipe when the hydrant was on is transferred to the reservoir located below the frost line to prevent freezing of the hydrant. One skilled in the art will appreciate that the water within the hydrant never has an opportunity to mix with groundwater, thus contamination of the water exiting the hydrant and/or the water source is prevented. Embodiments of the present disclosure use less moving parts and are easier to manufacture, install, maintain and repair than sanitary hydrants of the prior art. Although water has been indicated as the fluid being transferred, one skilled in the art will appreciate that sanitary hydrants (hereinafter “hydrant”) as outlined herein may be used with any fluid. In addition, although a cylindrical construction has been alluded to, one skilled in the art will appreciate that the pipes that make up the hydrants as shown and described may be of any shape that allows for the flow of a fluid.
[0014] It is another aspect of hydrants according to embodiments of the present disclosure that such hydrants be constructed of commonly used materials and processes.
[0015] Embodiments of the present disclosure employ the head, operating pipe, external construction, etc. as other hydrants known in the art. One major difference is that embodiments of the present disclosure employ at least one movable piston as opposed to a venturi to provide a mechanism that transfers fluid from the reservoir. The housing that defines the upper portion of the reservoir may include at least one valve to facilitate expulsion of the fluid in the reservoir and, conversely, movement of the piston to allow the reservoir to be filled after the hydrant is shut off.
[0016] The Summary of the Disclosure is neither intended nor should it be construed as being representative of the full extent and scope of the present disclosure. That is, these and other aspects and advantages will be apparent from the disclosure of the disclosure(s) described herein. Further, the above-described embodiments, aspects, objectives, and configurations are neither complete nor exhaustive. As will be appreciated, other embodiments of the disclosure are possible using, alone or in combination, one or more of the features set forth above or described below. Moreover, references made herein to “the present disclosure” or aspects thereof should be understood to mean certain embodiments of the present disclosure and should not necessarily be construed as limiting all embodiments to a particular description. The present disclosure is set forth in various levels of detail in the Summary of the Disclosure as well as in the attached drawings and the Detailed Description of the Disclosure and no limitation as to the scope of the present disclosure is intended by either the inclusion or non-inclusion of elements, components, etc. in this Summary of the Disclosure. Additional aspects of the present disclosure will become more readily apparent from the Detail Description, particularly when taken together with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the disclosure and together with the general description of the disclosure given above and the detailed description of the drawings given below, serve to explain the principles of these disclosures.
[0018] FIG. 1 is a cross-sectional elevation view showing a hydrant of one embodiment of the present disclosure;
[0019] FIG. 2 is a detailed view of FIG. 1 showing hydrant just before it is turned on;
[0020] FIG. 3 is a detailed view of FIG. 1 showing the hydrant after it is turned on;
[0021] FIG. 4 is a detailed view of FIG. 1 showing the hydrant just prior to full flow;
[0022] FIG. 5 is a detailed view of FIG. 1 showing hydrant during full flow;
[0023] FIG. 6 is a detailed view of FIG. 1 showing the hydrant as it is beginning to close;
[0024] FIG. 7 is a detailed view of FIG. 1 showing the hydrant as is being closed, wherein fluid is entering a fluid storage reservoir;
[0025] FIG. 8 is a perspective and detailed view of FIG. 1 ;
[0026] FIG. 9 is a detailed elevation view of FIG. 1 showing the hydrant head during fluid flow;
[0027] FIG. 10 is a detailed elevation view of FIG. 1 showing the hydrant head when the hydrant is closed; and
[0028] FIG. 11 is a perspective view of FIG. 10 .
[0029] To assist in the understanding of one embodiment of the present disclosure the following list of components and associated numbering found in the drawings is provided herein:
[0000]
#
Component
2
Hydrant
6
Casing
10
Fluid pipe
14
External pipe
18
Cap
22
Head
26
Canister
30
Frost line
34
Fluid supply
38
Knob
42
Piston head
46
Outlet
50
Reservoir
54
Fitting
58
Inner surface
62
O-ring
66
Fluid inlet
70
Inlet valve
78
Floor
82
Fluid
84
Sealing plate
86
Boss
90
First check valve
92
Hub
94
Valve stem
98
Plunger
102
Seat
106
Valve guide
110
Spring
114
Wall
118
Internal wall
122
Internal wall
126
Seal
130
Seal
134
Air
138
Lower portion
142
Inner portion
146
Fluid channel
150
Opening
154
2nd check valve
158
Seal
162
Canister end
166
Screw
170
Bushing
174
Nut
178
Stem screw
182
Yoke nut
186
Collar
190
Fluid inlet opening
194
Inner annulus
200
Diverter valve
204
Fluid outlet opening
208
Fluid conduit
[0030] It should be understood that the drawings are not necessarily to scale. In certain instances, details that are not necessary for an understanding of the disclosure or that render other details difficult to perceive may have been omitted. It should be understood, of course, that the disclosure is not necessarily limited to the particular embodiments illustrated herein.
DETAILED DESCRIPTION
[0031] FIG. 1 shows a hydrant 2 of one embodiment of the present disclosure that comprises a casing 6 (also referred to herein as a lower pipe) that supports a fluid pipe 1 (also referred to herein as an inner pipe or operating pipe). The casing 6 may, but need not, be cylindrical. In some embodiments, the fluid pipe 10 is a one-fourth inch Schedule 40 galvanized pipe. Use of a narrow fluid pipe 10 (e.g. a fluid pipe having an inside diameter of one half of an inch or less, or of three eighths of an inch or less, or of one quarter of an inch or less, reduces the amount of fluid contained within the fluid pipe 10 when the hydrant 2 is turned off, and thus reduces the amount of fluid that needs to be stored after shut-off and thus the required volume of the fluid storage reservoir.
[0032] The fluid pipe 10 is positioned within an external pipe 14 (also referred to herein as an upper pipe or an outer pipe) interconnected to the casing 6 by a removable cap 18 . An aperture or opening in the removable cap allows the external pipe 14 to pass through the removable cap 18 and into the casing 6 . The external pipe 14 is interconnected to a hydrant head 22 on one end, and to a canister 26 (also referred to herein as a reservoir pipe) at another end. The canister 26 receives fluid from the head 22 and the fluid pipe 10 after the hydrant 2 is shut off. The canister 26 is positioned beneath the frost line 30 and is interconnected to a fluid supply 34 .
[0033] In operation, the fluid pipe 10 is transitioned downwardly when a knob 38 associated with the head 22 is turned. As the fluid pipe 10 moves, a piston head 42 interconnected to an end of the fluid pipe 10 forces air and water from the canister 26 into the fluid pipe 10 . Further movement of the fluid pipe 10 will open an inlet valve 70 that allows fluid to pass into the fluid pipe 10 . Opening the inlet valve 70 allows fluid stored within the canister 26 and fluid from a fluid supply 34 to flow from an outlet 46 of the head 22 . Turning the knob 38 in the opposite direction closes the hydrant 2 by pulling the fluid pipe 10 upwardly, which closes the inlet valve 70 and opens the canister 26 to create a fluid reservoir 50 that receives fluid from the head 22 and the fluid pipe 10 . After the knob 30 is closed, fluid previously within the head 22 and the fluid pipe 10 drains into and is stored within the fluid reservoir 50 of the canister 26 below the frost line 30 .
[0034] The canister 26 can be removed if the hydrant 2 is not operating correctly, by removing the cap 18 and pulling the external pipe 14 interconnected to the canister 26 from the casing 6 . This feature is desirable as the casing 6 can remain in place, such that no excavation of or around the hydrant is needed. Because the inlet valve 70 of one embodiment is integrated with the canister 26 , the fluid supply 34 must be shut off to make repairs. A new external pipe 14 and interconnected canister 26 can then be inserted into the existing casing 6 , or the damaged components of the existing external pipe 14 , head 22 , or canister 26 can be repaired and replaced within the casing 6 . In other embodiments, the casing 6 may be provided with an automatic shutoff valve that closes when the canister 26 is removed. For example, the automatic shutoff valve may comprise a spring-loaded valve that is held in the open position when the canister 26 is installed, but that springs into the closed position when the canister 26 is removed. In still other embodiments, the inlet valve is connected to the casing 6 and remains fixed when the canister 26 is removed.
[0035] FIGS. 2-8 show the canister 26 and associated components of one embodiment of the present disclosure in detail. Here, the canister 26 includes a fitting 54 interconnected to the external pipe 14 . The canister 26 is interconnected to an inner surface 58 of the casing by way of an o-ring seal 62 , and the canister 26 is slidingly interconnected in the casing 6 to facilitate removal thereof for repair or replacement. The external pipe 14 accommodates the fluid pipe 10 that, along with providing a fluid conduit from the fluid inlet 66 to the head 22 , acts as a control rod for the piston 42 that selectively opens the inlet valve 70 . In operation, which will be described in further detail below, as the piston head 42 is transitioned downwardly by rotation of the knob 38 , fluid within the reservoir 50 is forced out of the canister 26 through the fluid pipe 10 and out of the head 22 . As the hydrant 2 is shut off by counter-rotation of the knob 38 , the piston head 42 moves upwardly, away from the canister floor 78 , thereby creating the reservoir 50 that accepts fluid from within the fluid pipe 10 and the head 22 . In some embodiments, the upward movement of the piston 42 within the canister 26 after the inlet valve 70 has closed creates a vacuum that suctions water from the head 22 and the fluid pipe 10 into the reservoir 50 .
[0036] FIG. 2 shows the canister 6 just before the hydrant knob 38 is turned to open the hydrant 2 to fluid flow. Here, the fluid pipe 10 and interconnected piston head 42 are positioned near the fitting 54 . In this configuration, a reservoir 50 is provided that contains fluid 82 that drained from the head 22 and the fluid pipe 10 after the hydrant 2 was previously shut off. A movable sealing plate 84 is positioned within a boss 86 extending from the canister floor 78 . The canister floor 78 also includes a first check valve 90 , which will be described in further detail below. The sealing plate 84 includes a hub 92 interconnected to a valve stem 94 . The valve stem 94 is interconnected to a plunger 98 shown engaged onto a valve seat 102 which closes the hydrant 2 to fluid flow. The valve stem 94 is held in place by a valve guide 106 that allows the valve stem 94 to slide along the longitudinal axis of the hydrant 2 . Fluid pressure acting on lower surfaces of the valve plunger 98 keeps the valve closed. A spring 110 position between the sealing plate 84 and a wall 114 of the canister floor 78 prevents the sealing plate 84 from undesired downward movement, which would unseat the valve plunger 98 and allow water to enter the canister 26 . The spring 110 of one embodiment of the present disclosure is a wave spring.
[0037] FIG. 3 shows the canister 26 configuration just after the knob 38 is turned to open the hydrant to fluid flow, but before full flow. To initiate full flow, it is necessary to exert a downward force on the sealing plate 84 with the piston 42 , so as to unseat the valve plunger 98 and allow water from the fluid supply 34 to enter the hydrant 2 . As the piston 42 transitions downwardly within the canister 26 along Arrow A, the piston head 42 will exert pressure on the stored fluid 82 in the reservoir 50 and expel the fluid 82 upwardly through the fluid pipe 10 and the hydrant head 22 . During this downward movement and before the piston 42 reaches the canister floor 78 , the valve plunger 98 stays engaged onto the valve seat 102 , preventing fluid flow from the inlet 66 into the hydrant 2 . The piston head 42 includes an internal wall 118 that selectively cooperates with the boss 86 before the sealing plate 84 is contacted, which will be described in further detail below. The piston head 42 also engages an internal wall 122 of the canister 26 by way of an o-ring seal 126 , one of the few “dynamic seals” (e.g. seals between system components that move relative to each other) of the system.
[0038] FIG. 4 shows the final moments of canister fluid evacuation. The internal wall 118 of the piston 42 will eventually contact a seal 130 associated with the floor boss 86 . Here, the reservoir 50 is substantially drained and air 134 resides over the piston head 42 . But fluid 82 still resides within a lower portion 138 of the reservoir which must be expelled. In addition, at this stage the plunger 98 remains engaged to the valve seat 102 . FIG. 4 also shows an inner portion 142 of the piston head 42 contacting the sealing plate 84 . As the piston head 42 moves further down, the inner portion 142 will force the sealing plate 84 downwardly to compress the spring 110 and force the plunger 98 from the seat 102 to open the inlet valve.
[0039] FIG. 4 also illustrates how the first check valve 90 works. When the piston head moves downwardly, the remaining fluid 82 within the lower portion 138 of the reservoir is expelled through the first check valve 90 integrated into the canister floor 78 . The first check valve 90 is a one-way check valve, so fluid can only flow in the direction of Arrow B through the fluid channel 146 provided between the piston head 42 and the floor 78 . Fluid within the fluid channel 146 moves through the wall 114 by traveling through at least one opening 160 (see FIG. 8 ).
[0040] FIG. 5 shows the hydrant at full flow. In this configuration, the piston head 42 is engaged with the canister floor 78 . More importantly, the inner portion 142 of the piston head 42 has transitioned the sealing plate 84 and the integrated hub 92 , which is associated with the plunger 98 or valve stem 94 , downwardly to open the inlet valve 70 .
[0041] FIG. 6 shows the hydrant 2 as the knob 38 is being closed. As will be understood further upon review of FIGS. 9-11 , closing the knob 38 will move the fluid pipe 10 and interconnected piston head 42 upwardly along Arrow C. One of ordinary skill in the art will appreciate that pulling the piston head 42 from the floor 78 may produce negative pressure between the piston head 42 and the floor 78 , which may make movement of the piston head 42 difficult. In addition, air pressure within the canister 26 and the annulus between the fluid pipe 10 and the external pipe 14 may adversely affect piston head 42 movement. To ensure the piston head 42 can move upwardly, a second check valve 154 is provided to allow air 134 to move in the direction of Arrow D from above the piston head 42 to below the piston head 42 . The second check valve 154 does not allow fluid or air to move into the canister as the piston head moves downwardly. Additionally, the second check valve 154 may be calibrated to open only when the pressure on one side of the valve differs from the pressure on the other side of the valve by a certain amount that is exceeded when the piston 42 is initially lifted off of the canister floor 78 (e.g. before water from the fluid pipe 10 and the hydrant head 22 can fill the space between the piston 42 and the canister floor 78 to equalize the pressure), but that is not exceeded after the piston 42 reaches a height sufficient to break the seal between the internal wall 118 and the seal 130 , such that water from the fluid pipe 10 and the hydrant head 22 can drain into the reservoir 50 to equalize or reduce the difference between the pressures above and below the second check valve 154 . Those of skill the art will appreciate that other methods of breaking the vacuum may be employed without departing from the scope of the disclosure.
[0042] In the configuration of FIG. 6 , the first check valve 90 is closed. Movement of the piston 42 upwardly also allows the spring 110 to relax and to push the sealing plate 84 away from the canister floor 78 , which allows the valve plunger 98 to move upwardly into engagement with the valve seat 102 to close the inlet valve 70 .
[0043] As the internal wall 118 is pulled from the boss, fluid within the hydrant head and the fluid pipe 10 can flow into the reservoir 50 as shown in FIG. 7 . The first check valve 90 is not opened by this action as the fluid pressure within the reservoir 50 is not as great as it is in FIG. 4 where fluid is being squeezed through the first check valve 90 at high pressure. Again, air (or water, to the extent water has escaped into the portion of the canister 26 above the piston 42 ) can move through the second check valve 154 and under the piston head 42 as the negative pressure created by the moving piston head 42 does open the second check valve. However, second check valve 154 does not fully equalize the pressures above and below the piston head 42 as the piston head 42 transitions upwardly, and the negative pressure within the reservoir 50 is great enough to suction the fluid from the head and the fluid pipe 10 . In this fashion, the reservoir 50 is filled quickly as the piston head 42 is moved upwardly.
[0044] FIG. 8 is a perspective view showing the components of one embodiment of the present disclosure. Here, the way the spring 110 interacts with the sealing plate 84 can be understood. In addition, the hub 92 is interconnected to the upper end of the valve stem 94 and is also interconnected to the sealing plate 84 . FIG. 8 further illustrates the features of the hydrant 2 that allow removal of the canister 26 . That is, the canister 26 is slidingly interconnected to the fluid inlet 66 by way of at least one of o-ring seal 158 . After removal of the cap 18 interconnected to the casing, as shown in FIG. 1 , the canister 26 may be pulled from the casing 6 by moving the external pipe 14 upwardly. As external pipe 14 houses the fluid pipe 10 and is interconnected to the canister 26 , pulling the external pipe 14 from the casing 6 will disengage a canister end 162 from the inlet 66 , such that the entire assemblage may be removed.
[0045] Following removal of a canister 26 in the manner described above, installation of a new or repaired canister 26 may be accomplished by interconnecting the new or repaired canister 26 to the external pipe 14 , slidingly inserting the new or repaired canister 26 and the external pipe 14 into the casing 6 until the canister end 162 (with the at least one seal 158 ) engages the inlet 66 , and replacing the cap 18 .
[0046] FIGS. 9-11 show the inner workings of the head 22 of one embodiment of the present disclosure. The knob 38 is operatively associated with a bushing 170 interconnected to the head 22 by way of a nut 174 . The knob 38 is also interconnected to a stem screw 178 by way of a screw 166 . The stem screw 178 has a plurality of threads engaged with corresponding threads in a yoke nut 182 , wherein rotation of the stem screw 178 will move the yoke nut 182 along a longitudinal axis of the hydrant. The yoke nut 182 is interconnected to the fluid pipe 10 by way of a collar 186 , wherein movement of the yoke nut 182 initiated by rotation of the stem screw 178 will selectively open and close the hydrant 2 to fluid flow.
[0047] FIG. 9 shows the configuration of the head during full fluid flow. Here, the yoke nut 182 has been moved downwardly to force the fluid pipe 10 downwardly as described above. The downward motion of the yoke nut 182 is initiated by rotation of the stem screw 178 . As shown, fluid flows through the fluid pipe 10 through the yoke nut 182 and out of a fluid inlet opening 190 provided in the yoke nut. Fluid flows from the fluid inlet opening 190 into an inner annulus 194 provided between the stem screw 178 /yoke nut 182 and the inner surface of the head 22 . Fluid then flows from the inner annulus 194 through the fluid conduit 208 and through the hydrant outlet 46 .
[0048] Because there is a volume of air within the canister and the fluid pipe 10 which must be displaced to allow fluid to flow, some embodiments of the present disclosure employ a diverter valve 200 . In operation, the diverter valve is normally open, which allows air within the fluid pipe 10 , inner annulus 194 , and other portions of the head 22 to be expelled before fluid enters the head 22 . Pressure within the head 22 will increase as fluid enters, which will cause the diverter valve 200 to close wherein fluid is provided only one exit, that being the outlet 46 of the hydrant 2 . Diverter valves 200 of this type are well known and should be understood by those of skill the art.
[0049] FIGS. 10 and 11 show the configuration of the head 22 after the inlet valve 70 is closed. Here, the knob 38 (not shown in FIG. 10 ) and stem screw 178 have been turned in such a way as to draw the yoke nut 182 upwardly towards the knob 138 . As described above, this process will draw the fluid pipe 10 upwardly, thereby closing the inlet valve 70 and ceasing fluid flow out of the hydrant outlet 46 . Accordingly, fluid within the head 22 and the fluid pipe 10 can now drain into the canister 26 and be stored in the reservoir 50 created between the piston head 42 and the canister floor 78 in the canister 26 .
[0050] FIG. 11 specifically shows that when the yoke nut 182 is drawn upwardly, a fluid outlet opening 204 of the yoke nut 182 is exposed. The fluid outlet opening 204 creates a path from the head 22 through the yoke nut 182 , between the inner surface of the yoke nut 182 and the stem screw 178 , and into the fluid pipe 10 . When fluid flows from the head 22 , the diverter valve 200 is closed. However, draining water from the head 22 into the fluid pipe 10 creates a negative pressure in the head 22 which is accommodated by automatically opening the diverter valve 200 to allow air into the head 22 . The diverter valve 200 remains opened until the hydrant 2 is next opened to fluid flow.
[0051] Although the embodiment described above utilizes a knob 38 interconnected to a stem screw 178 to raise and lower the fluid pipe 10 , other embodiments of the present disclosure may use different lifting mechanisms to raise and lower the fluid pipe 10 . Any suitable lifting mechanism may be used, including, for example and without limitation, lifting mechanisms that utilize one or more levers, gears, pulleys, or cranks. For example, in some embodiments, the fluid pipe 10 is interconnected via a piston rod to one end of a lever rotatably mounted to the head 22 above the inner annulus 194 . The free end of the lever can then be raised to push the piston rod—and therefore the fluid pipe 10 and the piston head 42 —down and turn on the hydrant 2 . The free end of the lever can be lowered to pull the piston rod—and therefore the fluid pipe 10 and the piston head 42 —up and turn off the hydrant 2 . In another embodiment, an upper end of the fluid pipe 10 may be interconnected to a vertically oriented rack (e.g. a linear gear), which may engage and/or be engaged by a pinion (e.g. a circular gear) mounted on or in the head 22 . The pinion may be interconnected to a crank, rotation of which in a first direction causes the fluid pipe 10 to move up, thus raising the piston head 42 and turning off the hydrant, and rotation of which in a second direction causes the fluid pipe 10 to move down, thus lowering the piston head 42 and turning on the hydrant.
[0052] While various embodiments of the present disclosure have been described in detail, it is apparent that modifications and alterations of those embodiments will occur to those skilled in the art. It is to be expressly understood that such modifications and alterations are within the scope and spirit of the present disclosure, as set forth in the following claims. Further, it is to be understood that the disclosure(s) described herein is not limited in its application to the details of construction and the arrangement of components set forth in the preceding description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. | A sanitary hydrant comprises an isolated reservoir that can be positioned below a freeze level at the location of installation. A piston within the isolated reservoir is operable to expel, during a downward stroke, stored fluid from the reservoir before actuating a valve that allows fluid to flow from a fluid supply source through the hydrant. On an upward stroke, the piston releases the valve and generates a negative pressure within the reservoir that draws fluid from within the hydrant into the reservoir. | 4 |
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